Photographic Chemicals
and Solutions By J.
I.
CRABTREE
and G.
Kodak Research
E.
MATTHEWS
Laboratories
Rochester, A". T.
AMERICAN PHOTOGRAPHIC PUBLISHING BOSTON, MASS. 1938
CO.
Copyright 1938
By
J.
I.
Made and
Crabtree and G. E. Matthews
Printed in the United States of America
by the Plimpton Press
•
Norwood
Massachusetts
PREFACE This book represents some of the knowledge acquired during the past twenty-five years in
compounding photographic
their application to
photography
in the
solutions
and studying
Research Laboratories of the
Eastman Kodak Company.
ERRATA Page 337
— Formula DK-20R — Replenisher Solution should read:
Kodalk Potassium Sulpliocyanate (Thiocyanate)
2 ounces, 290
grains
20.0
grams
290
grains
5.0
grams
Pages 341, 343, 345 Firm name should be spelled as follows: Lalance
&
Grosjean Corp.,
Woodhaven, N. Y. Page 359
— Index
Reference should read as follows: Fine-grain development 295, 337.
ui
November
1938.
i-K.
i»i rt 1 1
n n. WO"
Made and
Printed in the United Stales of America
by the Plimpton Press
•
Norwood
Massachusetts
PREFACE This book represents some of the knowledge acquired during the past twenty-five years in compounding photographic solutions and studying their application to
photography
Research Laboratories of the
in the
Eastman Kodak Company. The nucleus of this work was contained pare Photographic Solutions " (Brit.
quently
many
scientific
by the authors and in these
J.
How
Phot. 66: 365, 1919).
to Pre-
Subse-
papers cognate to this subject were published
their co-workers
and the material of practical value
papers has been extracted and combined
for reference purposes.
''
in the article
To
this compilation
in this single
volume
has been added consider-
able hitherto unpublished information.
The requirements
of the small as well as the large user of photographic
chemicals have been kept in mind throughout and
book
will therefore
be of value to
all
it
is
hoped that the
types of photographers including
amateurs, professionals, scientific investigators, x-ray, photofinishing,
photo-mechanical, and motion-picture workers.
Acknowledgment
who generously
is
due
to the various
manufacturers of equipment
supplied data and photographs, to Mr. C. E. Ives, to
Mrs. R. F. Quirk, and to our other numerous colleagues
in the
Kodak
organization for their suggestions and helpful criticism. J. I.
G. E.
November
1938.
Crabtree
Matthews
Digitized by the Internet Archive in
2010
http://www.archive'.org/details/photographicchemOOcrab
CONTENTS
Preface
.......... .........
PAGE iii
Introduction CHAPTER I.
II.
III.
...... ......
Terminology and Arrangement of Photographic Formulas Photographic Arithmetic and Conversion of For MULAS Apparatus and Methods of Use
IV. Materials for
....
Construction of Photographic Proc
ESSiNG Apparatus V.
Temperature Measurement and Control
...... ...... ......
VI.
Effect of the Water Supply on Photographic Solu
VII.
Technique of Mixing and Using Photographic Solu
tions
tions VIII.
6 15
Handling Solutions at High Temperatures
51
79
100
114 178
IX. Storage and Transportation of Chemicals and Solu
tions
X. Substitution of Chemicals XI. Stains on Negatives and Prints XII. Cleaning Photographic
191
214 230
Processing Apparatus and
Removal of Stains from the Hands and Clothing
262
.....
270
XIII. General Suggestions and Precautions
Photographic Chemicals XIV. Appendix
on Handling
....... ....... ....... .... ...... .........
A.
Formulary
B.
Table of Solubilities of Photographic Chemicals
C. List of
279
338
Manufacturers of Apparatus and Sup-
plies
341
D. Conversion Table of Fahrenheit, Centigrade,
AND Reaumur Degrees
347
Index of Formulas by Purpose
348
Subject Index
358
INTRODUCTION Chemicals chemicals, or
for 2.
photographic work are supplied either as
i.
individual
as mixtures of dry powders or solutions requiring only
the addition of water to prepare
them
for use.
The majority
photographers prefer to purchase their chemicals
in the
of
amateur
prepared form.
Within recent years an increasing number of advanced amateurs, pro-
and photofinishers have
fessional photographers,
age chemicals more extensively, but
also
begun
many workers and
to use pack-
the majority of
motion picture laboratories prepare their photographic solutions from the
component chemicals. It should be understood clearly, however, knowledge of the fundamental principles of solution preparation
that a
and use
is
important w^hether prepared powders or component chemicals
are preferred.
It is the
purpose of
this
book
to
supply such information.
In order to be able to prepare correctly any and every solution used in
photography, a knowledge of the properties of the chemicals used and
of the chemical reactions involved during the mixing
is
essential,
though
by adhering strictly to printed directions it is usually possible for an unskilled worker to prepare the developing and fixing solutions as generally used. However, instructions for the use of various materials differ; for example, in the case of some developing formulas it is recommended to dissolve the developing agent
should be dissolved tized
method
of mixing
first,
while according to others the sulphite
Both methods may be
first.
is
right,
followed, and especially
if
but
if
a systema-
the photographer
has a knowledge of the reactions involved, he can then proceed to mix
any photographic solution with confidence and, what is more, he will be able to locate the trouble if for any reason the solution does not work correctly after mixing.
In recent years automatic developing with processing machines has for motion picture and photofinishing work, and these machines necessitate the use of large volumes of solution which require special equipment for their preparation and handling. In each chapter, therefore, an attempt has been made to deal with specific meth-
been introduced, notably
ods for the handling of both small and large quantities of chemicals.
CHAPTER
I
TERMINOLOGY AND ARRANGEMENT OF PHOTOGRAPHIC FORMULAS A
solution of
any kind
is
obtained by uniformly mixing with and dis-
tributing a solid or a liquid through another liquid (or solid).
may
of gases in liquids
37% tion
is
a
solution of the gas, formaldehyde, in water; but this type of solu-
The substance being
rarely used in photography.
is
and the liquid The extent to which the
which
called the solute
in
solvent.
solute
its
Solutions
which
also be prepared, such as formalin,
and when the solvent
solubility
will
it
is
dissolved
dissolved
soluble in the solvent
is
is
called the
is
is
called
hold no more of the solute
it is
said to be saturated.
The degree
of solubility of
any chemical depends on the nature and
temperature of the solvent. a saturated solution
If
is
cooled
down
to a lower temperature, crystals
usually form which settle out until the saturation point
reached at that
is
particular temperature, though in the case of a substance like hypo, all
dust
is
called supersaturated solution of to
hypo grow
is
if
excluded, crystals do not separate out on cooling and a so-
added
is
until the saturation point
is
a small crystal
if
immediately form and continue
reached.
paring a saturated solution, therefore, water, cool to
However,
obtained.
to the solution, crystals
is
The
method
best
of pre-
to dissolve the chemical in hot
room temperature with shaking, allow
to stand,
and
filter.
For photographic work, saturated solutions are not recommended, because even though the solution care
any
taken to note
is
crystals
its
may
which
may have
been prepared correctly, unless
condition each time
it is
used, and to dissolve
have formed, serious errors
These errors can be avoided by
may
be introduced.
always using solutions of a definite per-
centage strength as will be explained
—
later.
Diluting to Volume. When a chemical is dissolved in water the volume of the solution is usually greater than that of the water used, because the particles or molecules of the chemical occupy a certain space
when liquid
in solution. is
In case two liquids are mixed, the final volume of the
not necessarily equal to the
before mixing,
it
may
be greater or
it
sum
may
of the volumes of the liquids
be
less.
Thus
fifty
volumes of
volumes of water at 7o°F. (2i°C.) produce ninety-seven volumes of the mixture and not one hundred. Moreover, equal weights of different chemicals do not occupy the same volume. alcohol
when added
to fifty
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
2
In photography
we
are concerned only with the weight or
volume
of
each chemical in a fixed volume of the solution, so that when mixing, the chemical should be dissolved in a volume of water appreciably less than
volume
that called for in the formula and then water added up to the stated.
Systems o£ Measurement.
— In photographic
practice, solids are
weighed and liquids are measured either by the metric or the avoirdupois system.
Although a large majority of photographers use the avoirdupois system of weights and measures, this system is inconvenient and complicated as compared with the metric system. The metric unit of length is the meter (m) (which means measure).
The meter
is
divided into one hundred parts called centimeters, abbre-
viated as cm.
The is
unit of
mass or weight
is
a platinum-iridium cylinder,
at the International
Bureau
of
the kilogram (kg) the original of which
which
is
in a special
thousandth part of the kilogram equals written g though preferably entiate
it
gram.
i
A
good rule
is
words of
to spell out all
in formulas.
unit of
volume
is
the
liter (1)
which
is
the
kilogram of pure water at the temperature of
namely 4°C. (39.2 °F.) and subjected Therefore,
The The gram may be
should be spelled out completely to differ-
from the term, grain.
one syllable
The
it
underground vault
Weights and Measures near Paris.
i
liter
of water weighs
one-thousandth part of the
The thousandth
part of a
liter
liter is
i
to
volume occupied by its
maximum
i
density,
normal atmospheric pressure.
kilogram or 1000 grams and
or the milliliter (ml) weighs
i
i
gram.
usually designated also as a cubic cen-
timeter (cc) although 1000 milliliters or
liter
i
equals 1000.028 cubic
centimeters {Report on Metric Units oj Volume, Brit. Standards Institu-
London, 1933). The difference between the two units is 28 parts which is so small as to be of no significance except in very precise scientific work. The term " cubic centimeter " has become so universally used that it is commonly accepted as the thousandth part tion,
in a million,
of a liter and will, therefore, be used in this
book with
this connotation.
For compounding metric photographic formulas, only grams, liters
in the case of the
U.
S.
currency which
is
a metric currency.
ginner should therefore think of grams and parts of a
were dollars and cents. 535 -iii grams.
100
and
cc,
are used, and fractions are always expressed as a decimal just as
gram
The as
if
be-
they
Thus, 5.35 grams corresponds to $5.35 or
TERMINOLOGY AND ARRANGEMENT In photography the following table
is
used:
Weight
drams (or drachms)
8
ounces
16
Volume
=
437"i grains
i
ounce
=1
ounce
=
pound
i
==
60 minims
drams (or drachms) 480 minims * 128 ounces
— Much confusion
Uniformity of Formulas. formulas could be avoided
Mees/
if
i
8 fluid
* 16 ounces
cation.
3
(or
=1
= = =
dram
fluid
drachm)
fluid
ounce
i
fluid
ounce
i
pint
i
gallon
in the conversion of
authors would adopt a standard for publi-
Ausserwinkler,- and others have suggested standards for
writing formulas but for practical use in publication, these have certain objections.
The
simplest standard, perhaps,
is
the liter (32 ounces) or
quarter fraction thereof, 250 cc, 500 cc, and 750 cc (8 ounces, 16 ounces,
and 24 ounces respectively) I
for tray dilutions,
and 4
liters
gallon) or quarter fraction thereof for tank dilutions.
always be published total
in
both metric and avoirdupois equivalents with the
volumes on the above
The
(128 ounces or
Formulas should
basis.
variation of the British measure from the American
is
sometimes
a source of confusion, because in the former, the British imperial gallon
(160 ounces) equals 4.546 3.785 liters (see page 6). tion of the British
liters
whereas the U.
It is
Chambers
of
S.
gallon (128 ounces)
is
encouraging to note that the Associa-
Commerce have by resolution suggested The Metric Committee of
the adoption of the liter as the standard.^
American Chemical Society have
the
equivalents should be published for
also
recommended
A very
recommended above.
that metric
photographic formulas
This world resolution
tion to avoirdupois values.*
the standard
all
is
in
in addi-
agreement with
clear article on the use of the
metric system in photography has been published by Chappell.''
Order of Chemicals
in a
Formula.
— When mixing photographic
solutions, the importance of following manufacturers' instructions can-
not be overestimated.
The
quantities
been established by extensive
tests
and the order of ingredients have to change them is very apt to
and
affect the useful properties of the solution. *
page
These are U.
S. units.
For
1
Brit. J. Phot. 64, 535 (ipi/)-
2
Phot. Rimd. 62, 130 (1925). Ind. Eng. Chcm. News Ed.
3
&
2, 2
(Oct. 10, 1924).
Amcr. Chcm. Soc. 81 (1925). Camera (Phila., Pa.) 47. i45-i55 (Sept. 1933)-
* Proc. 5
a discussion of the British imperial measure, see
6.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
4
The
order in which the ingredients are arranged in the formula
In some cases water
importance.
is
placed
first,
is
of
but
in other cases last,
as a general rule it should appear last and be written " water to make." With two- and three-solution developers, an exception to the rule maybe made if only one or two chemicals, such as sodium carbonate, are to be dissolved, when the total volume of water should be given first. It is also useful with most developer formulas (pyro and amidol excepted) to
include the expression, " water (about i25'-"F.) (52°C.) " at the top of
the formulas in a volume sufficient to dissolve readily It
is
all
the chemicals.
unnecessary, except in the case of difficultly soluble chemicals like
alum, borax, (52°C.).
to use
etc.,
Also,
water at a temperature higher than i2 5°F.
too hot water
if
is
used
much time may be wasted
in
cooling the solution to a temperature suitable for use.
When it is
mixing very large volumes of solution, as
sometimes simpler and more practical
will
be discussed
later,
to avoid the necessity of heat-
ing water higher than 65° to 7o°F. (18° to 2i°C.).
For simplicity, the volume given at the top of the formula should be
Then total volume of the solution. given as " cold water to make," the developer
an even quarter fraction of the the final dilution
more apt
to
is
be nearer the temperature for use than
if
if is
no instructions
were given.
Whenever a solution must be diluted for use, the expression " Stock Solution " should precede the formula. An example embodying these suggestions
is
as follows:
A
Stock Solution
Avoirdupois
Water (about
125° F.){52°C.)
Elon
Sodium
ounces
16
grains
60
Sulphite, desiccated
Cold water to
ounce ounce ounces
Vi Y^
Hydroquinone
make
32
Metric 500.0 cc 4. 1
15.0 15.0
grams grams grams
l.o liter
Stock Solution B Water
32
Sodium Carbonate, desiccated Potassium Bromide
30
The chemicals should be given dissolved, servative,
which i.e.,
in the case of a
V^
ounces ounce grains
in the order in
developer
sulphite, bisulphite,
is
1.0 liter
15.0 2.1
grams grams
which they are
usually as follows:
or metabisulphite;
2.
to i.
be
pre-
developing
agent; 3. accelerator or alkali such as carbonate; 4. restrainer or bro-
mide; If
5.
" water to
make."
a strong alkali, such as sodium hydroxide (caustic soda)
the water should always be written
first
and expressed as
is
given,
" cold
wa-
TERMINOLOGY AND ARRANGEMENT because on mixing, considerable heat
ter/'
is
5
evolved and the solution
is
apt to boil with explosive violence. If the formula contains sulphuric acid, the acid should appear at the end of the formula so that the concentrated acid will be added to the water. If this procedure is reversed, that is, the water added to the acid,
serious burns
may
be produced by a spattering of the acid caused by the
excessive heat generated on mixing.
Names and
Abbreviations,
— Although
it
common
is
designate particular chemicals by several different names,
practice to
it is
suggested
that the standard chemical terminology found in any good textbook of
Such archaic terms as carbonate of sodium, bichro-
chemistry be used.
mate etc.,
of potash, soda crystals, sulphuret of hydrogen, potassa carbonate,
In the same class
should be discarded.
carb., pot. bromide, ammonio-chloride, etc.
names
is
Sodium thiosulphate, used
commonly used
chemical
is
"'
name sodium
has been used for so
that practically everyone understands
it
is
commonly
is
This
not a fixing agent,
many years by photographers mean sodium thiosulphate.
in a formula,
preferably as a io9f solution to be added as so
than a dram
is
hyposulphite.
— When quantities
Small Quantities of Chemicals. i gram or 15 grains are included
under
to
It
in photographic practice.
quite a different substance and
but the term " hypo
be used.
of preferred chemical
as a photographic fixing agent,
called " hypo," an abbreviation of the
less
abbreviations like soda
list
given in the table of solubilities in the Appendix, page 338.
includes most of the chemicals
latter
fall
A
of chemicals
they are expressed
many
cc or drams.
If
required, an even quarter fraction thereof ought to
This plan avoids using " drops " as a unit of measure which
is
method of measuring the volume of a liquid. There is wide variation in the number of drops to a dram with liquids of different specific gravity. Even drops of the same liquid vary in size according to the shape of the mouth of the discharging vessel. Other a very uncertain
factors influencing the size of the drop are the rate of delivery of the liquid to
from the
vessel, the surface tension of the liquid,
which the mouth of the vessel
is
A
moistened.
and the extent
note published in the
some idea of the variation in shown is from 45 drops The average drop from with ammonia to 138 with ethyl alcohol (95 /c ) the usual dropping bottle or burette used in technical research work Photographic Journal of America
^
gives
volume which may occur. The range
in the table .
measures about
i
minim
or approximately one-twentieth of a cc.
Directions are given later for mixing percentage solutions. 8
Phot.
J.
Amcr.
S9,
412 (1922).
CHAPTER
II
PHOTOGRAPHIC ARITHMETIC AND CONVERSION OF FORMULAS In photographic practice, solids are weighed and Hquids are measured
by the avoirdupois
either
The
or the metric system.
following tables of weights and measures give
all
the equivalent
values required for converting photographic formulas expressed either in
metric or U.
S. liquid
measure.
Weights and Measures
— Conversion Tables
Avoirdupois to Metric Weight Pounds
:
..
ARITHMETIC AND CONVERSION OF FORMULAS Measure
British Imperial Liquid to Metric Quarts
Gallons
Drams
Fluid
(J'^x^s
CenUmeters
''»»*^^'»
1.0
4.0
160.0
1280.0
4546.0
4.546
0.25
1.0
40.0
.UO.O
1136.0
1.0
8.0
1.136 .02841
0.003125 0.2200
0.125 0.03520 35.20
0.8800
28.41
1.0 (60
min.)
3.551
0.2816 281.6
.003.551
.001
1.0
1000.0
1.0
Solid Conversion Values Grains
tirains
1
.,
l
<>
niiart
per British imperial quart multiplied by 0.833 = ounces f,, «,;! ,' .rlT.- ..^ (40 fluid ounces) pounds ^^^ ""''' """•^'^s) Grains per British imperial quart multiplied by 0.05696 = )>rams per liter = ftrams per liter Ounces per British imperial quart multiplied by 24.92 = grams per liter Pounds per British imperial quart multiplied by 398.7 = grains per British imperial quart Grams per liter multiplied by 17.54 = ounces per British imperial quart Grams per liter multiplied by 0.0401 Grams per liter multiplied by 0.002506 = pounds per British imperial quart
Ounces Pounds
]
Ounces
(fluid)
per British imperial quart multiplied by
Ounces
(fluid)
per British imperial quart multiplied by 25.00 = cubic centimeters
j
Liquid Conversion Values 0.8
= ounces
(fluid)
per U. S.
quart per
liter
Cubic centimeters per
liter
= ounces
multiplied by 0.03999
(fluid)
per Brit-
ish imperial quart
British texts sometimes refer to the Winchester
which equals
2
im-
perial quarts.
Example
of a
— When
Formula Conversion. it may
pressed in grains, ounces, anci pounds,
a formula
is
ex-
be converted into a metric
formula by using the above conversion values which take into account the difference between 32 ounces and
After a conversion has
liter.
i
been made, the values obtained should be rounded
off to
working quantities.
Tiie-errorintroduced in rounding
not be greater than
3%
and the
ratio
give convenient
off
a value should
between chemicals such as Elon
and hydroquinone or carbonate and sulphite should not be changed. Thus a developer formula for a 3^ gallon tank would be converted as follows
T^ Formula ,
Water (about
125° F.) (52° C.)
1
149
Elon
Sodium Sulphite (desiccated) Sodium Bisulphite Hydroquinone Sodium Carbonate (desiccated) Potassium Bromide Cold water to
Water (about
125° F.) (52°
....
.
Hydroquinone Sodium Carbonate (desiccated) Potassium Bromide
make
1 ounce 139 grains 83 grains 3hi gallons
Direct ounces 32 423^ grains
C).
Sodium Sulphite (desiccated) Sodium Bisulphite
ounces 240 grains grains grains
Gallon (Avoirdupois)
1
Elon
Cold water to
96 288
make
Conversion to
gallon grains
10
3
27'^ 82J4 165 23?^ 1
ounces 4 grains grains grains grains grains gallon
Rounded
Off 32 ounces 43 grains 3
ounces
28 grains 82 grains 165 grains 24 grains 1 gallon
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
8
Conversion to 4 Liters (Metric) Rounded
Direct
Water (about
125° F.) (52° C.)
10
..
Sodium Sulphite (desiccated) Sodium Bisulphite Hydroquinone Sodium Carbonate (desiccated) Potassium Bromide
make
Cold water to
liter
Off
1.0 liter 2.9 ftrams
2.94 grams 90.3 grams 1.88 grams 5.64 grams 11.28 grams 1.62 grams 4.0 liters
Elon
90.3
grams
1.9 grams 5.6 grams 11.3 grams 1.6 grams 4.0 liters
a formula called for 453^ grains and this quantity were cut to an
If
even 450, the difference would not be detectable by photographic means, though if a quantity of 6^ grains were cut to 5 grains, the error (23%) would be serious. In rounding
when
3.82
rounded off to
the quantity, for example, of Elon, in a formula, an
off
4.7% may
error of
grams
off in the
25.0 grams, a
separately
is
be introduced in bringing
made
is
opposite direction, that
7%
error
is
is,
if
if
to a certain value, as
the hydroquinone
26.8 grams
between the Elon and hydroquinone
do not change the
ratio
is
12%
is
which
is
in
rounding
between the constituents of a formula.
i
liter
the basic
liter
Liter
or :
pound
some value
practice of con-
in the avoirdupois
later time, reconverting the 8 gallon
liters is
fundamentally unsound.
i
quart formula.
120 Gallon Conversion.
a metric formula (grams per
I
The common
quart.
The 96
formula should be obtained by a direct conversion from
because each gram to
best
derived, whenever possible, from one
liter or i
96 ounces or to 3
ounce or 3 i
The
usually permissible in photographic work.
system such as 8 gallons and, at a
I
values
off,
verting a liter formula, for example, to
The
off
below 3%. is to keep the error, in rounding introduced would error that could then be be less than
basic formula, such as
to
in
changed.
watch that errors
Working formulas should be
formula
made
introduced and the
rule to accomplish this
The maximum
is
rounded
Neither of these errors taken
introduced.
It is important, therefore, to
6%
is
very serious in photography but since they were
opposite directions, a total error of nearly ratio
up
it
Then
4.0 grams.
in the
in the
i
liter) to liter
— A very rapid conversion
a 120 gallon
of
formula can be made
formula can be changed directly over
120 gallon formula with an error of
less
than 0.2%.
a simple matter to express fractions of a pound in ounces (avoir.) or to break the ounces into quarter fractions of an ounce. This scheme It is
is
of value, obviously, for large scale work.
—
In photography two kinds Percentage Solutions. are commonly used as follows:
of solutions
ARITHMETIC AND CONVERSION OF FORMULAS A A
A. B.
9
solid in a liquid.
liquid in a liquid.
The misunderstandings which have method
ing the correct
arisen from time to time regard-
of preparing solutions of a definite percentage
strength are due to the fact that there are three ways of doing
make a
example, we can
For
it.
s7( solution of potassium bromide as follows:
Dissolve 5 grams in loo cc of water. Dissolve 5 grams in 95 grams of water making 100 grams of solu-
1.
2.
tion.
Dissolve 5 grams in a
3.
In case
A
i.
little
we might have 102
chemist would use method
mass
water and add water to make 100
2.
because he
and not
of the solids in solution
and
cc of solution
is
in the
photographic work to
fill
cc. cc.
interested chiefly in the
volume, but method
used when preparing photographic solutions because tice in
about 97
in case 2.
common
it is
and
vessels to a definite level
3. is
prac-
it is
con-
venient to measure stock solutions or small quantities by taking a definite
volume of the
Method
solution.
i
not used for the reason that equal
is
weights of different chemicals do not occupy the same volume.
The percentage strength of a photographic solution, how much of the chemical is dissolved in 100
indicates
Table of Solubilities
(see
To
7%
prepare a
grams
cc.
ured
7
If
Appendix, page 338).
in
solution of potassium bromide, therefore, take 7
of the salt, dissolve
100
in a little water,
it
we now measure out 100
grams of the
I
10%
solution of a solid
ounce and making up to 10 ounces with water.
figures into solution.
to make we have meas-
and add water
cc of the solution
solid.
In the avoirdupois system a ing
therefore, merely
cc of the solution
grams and cc we have, roughly, 30 grams
Strictly speaking, this
is
in
not correct since
= 29.57
is
made by
tak-
Converting these
i
300
cc, or
ounce (U.
a
10%
S.)
ounce
=
28.35 grams and
i
10 fluid ounces
equivalent to 28.35 grams in 295.7 cc or 9.6 grams in
is
fluid
ounce (U.
S.)
cc so that
i
in
100. If a
photographic solution
or 3, the error involved
is
is
less
made by any
than
3%
of the above methods, 1,2,
and therefore
negligible for ordi-
nary photographic purposes, though since the correct method est, it
is
the easi-
should be followed.
Although somewhat of an anomaly, solution of a substance like
occupy a space of 100 cc)
A 10%
it is
possible to prepare a
100%
hypo by dissolving 100 grams (which do not
in sufficient
water to make 100 cc of solution.
solution of a liquid in water
is
made by
taking 10 cc of the
10
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
liquid
and adding water
to
make loo
cc.
The concentrated form of mean
certain liquids used in photographic practice does not necessarily
that the solution contains
ioo%
of the liquid or gas in question.
Sul-
phuric acid, pure concentrated, for example, represents a 95/^ solution; nitric acid, pure concentrated, 65%; hydrochloric acid, pure concentrated,
28%
35%;
37%
formalin,
ammonia
of
gas.
and ammonia,
of the gas, formaldehyde;
When
preparing a dilute solution of any of these
concentrated liquids for photographic use, however, their strength
100%.
usually taken as
prepared by taking
adding water
to
i
make
A 10%
solution of
ammonia,
When
diluting
most concentrated
the acid should always be added slowly to about sired
volume of water.
The
90% is
danger of the acid
articles,
much
the authors would clearly define the
if
Finally, water
the solution to volume.
In the publication of photographic
avoided
acids,
of the total de-
spattering on the hands and causing serious burns.
make up
is
solution should be stirred while adding the
acid to insure thorough mixing, otherwise there
should be added to
is
(28%) ammonia and
part of the concentrated 10 parts.
for instance,
whenever the term " percentage solution
" is
confusion would be method used by them
introduced.
Inconsisten-
and mistakes introduced by a lack of understanding of percentage solutions have been pointed out by Dobson ^ and Lockett.- Although cies
made is slight when small quantities are measured, it becomes when the percentage of the substance dissolved is 25%, 30%,
the error serious
or greater.
â&#x20AC;&#x201D;
Usefulness of Per Cent Solutions. The great advantage of any solution in parts per hundred is that a definite mental picture is at once created of its relative strength, and by means of a number of stock solutions it is possible to compound certain formulas by simply measuring out a definite volume of each solution thus dispensing with a balance. Thus supposing we have a 10% solution of potassium ferricyanide and of potassium bromide already at hand and it is
stating the strength of
make up
desired to
the following solution:
Potassium Ferricyanide Potassium Bromide Water to
then
it is
grams
2.3 grams 1.0 liter
only necessary to measure out 60 cc of the ferricyanide solu-
tion, 23 cc of the
solution
6.0
is
bromide solution, and add water up
made.
1
Camera Craft
2
Brit. J. Pilot. 70, 95 (1924).
2j, 2gi (1920).
to
1000 cc and the
ARITHMETIC AND CONVERSION OF FORMULAS In the case of very concentrated solutions
it is
11
not always possible to
use this method, though in view of the time saved and the accuracy of the
method
should be applied whenever possible.
it
Suppose a formula
gram.
calls for o.i
impossible to weigh this
It is
quantity accurately on the usual photographic scale, but by measuring out is
I
cc of a
less
10%
An
solved.
and adding
solution,
than lo cc
by means
is
end
mark and then allowed
until the liquid
The to
liquid
is
problem
a calibrated
is
sucked up into the tube
run out by placing the finger over the
even with the mark.
is
raising the finger slightly
which
of the chemical pipette,
tube with an orifice at one end. past the
this to the mixture, the
accurate and convenient method of measuring volumes of
It is
then discharged by
from the end.
â&#x20AC;&#x201D;
Photographic Arithmetic. much greater than
tity of solution
It is
often required to mix up a quan-
by the formula,
that given
in
which
case the photographer must perform a very simple exercise in arithmetic in
order to secure the desired result.
cate the
A.
method
Mix
The two
following examples indi-
of solution of such simple problems.
6 ounces of solution according to the following formula: Potassium Ferricyanide
4.0
Water
grams
10.0 grams 100.0 cc
Hypo to
(In order to simplify the arithmetic,
will
it
be assumed that
equals 30 cc instead of the more exact value, 29.57 cc.)
ounces
= 6 X 30 =
180
little
error introduced
is
X
^
ounce
X4=
6
7-2
18 grams of hypo.
Dis-
water and make up to 180 cc or 6 ounces.
The
grams of ferricyanide and 180/100 solve these in a
we need 180/100
Therefore,
cc.
i
Now,
1.7'
r
which
is
10
usually permissible in photographic
work. B.
How would
you mix
i
pint of a
7%
solution of sodium sulphite?
To make 100 ounces of a 7'^r solution we need 7 ounces of sulphite. i-i2 ounces Therefore, to make i pint (16 ounces) we need 0.16 X 7 i ounce dissolve therefore, or I ounce 53 grains. To prepare the solution, pint). ounces 53 grains of sulphite in water and make up to 16
= ( i
The Meaning
of " Parts."
â&#x20AC;&#x201D;
It is ofte^i
say, 10 parts of a solid in 100 parts of water. ingless because a solid chemical
though
if
the metric system
then grams and cc
may
is
is
recommended
weighed while a liquid
used, since
i
to dissolve,
Such a statement is
is
mean-
measured,
cc of water weighs
i
gram,
be considered synonymous with parts.
In the case of liquids, parts should be taken as meaning units of volume, and in the case of solids as units of weight. A " part " may there-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
12
fore
mean
either a gram, a ton, a cc, or a gallon so long as the other
same
quantities are reckoned in the
A
three partsl
B
one part
mav may mpan mean
V .
units of weight or volume.
(A ^oo
J
If the
and
avoirdupois system
liquids,
if
is
cc
^ IBioocc
A
1=;
^
ounces
1^5
ounces
f
nr or
J <
Thus:
J .
„
used and the formula contains both solids
ounces (liquid) and ounces (solid) are substituted for
" parts," the error involved falls within permissible limits.
Problem:
Mix
I
gallon of solution according to the following formula.
Sodium Sulphite
10 parts
Pyro
1
Water
Now,
I
part
100 parts
to
gallon equals 128 ounces.
Therefore, dissolve 12.8 ounces
of sulphite in water, add 1.3 ounces of pyro, and
make up
to
gallon.
i
For the sake of simplicity and clearness, however, exact quantities should always be given rather than " parts."
If this
is
done and a stand-
ard volume adopted for the total volume of the solution, directions for
mixing
will
be
much
easier to follow.
The Hydrometer
Test.
— Many photographers are accustomed
to
making up their stock solutions of hypo, carbonate, sulphite, etc., by means of the hydrometer. This method has the advantage that in case the hypo, for example, has become moist and contains an unknown quantity of water, a definite reading on the hydrometer will give a solution of the
When
same strength as
a stock solution
is
perfectly dry chemicals
if
had been used.
made from moist chemicals by
weighing, the
by the presence of water may be as high as 25% or 509^ The hydrometer method has the serious disadvantage that the ad-
error caused
•
justment of a solution to the required strength takes considerable time, the hydrometer reading does not convey
any idea
as to the percentage
strength of the solution, and the reading varies with the temperature.
For instance, say, 45 ister all
if
Baume
a stock solution
made with hot water and
this registers,
when
may
It is therefore absolutely necessary either to
48 or 50 Be.
readings
is
(Be.) on the hydrometer, on cooling, the liquid
the solutions have cooled to
room temperature,
reg-
make or to
prepare a table giving the variation of density of each solution with temperature.
For example, the
specific gravity of acetic acid at 59 °F.
(i5°C.) with increasing concentration of acid increases to a value of 1.07 at
A
hydrometer
80% is
and then decreases
to 1.058 at
99%
maximum
acid.
useful, however, in checking the strength of certain
liquid chemicals such as alcohol, acetic acid
and sulphuric
acid.
If
a
ARITHMETIC AND CONVERSION OF FORMULAS solution
known
is
13
pure ethyl alcohol and water, for ex-
to contain only
ample, then from the hydrometer reading at a definite temperature, the percentage strength can be determined with accuracy.
Mixing stock solutions by hydrometer cause
it is
much
simpler to
compound
hydrometer reading, however,
sometimes a rough check that the solu-
been mixed correctly.
tion has
A
is
recommended beby weighing. A subsequent
test is not
these
hydrometer
The only way
test of a
mixed developer has no meaning whatever.
to test a developer
tographic material for which
Hydrometer readings no relation
to the
it is
is
to
develop actually therein the pho-
intended.''
of acid hardening fixing baths also bear little or
time required for the film to clear and therefore repre-
method
sent an unreliable
of checking the condition of a fixing bath
(see further details on page 162).
as
Hydrometers are graduated according to many different scales such Baume, Twaddell, etc. Others read directly in specific gravity which
volume of the liquid to the weight same volume of water at a standard temperature. Dilution of Liquids. It is often required to reduce the percentage strength of a solution. For example: How would you mix two gallons gives the ratio of the weight of a given
of the
â&#x20AC;&#x201D;
of 289^ acetic acid, from a supply of glacial acetic acid?
To make 100 cc of 28% acid we need 28 cc of glacial acid. To make i cc of 28% acid we need 28/100 cc of glacial acid. To make 2 gallons 7570 cc of 28'/^ acid we need 28 X 75-7 ^2120 cc (71^ ounces) of glacial acid.
Therefore take 71? ounces 2120 cc of glacial acid and add water to
make
To
2
gallons 7570 cc.
dilute a solution three times
we do not add
three times the
of water but approximately twice the
volume and so on.
One volume
volumes of water
of solution plus about
solution which
is
2
volume
For example:
=
3
volumes of
one-third as strong or three times as dilute as the
original.
Stock Solutions.
â&#x20AC;&#x201D; A stock
solution
is
a concentrated solution to
which water is added before use. In the case of simple solutions containing only one salt such as potassium bromide, sodium carbonate, etc., a 10% solution is most convenient because by dividing the volume of the solution in cc by 10 we get the number of grams present in the solution.
Thus 3
"
75 cc of
10%
potassium bromide contains
Photographic Methods of Testing Developers Amcr. Ann. Phot. 36, 184 (1922).
^9> 153 (1922)
;
"
by
7.5
J. I.
grams. Crahtree.
Brit. J. Phot.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
14
The
limiting strength of solution
which
it is
possible to
make
particular case depends on the solubility of the chemical,
in
any
and as the
solubility diminishes with temperature a solution should not
be made
stronger than a saturated solution at 40째F. (4.4째C.), otherwise in cold
weather the substance would crystallize out (see table of
solubilities
given in the Appendix, page 338).
A sible
stock solution of sodium sulphite should be
(20%
tion oxidizes very slowly
solution
it
made
as strong as pos-
of the desiccated salt) because at such a strength the solu-
and
will therefore keep,
combines with the oxygen
in the air
whereas in weaker
very readily and
is
then
useless as a preservative.
In making up any stock solution,
its
strength should be such that
can be diluted easily to give a solution of working strength. ample, hypo
often mixed as a
is
volume of water a triple, or
2 5
%
solution
50% is
solution
it
For ex-
and then by doubling the
This plan of mixing double,
obtained.
quadruple strength stock solutions
is
often a valuable
means
of
saving both space and time.
The term is
"
Stock Solution " should precede a published formula that
to be diluted for use, as otherwise there
a formula
may
is
always the possibility that
be mistaken for a working solution.
CHAPTER
III
APPARATUS AND METHODS OF USE
—
Types of Weighing Devices. Apparatus for weighing chemimay be classified conveniently into several sizes according to the maximum volume of solution to be prepared as follows: Four Liters (i Gallon). A small double pan scale weighing to cals
—
100 or 200 grams {y\ to studio use.
Fig. ia
Two common
— Small studio
One Hundred of
ounces)
7
is
satisfactory for amateur or small
types are shown
in
Figures
i.A
or lal)oiator>- scale, capacity 100 prams
—A
Liters (25 Gallons).
for the
moderate
size studio,
ounces).
(3'.
scale having a capacity
5000 grams (about 10 pounds) should be provided.
ample
and iB.
It
should be
photofinishing plant, and x-ray
laboratory (see Fig. iC).
Four Hundred Liters (100 Gallons).
— For
large commercial es-
tablishments, photofinishing plants, and small motion picture laboratories a scale
weighing from 8 to 10 kilos
(
18 to 22 pounds)
is
required.
shown in Figure iD is very satisfactory. Oscillations of the pointer are damped by an oil dash pot. The capacThis model may ity of the model shown is 12.5 kilos (27-^ pounds). also be used for small scale weighing by removing the large scoop and its For. rapid weighing, the type
tare weight.
Two Thousand Liters weighing
in either
(500 Gallons) or More.
— Platform
scales
kilograms or pounds (and ounces) should be pro-
A
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
16
Two
vided for work requiring very large volumes of solutions. are
shown
These are satisfactory
in Figure 2.
for large
types
motion picture
laboratories or very large commercial plants. It
may
be desirable to have two or more types of scales in the larger
establishments to facilitate rapid mixing of small as well as large vol-
umes
of solution, such as the type
shown
in
Figure
iD and
Figure
2
and 2B.
Fig.
Small laboratory scale, capacity 500 grams (i pound). Torsion Balance Co., New York, N. Y.
IB
Weighing Very Small Quantities sionally required to
mix very
of Chemicals.
gram
is
needed which
will
For such work, a sensitive
weigh accurately
(or fractions of a grain).
Figure
3.
Type A with
general use.
Two
is
0.02
in
hundredth parts of a
types of balances are illustrated in
the hinged glass cover
Its sensitiveness
It is occa-
dilute solutions of chemicals, particularly
of dyes for toning or desensitizing baths.
balance
â&#x20AC;&#x201D;
Courtesy
gram
(
is
a practical balance for
1/32 grain) and
its
capacity,
120 grams (4 ounces).
Type B
represents a
more accurate balance commonly used
in
ana-
APPARATUS AND METHODS OF USE lytical
work.
rider as
It is
equipped with a calibrated chain instead of a movable
One end
on type A.
arm, the other to a vernier weight of the chain
The chain
is
17
is
added
moved by
of the chain
is
attached to the balance
As the vernier scale is lowered, more the balance arm and less as it is raised.
scale.
to
rotating a crank extending through the side of
the balance case.
Fig. ic
â&#x20AC;&#x201D; Double
pan
scale,
Courtesy Torsion
capacity 5 kilos (10 pounds).
Balance Co.,
New
York, N. Y.
Balance pans should preferably be made of a non-corroding metal, such as nickel, 18-8 stainless steel,* or nickel-plated brass, although porcelain pans are also satisfactory.
Containers for Mixing. glass flasks
*
known
â&#x20AC;&#x201D; For small volumes
as Erlenmeyer
flasks are the
There are several manufacturers of the type of
(18% chromium-8%
The
of solution, conical
most suitable mixing
stainless steel
known
as
18-8
i8-8 stainless steel to photographic solutions varies somewhat, however, depending on the content of carbon, molybdenum, titanium, zirconium, selenium, etc. and the heat treatment which the steel has received at the mill. A method of testing 18-8 stainless steels for their resistance to corrosive attack by photographic solutions is described on pages 53-57-
Two
nickel).
corrosion resistance of
recognized text books on stainless steel are the following
:
" Stainless Iron
and
Steel," by J. H. G. Monypenny, Chapman & Hall, London, 1926, and "The Book of Stainless Steel," Amer. Soc. of Steel Treating, 7016 Euclid Ave., Cleveland, Ohio.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
18
vessels.
(see Fig.
For larger volumes use enameled pails or hard rubber buckets 32D, page 66) For still larger volumes, tanks, drums, or crocks .
of a suitable material such as
ware, or an 18-8 stainless
Fig. id
wood, Alberene stone, hard glazed stone-
steel,
â&#x20AC;&#x201D; Single pan and scoop
such as Allegheny metal (Fig. 4)
scale.
may
Courtesy Fairbanks, Morse & Co., Chicago, 111.
be used.
For large scale work the solution should be pumped or emptied
by gravity
into a larger storage tank
mechanical
stirrers
and allowed
where
to clear
by
it is
thoroughly mixed with
settling before
emptying into
the circulating tank (see Fig. 19, page 39).
Weighing and Measuring.
â&#x20AC;&#x201D; Chemicals
should
preferably
be
room which is separated from the developing room and care should be taken when handling such
weighed out and the solutions prepared
in a
substances as hydroquinone, resublimed pyro, potassium ferricyanide, etc.,
not to shake the finer particles into the
air,
otherwise they
may
enter
the ventilating system and settle out on benches or shelves where negatives
and prints are stored.
Such chemical dust almost invariably pro-
APPARATUS AND METHODS OF USE
19
duces spots and stains (Fig. 5) particularly if the sensitive materials are wet when contaminated by the dust particles. It is good practice to
mix developers and
fixing baths in separate rooms, in order to avoid
possible contamination of developers
â&#x20AC;&#x201D; Platform
Fig. 2\-
with beam.
scale
Fairbanks, Morse
&
Fig. 2B
and
mixing vessel do not shake the paper but drop water to flow over
it
â&#x20AC;&#x201D;
dial.
111.
pieces of paper
any
bath chemicals.
fixing
Platform scale with Courtesy Toledo Scale Co., Toledo, Ohio.
Courtesy
Co., Chicago,
Weigh out chemicals on
by the
after transferring to the
it
into the sink
so as to dissolve the dust.
and allow
Larger quantities are
most conveniently weighed out in buckets. Shallow wooden trays about 16 by 20 inches and lined with rubberized cloth are useful containers for weighing out large quantities of chemicals previous to dissolving (Fig. 6).
A
different tray preferably should be used for each chemical
by marking the or
tray.
Metal scoops made of aluminum,
and
labelled
stainless steel,
Monel may be used effectively for weighing large quantities of chemiThey should be washed out carefully after weighing each different
cals.
chemical to avoid contamination.
The
zero points on
quent intervals tant
all scales
and balances should be checked at
to insure accurate weighing.
when using
This
is
fre-
especially impor-
sensitive balances for weighing small quantities.
For small volumes
of liquids a glass graduate
marked
off in cc or
V
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
20
For larger volumes use a bucket previously
ounces should be used. graduated, or
mark
off the inside of the
tank or crock used for mixing
(see discussion on paddles on pages 24-2 7 )
When
.
measuring a liquid
a glass graduate place the eye on a level with the graduation
Fig. 3A
â&#x20AC;&#x201D; Chemical and dyestuffs balance with sion Balance Co.,
New
in the liquid until the lowest part of the
with
this level.
it
warm
is
drawn up the
sides so that
made
as
shown
liquid contracts
Dissolving.
in Figure 7
and
at
its
solubility
and degree
temperature of the solvent, and the rate of
effect
is
side-
All readings
room temperature because
on cooling.
â&#x20AC;&#x201D; The rapidity with which a substance
solvent depends on
stirring
on viewing
appears as though the liquid has two surfaces.
should be a
curved surface coincides
to capillary attraction the liquid in contact with
the walls of the graduate
ways
Courtesy Tor-
calibrated rider.
York, N. Y.
pour
Owing
in
mark and
dissolves in
any
of fineness, the nature
and
stirring.
The method
of
very important and the shape of the paddle has considerable
on the rate of dissolution (see paragraph discussing paddles on
pages 24-27).
Most
solutions are rendered completely
homogeneous
APPARATUS AND METHODS OF USE
21
only with difficulty. caustic soda, will
if
For example, when mixing solutions containing they are not thoroughly agitated the heavier caustic liquid
remain at the bottom and when used the solution
form composition.
them thoroughly
Fig. 3B
It is
warm is
water with
usually
The
way
is
is
usually
more
stirring.
warm enough
Water
to dissolve
is
be of uni-
solutions to stir
Courtesy Christian Becker,
soluble in
of mixing a solution
will not
all
complcttYl and before use.
balance using calibrated chain. Inc., New York, X. Y.
Since a chemical the quickest
after the mixini:
:it:;)in
— Chemical
important, therefore, with
to
warm
water than
in cold
powder and dissolve
at a temperature of
it
in
i25°F. (52°C.)
most photographic chemicals
readily.
use of water at higher temperatures, especially boiling water,
is
not
recommended because there may be danger of decomposing the chemical and if the solution is to be used immediately, it will require considerable time to cool the solution to the required temperature. Since most solutions are intended for use at ordinary temperatures (65° to 7o°F.) (18° to 2i°C.), the solution
must be cooled
off
if
very hot water
again
if it is
is
used for dissolving,
required for immediate use,
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
22
though usually the time taken to do
would be taken up
this is less
than the extra time which
in dissolving the chemicals in cold water.
When
mixing, therefore, as a general rule, dissolve each chemical in as small
a volume as possible of water at about i25°F. (52°C.), cool, and dilute
Fk;. 4
— Stainless
stt'cl
(iS-S) mixinti tank and
The gallons or 75 liters capacity). hard rubber faucet and pipe is inserted through a stirrer
(20
and held
soft rubber stopper
in place
with a metal
plate.
with cold water.
oughly
if
After diluting with water, shake the solution, thor-
in a bottle,* or stir
if
in a tank, otherwise the
water added will
tend to float on top of the heavier solution.
When
mixing a solution
in
a tank,
it is
possible to proceed in one of
two ways A. Dissolve the chemicals separately in buckets or small vessels, add
each solution to the tank
ume B.
Add
filled half
*
in the
necessary order, and then dilute to vol-
with cool water. the solid chemicals directly to the large mixing tank which or three-quarters full with water at 65° to 75°F.
To permit thorough mixing,
the capacity of the bottle should be
than the volume of the solution to be mixed.
is
(18° to
somewhat larger
APPARATUS AND METHODS OF USE 24°C.).
23
After diluting to volume with cool water, the temperature of
the solution will be about right for immediate use.
It
is
very important,
however, when mixing very large volumes of solution, such as looo gallons (4000 liters) or more, to avoid the necessity of cooling the final solu-
FiG. 5
— Spots produced
on film by chemical
dust.
Hypo
(left)
and potassium
ferricyanide (right).
Fig. 6
— Trays lor weighing chemicals.
tion, as this operation takes considerable time,
which
may
be shortened
only by the use of an expensive refrigeration installation.
For large scale mixing, method B.
is
usually to be preferred.
practice to dissolve the chemicals directly in the tank w^hich
developing and
facilities
is
It
is
should be provided for filtering the solution at
some point between the mixing and developing tanks. When dissolving finely powdered Caking of Chemicals.
—
cated
salts,
there
is
bad
used for
a tendency for the salt to form a hard cake
quantities of the chemical are
dumped
if
desic-
large
into the water without stirring,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
24 or
if
the water
is
added
This
to the chemical.
is
due
to the
tendency of
the desiccated salt to combine with water to form a crystalline compound.
This cake dissolves very slowly and
by pouring the
salt slowly into the
formation should be avoided
its
water while agitating the solution
vigorously.
30
UQ ^ \0
*v_y Fig.
7
â&#x20AC;&#x201D; Position
of eye
when judging
level
Another way of decreasing the caking
is
of liquid in a column.
to use chemicals
not too finely powdered, since the smaller the particle
size,
which are the greater
the caking tendency, especially with chemicals such as sulphite and car-
bonate.
now
So called granulated samples of
many
desiccated chemicals are
more quickly, have less tendency to float on the surface of the water, and are practically dustless when handled. The monohydrated variety of sodium carbonate, howavailable which pour easily, dissolve
ever, does not appear to
have any
less
tendency
to
cake than the desic-
cated variety.
As a general working rule, however, for all desiccated salts, the chemialways be added slowly to the water with stirring and not water to the chemical, or some caking trouble may be encountered. Equipment for stirring chemiMethods of Stirring Solutions. cal should
â&#x20AC;&#x201D;
cals
when mixing
as the mixing
solution
up
is
solutions
done:
to 100 or
i.
may
be classified into two types according
by hand
or 2.
by machinery.
200 gallons, hand mixing
is
For volumes of
usually employed, but
APPARATUS AND METHODS OF USE for larger volumes,
mechanical
more
stirrers are
efficient.
chanical stirrers also offer advantages for mixing volumes of
25
Small me2 5
gallons
or more.
The
simplest type of stirring device
either as a solid rod or as
Fig. 8
â&#x20AC;&#x201D; T> pes of hand A
sealed at both ends (see Fig. 8).
which
fits
is
a rod, preferably
heavy walled tubing (about
made
of glass,
| inch diameter)
stirring devices.
rubber hose or jacket (i inch long)
snugly around the end will usually prevent breakage of either
the rod or the vessel in which
used.
it is
A
stirring rod is only satisfac-
tory for use with very small volumes of solution, usually not greater
than
2
gallons.
If a glass
tube
is
chosen, a cork
may
be forced tightly
into the glass tube before sealing the ends in such a position that the
bottom of the cork
will serve as a
measure of volume when the rod is Additional volume calibra-
held upright in a particular mixing crock. tions
may
be made
in several
by choosing the length 2. by marking by putting more than one cork in the
ways as follows
:
i
.
of the cork so that both ends represent definite volumes,
the side of the cork with ink, or
3.
26
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
tube.
Too many
confusing.
A
calibrations should not be
made
become should be wedged
or they will
small card explaining the calibrations
into the tube.
For mixing volumes of solution from 8 in size, a useful
Fig. 9
to
40
liters (2 to
10 gallons)
mixing device consists of a metal rod (Monel, nickel,
â&#x20AC;&#x201D; Motion of paddle
for efficient agitation of deep nar-
row width
tank.
or Allegheny metal) with a metal disk fastened to one end (Fig. 8).
This
stirrer is
used
much
like the old-fashioned
hand churn by moving
up and down inside the mixing vessel. A wooden stick or paddle made of hard wood such as maple or cypress is a convenient form of stirrer for volumes up to 100 or 200 gallons (400 or 800 liters), but a separate paddle, marked with the name of the soluthe handle
tion,
should be used for each solution, to eliminate the possibility of con-
tamination.
Wooden
paddles should not be wax impregnated to resist
the action of the solution, because this treatment decreases their
resili-
ency and with hot solutions some of the wax is apt to melt and get into the solution. When the solution becomes cool, the wax particles, unless filtered out,
may
settle
on the surface of the
film.
The paddle shown second from the right in Figure 8 deep tanks by pushing it vertically down along one or crock,
is
used
in
narrow
side of the tank
moving it across the bottom by using the top edge of the vessel and drawing it upwards along the opposite side of the
as a fulcrum, vessel.
The paddle on
type which
is
the extreme right in Figure 8
used most effectively by thrusting
it
is
the conventional
vertically inside a
APPARATUS AND METHODS OF USE
27
tank along one wall and moving the blade through an arc by using the top edge of the tank as a fulcrum as shown in Figure 9. Considerable agitation may be secured with this type of paddle, providing the diameter of the tank
is
enough
large
to permit the
movement
of the paddle
through a fairly wide arc.
Fig. 10
â&#x20AC;&#x201D;-Portable
stirrer installed in a large
mixing tank.
Courtesy
M-G-M
Laboratories, Hollywood, Calif.
Notches cut
in the side of a
wooden paddle may
measuring a definite volume of solution
serve as a
in a particular
means
of
tank or crock by
holding the paddle vertically and adding water to the mark.
Mechanical Stirrers. types, namely, portable in
â&#x20AC;&#x201D; Mechanical
and stationary.
stirrers
two general is
supplied
a variety of sizes with telescoping metal shafts which, for photographic
solutions, should be stirrers
may
made
of nickel,
Monel, or 18-8
stainless steel.
The
be clamped onto the edge of the vessel or tank, as shown in
Figure 10, which represents an actual illustration
a large motion picture laboratory. is
are of
The former type
attached to the
stirrer.
in
a mixing room of
The motor
( 1/20 to 10 horse power) The blades are arranged to create an upward
current which insures thorough mixing, as shown in Figure iiA.
The two most common
types of stationary mechanical stirrers are the
mixing
tank
(Fig.
11 A)
and
1.
those
2.
those installed horizontally, through the side and near the base of the
installed
vertically
in
28
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
tank (Fig. iiB).
A
suitable stuffing
box
is
fitted at the point
where
the drive shaft enters the tank to prevent leakage.
In general, an electric motor should never be placed directly over a solution unless
it is
enclosed tightly, owing to the danger of contamina-
tion with oil from the
motor
shaft.
— Agitation
Fig. iia^
able vertical stirrer.
currents formed by port-
Courtesy Mixing Equipment
Co., Rochester, N. Y.
Theory
of Stirring/''
— Most
photographic chemicals are fairly
soluble in water at normal temperature and the majority are readily solu-
The method of stirring is not so imwhen mixing small volumes of solution, but it is of importance
ble in water at 125° F. (52°C.).
portant,
from the standpoint
of time saved, cost of labor,
when large volumes are The movement of the paddle
solution
to
and
clarity of the final
be mixed.
or stirring device
may
be considered
from several standpoints according to the nature and effectiveness of the motion produced. These different movements are as follows: * The authors are indebted for many Equipment Co., Rochester, N. Y.
of
tlie
ideas in this section to the
Mixing
APPARATUS AND METHODS OF USE I.
Free Rotational.
stirring
movements.
— This ^
It is
one of the most
is
tical shafts
supported
sets of horizontal paddles as
Fig.
I
common
types of
usually effected with stirrers which have ver-
one or more
of stirrer tends to set
29
in the center of the
mixing tank and which have
shown
in
Figure 12.
This type
up one or more horizontally moving layers
IB
— Agitation
in the
currents set up by hori-
Courtesy Mixing Equipment Co.,
zontal stirrer.
Rochester, N. Y.
mixing vessel (according to the number of paddles) and rate of solution.
slow
If the solution contains an alkali of heavier density
than water, the solution
probably tend to be denser at the bottom
will
than at the top. 2.
effects a
Impeded Rotational.
— This movement
is
similar to the free ro-
around the side of the tank created by the uniform motion
tational except that there are baffles installed
which tend
to
break up the stratification
of horizontally
moving paddles.
cals results with a
tendency 3.
mixer of
More
this type,
rapid dissolution of the chemi-
but there
is still
a fairly strong
for separate layer formation.
Vortex Movement.
— When a propeller type
of stirrer
is
placed
near or in the center of a liquid column, the rotation tends to create a
downward time.
swirling motion which assumes a vortex shape in a very short
This stirring motion
is
useful
when
dissolving a light fluffy solid
on the surface, but a considerable quantity of air This latter feature is is introduced into the solution at the same time. photographic somany because objectionable in photographic practice
which tends
to float
2
PHOTOGRAPHIC CHE^HCALS AND SOLUTIONS lutions are oxidizable
by
Furthermore, the entrapped
air.
air
bubbles
tend to cling to film surfaces and produce airbell markings. 4.
â&#x20AC;&#x201D; Most
Controlled Directional Flow.
liquid or liquid-liquid solutions
is
effective
mixing of
solid-
secured by stirring devices which in-
sure a controlled directional flow of the liquid within the mixing vessel.
Fig.
Motor driven
1
Paddle
vertical
shaft.
stirrer.
This flowing motion should be largely vertical and of drive
the top. ler,
heaw
any
solid or liquid portion
Such motion
is
best secured with the aid of a rotating propel-
the blades of which thrust
tion.
The
entire
mix
in a vertical plane.
same shaft
if
in a
is
sufficient force to
from the bottom of the vessel to
downward
in
an angular off-center posi-
thereby turned over and over from bottom to top
Two
or
more propellers ma}' be employed on the
deep tank (4 to 8
feet)
but their action should not be
opposed or their efficiency will be reduced. are used, the bottom blade
is
unable to
lift
\Mien opposed propellers
materials of different densities
APPARATUS AND METHODS OF USE
31
from the tank bottom, because of the retarding downward current of the upper blade. Propellers of the type described are
shown
tached to a portable stirring device and
motor
Figure
fitted to a shaft entering the side of the tank.
preferred for almost
all
Fig. 15
The
1
1,
A and
if
B, at-
a gear drive
Type A
is
to
be
photographic mixing operations on a large scale.
â&#x20AC;&#x201D; Glass funnel
fitted
with
filter cloth.
position of the propeller in relation to the tank design
Xow,
tant.
in
this, in turn, to
the tank
best results are secured
is
is
impor-
considered to be di\ided into four quadrants,
when
the stirrer
is
attached to the wall and in-
own quadrant.
In very
clined so that the shaft will rotate within
its
large tanks of
installation should be used.
The
3000 gallon capacity, a side
shaft should enter the tank on a line parallel with but off the center
line to insure a controlled directional flow.
These types of
stirrers represent
more rapid mixing with which have
less
free rotational or
is
to
dust in
is
possible with mixers
impeded rotational motion.
â&#x20AC;&#x201D;
The purpose of filtering and clarifyremove suspended matter such as dirt caused by the presence of the chemicals used and also any residue or undissolved particles
Filtering and Clarifying. ing
compact mechanisms which insure
power outlay than
which might
settle
on the sensitive photographic material during de-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
32
Furthermore, while some solu-
velopment, and produce spots or stains.
and
tions are being exhausted, for example, certain developers
fixing
and and scum which should be removed
baths, they tend to accumulate a sludge consisting of by-products
foreign matter, such as gelatin, dirt,
from the solution several times during
its
in order to prevent the
life,
sediment from adhering to the emulsion surface and causing spots and stains.
Filtration
may
be defined as the act of separation of a solid from a
by passing
liquid brought about
through the
filter is
known
to clear
allowing the particles
them by
The
etc.
liquid
which passes
as the filtrate, whereas the solid remaining
Clarification
in the filter is called the residue or filter cake.
term meaning
medium
the liquid through a filtering
such as cloth, paper, charcoal, sawdust,
a broader
is
up a suspension or cloudiness in a solution by to settle out by sedimentation, or by removing
In photographic work, the purpose of filtering
filtration.
is
usually to remove a small quantity of solid from a large volume of liquid.
The
filtration of
water to be used for mixing photographic solutions
represents a specialized application of filtration and
is
discussed in
Chapter VI, page 107.
The removal
of particles
remaining
in a solution after
may
mixing
be
accomplished by any of the following methods: A. Allow the solution to stand and draw pernatant liquid.
pended matter
is
This method so fine that
it
is
off or
decant the clear su-
particularly useful
will pass
when
through a coarse
the sus-
filter.
Since coarse particles settle quickly, the rate of settling of a semicolloidal sludge
can usually be hastened by mixing the solution
in
hot
water, because the heat tends to coagulate the suspension and causes the particles to cluster together.
Thus
crystals of
if
sodium sulphide
which are brown from the presence of iron are dissolved
in
hot water
the colloidal iron sulphide coagulates and settles out rapidly leaving a perfectly colorless solution.
B. Filter the solution through fabric or (Fig. 13).
Filtering through paper
is
filter
continual dropping of the solution exposes oxidation.
It
is
usually sufficient to
paper held
in a funnel
usually a slow process and the
filter
it
to the air, thus causing
through very
fine cloth or
muslin suspended from the edge of a glass funnel or an enameled
New
pail.
washed thoroughly, otherwise the sizing matter in the fabric will be washed into the solution and settle out as a sludge. C. As a modification of method B, when mixing a quantity of solution in a tank, stretch a filter bag made of strong toweling cloth (28 mesh) cloth should be
APPARATUS AND METHODS OF USE
33
over the tank, place the chemicals in the bag (about 6 inches deep) and allow hot water to flow into
and the solution
it.
filtered at the
In this
same
way
used for each solution so as to eliminate
Fig. 14A
Fig. 14B
The method is
fitted
â&#x20AC;&#x201D; Frame support
over a wooden frame and
less steel
bag is
A
all risk
for filter bap:
â&#x20AC;&#x201D; Method of supporting
of supporting the
the chemicals are dissolved
time.
filter
is
separate bag should be of contamination.
on deep tank.
bag over top of deep tank.
shown
in
Figure 14A.
held in place by
means
The bag
of four stain-
bars passing through loops along the edges of the bag.
In the case of deep tanks, the wooden frame can be dispensed with
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
34
by adopting the arrangement shown in Figure 14B. The cloth bag 5 inches deep is supported by means of bars passing through seams along opposite edges of the bag, and in turn the bars are held in place either by means of two pieces of wood passing over the ends of the bars as shown, or by metal stirrups fitted to the sides of the tank. It is important, when filtering chemicals through a bag, to add only comparatively small quantities of the chemical to the bag at one time. about
Warm water bag
(about i25째F.) (52째C.) from a hose should be run into the
slow stream, and as the chemicals are dissolved, more of the
in a
solid should be added.
If too
much
solid
and
for caking with desiccated salts
is
added, there
this interferes
is
a tendency
with the rapid dis-
solving of the chemical.
Some substances
are so finely divided that they will pass through a
bag unless one
filter
of very fine
mesh
is
used.
This
is
true of most de-
veloping agents, which therefore should be dissolved separately in as small a volume as possible of water at i25째F. (52 째C.) and then the solution poured into the filter bag.
The
sulphite
and carbonate compo-
nents of a developer may, however, be mixed and filtered by the bag
method.
In preparing large volumes of stock solutions of single chemi-
cals such as
hypo
or carbonate the filter
bag plan
offers
a rapid and
thorough method. It
is
important that the bag used should be wide and not too deep,
otherwise
will dip into the solution
it
and the chemicals
will dissolve
very slowly.
D.
A
A and C
combination of methods
is
the best and most desirable
as follows
For quantities of solution up
to 5 gallons, filter
through a cloth into
a bottle or crock fitted with a side tube of hard rubber inserted through a soft
rubber stopper (see Fig. 79, page 196). In this way the fine parout but the drainage tube is sufficiently high so as not to
ticles settle
disturb the sediment.
Charles
^
has described a number of useful methods of dissolving
chemicals which involve the suspension principle.
As one scheme, he
suggests adding the solid chemicals to a perforated earthenware pot
(such as
is
sold for electroplaters' use)
entirely below the surface of the water. inside the pot so that the solution
is
and suspending
A
filter
filtered as
this
pot almost
cloth could be placed
soon as the chemicals are
dissolved.
For small scale plants, the solutions should be mixed 1
Brit. J. Phot. 71, 519 (1924).
in
separate
APPARATUS AND METHODS OF USE
35
wooden vats or stoneware crocks in the chemical room, where they can by settling before transferring the clear liquid to the darkroom.
clarify
A
simple device for developer clarification consists essentially of a
water pump, a trap, and a vacuum nozzle as shown
FiG.
â&#x20AC;&#x201D; Suction
15-
device
and de-
in Fig. 15
removal of developer tank
for
sludge.
scribed
by
Ives, Miller,
and Crabtree.-
to stand overnight or until clarified
moved by
inserting the
tice,
the bulk of
much
solution should be allowed
bottom
in the
re-
nozzle in the solution and moving
it
up the sludge. With practhe sludge may be withdrawn rapidly without removing
carefully along the
very
vacuum
The
and the sediment
bottom so as not
to stir
of the liquid developer.
In a recirculating system as used on automatic developing machines for
motion picture work (see Fig. 90, page 211),
the sludge
by
on the return or suction
inserting a filter line
filters
it is
from the machine
to the circulating tank.
as used in other chemical processes
rapid filtration (Figs.
In addition to the
possible to
remove
at some point in the system, for example,
may
Pressure
be necessary for
16A and 16B).
filtering
media described, several others are
avail-
ble as follows: 1.
Sawdust contained
in a perforated
bulky and inconvenient 2.
-
to
Several types of charcoal. J.
box or
vessel.
This
handle when replacing the
Soc. Mot. Pict. Eng. 17, 26 (July 1931).
is
rather
filter.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
36
form of powder or cakes.
3.
Silicious materials in the
4.
Fine wire and glass-cloth screens.
5.
Paper pulp,
Fig.
To
i6a-
etc.
Small plate pressure filter showing construction. Engineering Co., New York, N. Y.
date, few of these materials
Courtesy Alsop
have been used by the photographic
industry but some of them will undoubtedly find extensive use in the future.
In the filtration of a gelatinous precipitate, such as a silver chloride sludge, a simple working
filter
can be constructed economically by lining
wooden box with canvas (Fig. 17). The box should be about 8 inches wide, 2 feet deep, and 4 feet long, or, if smaller, of about the same proportions. Since the perforations weaken the strength of the sides, these should be held together preferably at each end by a perforated
several metal bolts of 18-8 stainless steel. filtration to
add some
silicious
powder
It is
necessary for efficient
to the solution to
be
filtered to
prevent the gelatinous sludge from plugging up the pores of the canvas.
Such filters
filter
(see
aids are obtainable from several companies manufacturing
Appendix, page 342).
APPARATUS AND METHODS OF USE When quired. large so
filtering a silver sulphide sludge,
37
a different type of box
The box should be a shallow one, about 6 inches deep and that the sludge, when settled, will represent a thin cake.
A
box should be perforated and lined with canvas.
filter
aid
is
is
re-
fairly
The
necessary
to prevent stoppage of the pores in the canvas.*
Fig. i6b
â&#x20AC;&#x201D; Detail
of plate pressure
filter
Alsop Engineering Co.,
One
useful type of mixing
and
showing construction. York, N. Y.
filtering
apparatus consists of an enamel
lined mixing tank fitted with a portable stirrer.
through a small gear is
pump
to a
connected to the storage tank.
pressure
forated metal screen cylinders separated
paper or
filter
cloth
(Fig. i8).
is
filter
is
placed.
forced through the sides
*
The authors are indebted embodied
in this section.
to
Mr. R.
is
connected
which, in turn,
consists of
by a wrapping
a pressure of about 25 pounds per square inch.
tions
filter
These three units
cylinder on which a tightly fitting cover
the base of the column and
This tank
compact pressure
The
Courtesy
New
fit
two per-
of either
filter
inside a metal
The
liquid enters
by the pump under
The pump may
also
S. Scott for several of the filtering sugges-
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
38
be operated independently of the in the
filter
(see list of filter manufacturers
Appendix, page 342 )
^ 00000 o o o * * 00*-* O o
*
*
» -
-i
»
A Fig. 17
Fig. 18
— Canvas lined
— Cylindrical pressure neering Co.,
wooden
filter
box.
Courtesy Alsop EngiYork, N. Y.
filter.
New
Apparatus Arrangement for Large Scale Mixing.
— For mo-
work or large photofinishing establishments, the chemical room should be situated on the floor above the developing room when-
tion picture
ever possible so that there
is
no chance of contamination of the develop-
ing and drying rooms with chemical dust, while the solutions
may
be
APPARATUS AND IMETHODS OF USE piped to the various rooms without the use of pumps. cal solutions directly
avoided because this settles as
it is
in
fixing
Mixing of chemitanks should be
the dirt
when mixing, and
the developing and
impossible to
filter
out
all
39
a sludge at the bottom of the tank (see Chapter
IX
further details on conveying solutions; also Chapter IV' on suitable terials for the construction of
for
ma-
apparatus).
GRAVITV rCElO
Fig. 19
â&#x20AC;&#x201D; Mixing
tanks using (A) gravity feed, and (B)
pump
feed to storage tank.
When the mixing room is located above the developing room, the may be fed by gravity from the mixing tanks through a cloth
tions
A
solufilter
Hgure 19. Most efficient filtering with a cloth filter is accomplished by using a cloth of sufficient size to permit of occasional movement of the cloth across the into the feed or circulating tank as
shown
in
of
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
40
top of the
system
is
box
filter
so as to expose a fresh filtering surface.
pump would need
a recirculating one, a
If the
to be used to return
In some laboratories, it is inconvenient room on the floor above the processing room and it on the same floor or the floor below (B in Fig. 19).
the solution to the feed tank. locate the mixing
placed either
Fig. 20
Removing Scum. scum usually
skimming
off
If solutions are not filtered
This scum consists of
with a towel or a skimmer
is
device.
after mixing, a
has been allowed to
rises to the surface after the solution
stand a few hours.
be skimmed
—
— Solution
to
fibers, dust, etc.,
made
and
it
should
of several thicknesses of
cheesecloth stretched on a wire frame (Fig. 20).
When
a fixing bath has been used for some time and
is
allowed to
stand undisturbed for a few days, any hydrogen sulphide gas which
may
be present in the atmosphere forms a metallic looking scum of silver sulphide at the surface of the liquid and on immersing the film, this attaches
itself to
the gelatin and remains even after washing
Before the solution
is
used, any such
(
scum should be removed
scum
Fig. 21).
carefully
with a sheet of blotting paper or by using a cheesecloth skimmer as described above.
Layout o£ Chemical Mixing Room. will
vary
— The chemical mixing room
in size according to the extent of the
requirements of the user.
For the commercial photographer with a small business, necessary to build a small cupboard such as is
of sufficient size
and capacity
is
to hold the
shown
done.
The scale
rests
is
The door
lowered when there
on a wooden base which
it
may
only be
Figure 22, which
dry and liquid chemicals,
the scales, bottles, and a few other accessories. section holding the small scale
in
slides
is
of the center
weighing to be
on two guides.
APPARATUS AND METHODS OF USE
41
In large laboratories, the chemical mixing and storage room
occupy considerable
floor
may
Dry chemicals
space (see Fig. 82, page 200).
are received in barrels, drums, and cans and liciuid chemicals in cans,
and carboys.
barrels,
room
These should usually be stored
a separate
in
closely adjoining the mixing room.
-^"J^^^V
Fig. 21
â&#x20AC;&#x201D; Spot on film caused by
silver sulphide
scum.
(200 x)
Waterproof Floors for Chemical Mixing Rooms and DarkThe floors of rooms where photographic chemicals and solu-
rooms/''
â&#x20AC;&#x201D;
tions are to be handled should be constructed of waterproof materials to
prevent chemical attack and to permit easy washing.
Existing floors
wood and concrete. Xo attempt should be made to lay a waterproof floor over another floor, however, unless the latter is in good condition. All boards of wooden
are usually of two types:
floors
should be solid and fastened securely
move, they
If the
in place.
break up the waterproofing.
will
boards can
Concrete floors must be
smooth and should show no signs of disintegration. There are four general types of waterproofing materials as A. hard rubber
tile
blocks;
B.
mastic
(applied
hot);
*
The authors
are indebted to the Engineering Dept. at the
many
follows:
asphalt-
The rubber
concrete (applied cold); and D. reinforced concrete.
Rochester, N. Y., for
C.
tile
Kodak Park Works,
suggestions incorporated in this section.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
42
to
wood only, the mastic and asphalt-concrete on wood or and the reinforced concrete on concrete. All laboratory floors should be equipped with a side curb and drain permit easy washing with a hose (see drain construction in Fig. 23).
A
false floor
is
usually laid on
concrete,
made
of cypress should be built over the
main
floor at
such
height as to facilitate easy access to deep tanks.
Fig. 22
The Use
of a Fabric
â&#x20AC;&#x201D; Chemical
Membrane.
cupboard.
â&#x20AC;&#x201D;
It is general practice
when
constructing any of the waterproof floors listed above to lay a fabric
membrane in pitch before the waterproof floor is laid. A pitch-saturated open mesh cotton fabric is recommended. Paper membranes crack easily
The
and are not as satisfactory clean dry surface should
point) with waterproofing pitch.
with strips of fabric, allowing a
mopped with hot
as cloth.
be mopped (beginning at the lowest The hot pitch should then be covered 2 -inch overlap. The edges should be
first
pitch before the seams are overlapped.
layers of fabric should be applied over the first layer
should separate each layer.
Each ply
Two
additional
and a layer
of pitch
of fabric should be staggered
APPARATUS AND METHODS OF USE
43
about 24 inches from the hip of the previous hiyer. Fabric should not touch fabric at any point and no wrinkles should exist.
When
the third ply has been laid, the entire top should be
with hot pitch before
it is
covered with the specified
mopped
floor finish.
-3fc Wi°^' "•JT
"
SLOPE BOTH SUnrACCS TOWARD DRAIN V3 PLV WATER PROOriNQ MEMBRANE
^/ATtR PROOrcD
MEMBRANE SECURELY CLAMPED BETWEEN CLAMPINGi RINCa AND DRAIN. CLAMPINCi RIN& HAS SLOTS AT THE BOTTOM TO ALLOVrf WATER TO DRAIN OTF TOP OF MEMBRANE
NOTE: -^ TOP COURSE l» PLACED MONOLITHIC WITH XI' BASE
-5
\
COURSE Fig. 23
— Detail
of waterproof concrete floor construction showing arrangement of tank support and drain.
The membrane should be
carried
up 4 inches on
walls above the top of the finished floor.
the floor (see
D below)
A
all
pipe sleeves and
cove built monolithic with
should protect the membrane on the walls.
When
the fabric and cove are constructed against an existing plastered wall, the plaster is first removed to a point 3 inches above the top of the cove and then replaced to rest on the cove. Details on the various methods of waterproofing are as follows: Hard rubber tile may be A. Hard Rubber Tile Over Wood. laid down with waterproof cement on the waterproof fabric membrane.
—
If
much weight
tiles
is
to be placed
should be fairly thick,
-^-
to
on the i
floors,
at the corners.
B. Mastic Over
Wood
from trucks or tanks, the
inch, because the thin tiles will break
or Cement.
— !Mastic
sand, pea stone and fluxed asphalt mixture and
is
consists of a silica
obtainable from con-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
44
tractor supply houses.
It is
applied hot and,
when cool, varies in hardThe most waterproof
ness according to the ratio of sand to asphalt. floor
secured with a small proportion of sand.
is
not be used, however,
warm
weather.
if it is
Mastic
much
to receive
floors
which
will
traffic
Such a
should
floor
because
it
softens in
be walked on considerably
The surface will crack, The mastic should preferably be laid over a
should have more sand in proportion to asphalt.
however,
if it is
too hard.
waterproof fabric as described previously. All tanks should be supported on concrete blocks or curbing covered
over with a piece of sheet lead. sides until
it
The
laps over the mastic.
lead should be bent
No
down over
the
supports should rest directly on
the mastic floor or they will gradually sink through the mastic and cause leaks.
Wood
Asphalt-Concrete Flooring Over
C.
or Concrete.
â&#x20AC;&#x201D;
This consists of a mixture of cement, sand, emulsified asphalt, and pea stone.
It is laid
^ to
i
inch thick on top of the three-ply asphalt satu-
wood
rated waterproofing fabric placed over the
or concrete
and provides
a somewhat harder surface than the hot mastic type.
D. Waterproof Concrete Floor Finish for Concrete Floors.
â&#x20AC;&#x201D; Where new
waterproof conditions are desired for large laboratories or
buildings, a reinforced concrete finish, 23 inches thick, should be laid
on the waterproofed fabric membrane (see previous description, page 42).
Special brass floor drains with clamping rings should be used,
which
in addition to draining
off
water from the
any water which reaches the top
The
concrete finish that
soft.
The lower
and
is
layer
mixed as
is
is
constructed in
layers laid
the upper layer should be poured while the
lithic,
is,
floor finish will also drain
membrane. the form of two
of the
layer containing a welded steel fabric i
layer
first
is i
monois still
j inches thick
part cement and 3 parts standard concrete.
This
divided into sections of about 10 feet square, or smaller, and
the sections are separated from each other
by the use
of strips of elastite,*
or similar asphalt impregnated material, \ inch thick.
The
top layer
is
laid f inch thick
and
is
composed
of
i
part cement
sand (uniformly graded), with 3.5 gallons of water per bag of cement. This top layer is spread, tamped, screeded, and to 3.1 parts silica
leveled,
and then treated with a heavy power
float.
The
joints in the top
layer are ^ inch wide and are constructed directly over those in the
lower layer by the use of an edging tool for this purpose. *
Manufactured by Phillip-Carey
mason supply
dealers.
Co.,
Cincinnati,
Ohio,
After the
and obtainable from
APPARATUS AND METHODS OF USE completed
finish
has been cured for ten days, the ^-inch joints are care-
compound.
fully filled with a plastic
Where extremely heavy would prevent the
tomary
them
to
45
finish
loads on the lloor are encountered, which
from assuming
its
proper shrinkage,
extend these foundations through the floor
finish
directly on the waterproofing cloth (see drawing).
it is
cus-
and
rest
Lighter loads
or smaller tank foundations are placed directly on top of the finished floor.
Useful suggestions on waterproofing of floors are contained phlet
No.
92, published
writers, 85
John
Fig. ^4
St.,
Nov.
New
15,
in
Pam-
1937 by the National Board of Under-
York, N. Y.
â&#x20AC;&#x201D; Alberene stone
sink
and
ledge.
Note rubber mat
on ledge and trough at back.
Finish of Walls, Benches and Sinks. mixing or processing room should be painted
â&#x20AC;&#x201D; The walls light
of a chemical
gray or green, or white
with a semi-gloss enamel paint which can be washed easily. tory wall paint walls since
it
is
Kodak Panchromatic Green,
especially for
reflects chiefly the light transmitted
by a
A
satisfac-
darkroom
series 3
Wratten
temporary walls of composition board are used for a developing room, they should be protected behind the tanks by strips of safelight.
If
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
46
asphalt roofing paper.
Several sheets
solutions will run to the floor
may
and not drip
be overlapped so that the
off
on the wall.
Permanent Koda-
walls should be painted with a chemically resistant paint such as
coat paint.
25
â&#x20AC;&#x201D;
Vitrolite ledge
Sinks should be
The
water.
sink
on Alberene stone
sink.
An
of
ample proportions and piped with hot and cold be of wood covered with lead sheeting (burned
hard glazed stoneware (Fig.
excellent covering for all stone surfaces, particularly
vessels are to be used, strip of this should
any stone ledges
right.
may
joints) or preferably of Alberene stone or
24).
Drying cabinet shown on
is
if
glass
ordinary black corrugated rubber matting.
be cut to
or tables
fit
A
the bottom of the sink and the tops of
where solutions are
to
be mixed or handled.
This scheme minimizes greatly the possibility of breakage and provides a surface that rosion.
A
may
be washed quickly, and which
is
not subject to cor-
trough leading into the sink and placed next to the wall at
the back of the working ledge as
shown
in
Figure 24 represents a useful
adjunct to the sink.
Bench tops where of
wood such
or left bare.
dry chemicals are
as hard maple,
and covered
to
be used are best constructed
either with battleship linoleum
In either case they should be treated with several coats of
a hard floor wax, rubbed
down
well,
and polished.
Although hard rubber
sheets have been utilized only to a limited extent to date for coverings
APPARATUS AND METHODS OF USE
47
chemical bench tops, they appear to possess satisfactory character-
for
istics for
such purposes.
The
sheets should be cut to
and cemented with a waterproof cement surface.
If
in close
fit
the bench top
contact with the table
chemical solutions are apt to be spilled on the bench, Alber-
ene stone, plate glass, or lead covered wood are satisfactory construction materials.
An
opal plate glass
known
as Vitrolite has been used to a
KEV A -MO AC C
-CUPBOARD
on- DRAWER SS-SNAP SWITCH
FO-TLOOR C3RAIN W-^VATER OW-Ot5Tli,UED WATER
MW-HOT WATER OMW-OISTILLEO HOT WATER IG- ILI-UMPNATING GAS
CA- COMPRESSED *IR SD-STORAGE DRAWER rOR DRY CHEMtCAl_S SO-STOCK DEVELOPER 0WH-01STIl_l_ED l_-
Fig. 26
â&#x20AC;&#x201D; Diagram
of a chemical mixing
SOV.
WATER HEATE
LIGHT
room.
and drain boards. It is easy to clean and ismost photographic solutions. A darktype of construction is shown in Figure 25.
limited extent for sink ledges
resistant to chemical attack of
room equipped with
this
Storage space should be provided for etc., its
and each
vessel or piece of
all
buckets, crocks, stirring rods,
equipment should be cleaned and put
in
place after using.
A
diagram of a chemical mixing room
weighing bench
and
sink.
is
is
shown
in
Figure 26.
The
located centrally and conveniently to the mixing bench
Storage drawers for bulk chemicals, such as sulphite and car-
bonate, are arranged under the weighing bench and bottles of developing agents, bromide, and alum, are placed on a shelf over the bench. solutions of developers
and
fixing baths are kept in
Stock
stoneware crocks
This mixing room would be the room. and portrait photographer or for a moderate size photofinishing plant. Acids should be placed on a shelf behind the sink. See also Figure 83, page 201 for a design of a chemical storage
and tanks on the
left side of
satisfactory for a commercial
,
and mixing room
A
in a
typical mixing
weekly
is
shown
in
moderate
size
room capable
photographic plant.
of handling several
hundred gallons
Note wooden
trays for holding
Figure 80, page 197.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
48
weighed chemicals and types of stoneware and wooden tanks
A
solutions.
mixing room
in a photofinishing plant is
for storing
shown
in
Figure
8i,page 199.
Wooden
barrels are used for mixing vessels, arranged in two rows,
The upper row
one row being on a level above the other. mixing and each unit
for
is
equipped with a mechanical
lower row represents storage tanks.
provided
is
The
stirrer.
Behind the upper row of barrels
is
a platform equipped with a large sink, weighing table, and storage bins Solutions are fed from the storage tanks to the defor dry chemicals. veloping machines and printing rooms on the floor below.
laboratory
is
A
large mixing
Chapter IX, Figure 82, page 200. Note the the mixing and storage tanks, each of which
illustrated in
sink located centrally to
feeds to the developing machines on the floor below.
Portable mechani-
cal stirrers are used.
Every chemical mixing room and darkroom should be well
A
1
ventilated.
0-inch propellor fan will handle about 300 cubic feet of air per
minute, and
is
large
enough
taining 4,000 cubic feet of
and greater
to give air.
adequate ventilation
Proper
in a
room concomfort
air circulation insures
efficiency of the occupants of a
darkroom.
General Hints on Cleanliness and Handling of Solutions. â&#x20AC;&#x201D; Whenever possible, all chemicals should be stored and solutions mixed in a separate room from the developing, printing, or drying rooms. Chemicals keep best when stored in a cool, dry place and all containers should be closed when not in use. â&#x20AC;˘
Chemical dust
may
arise
cans, barrels, kegs, etc.,
and ing.
3.
spilling of
2.
from the following sources: spilling of
i.
leakage from
dry chemicals during handling,
wet chemicals which subsequently crystallize on dry-
Such dust frequently gets into the ventilating system when
it
in-
variably produces spots on films and prints (see Fig. 5).
The
floor of the
mixing room should have a drain so that
flooded occasionally to
may
wash away any
have accumulated (Fig. 23).
kept scrupulously clean.
it
may
particles of chemical dust
be
which
Scales and mixing vessels should be
^Mixing vessels, measuring dishes, and stirring
paddles should be washed thoroughly at once after use. In the developing and printing rooms
handle the solutions with care.
A
fixing
it
is
even more important to
bath splashed on the
floor will
dry up and the hypo crystals formed, after being pulverized by persons walking 23). prints.
in the
room,
will get into the air
Particles of dust
and cause spots (Fig.
5,
page
on the negatives produce white spots on the
If prints are dried
on cheesecloth stretchers, the cloth should
APPARATUS AND :\IETHODS OF USE
49
be removed and washed regularly to avoid trouble from stains.
De-
velopers and fixing baths should be
skimmed each morning before use (see paragraph on page 40). The developing and printing room floors should be washed at least once a week by flooding with a hose if a drain is present or, if not, by mopping frequently. Deep tanks of wood or stoneware should be sterilized at intervals to kill
fungus growths as explained on page 265.
All bottles, crocks, jars, etc.,
which are used as storage containers
solutions should be labelled carefully. label
A
which
is
It
is
good practice
to lacquer
for
any
intended as a permanent legend of the vessel's contents.
satisfactory lacquer can be prepared
by dissolving
amyl
film scrap in
Zl
MAPLE TOP BENCH
STONEWARE. SINK
THICK
Ij^"
KEY A — 110 AC SS^-SNTAP SWITCH
SL-SArC U\GMT DR- DRAWER
A
C-CUPBOARO
a
|m
(t)l.
I
FS-FOOT SWITCH
4'!-
OH
W — WATER
I
I
HW— HOT WATER OR
Q-
DC-DRYING CUPBOARD I- ILLUMINATOR
FS
r^rt LINOLEUM toVEREDJ BENCH
1
R-RE.5ISTANCE: U-LlGiHT
SiL ^
Fig. 27
— Plan
of a small darkroom.
acetate until the solution has the consistency of molasses. solution should be covered
Layout of Darkroom.
when not
— A plan
This lacquer
in use.
darkroom suitable for is shown in Figure This design was adopted by the Photographic Chemistry Departof a typical
a professional photographer or an advanced amateur 27,
ment of
the
Kodak Research
Laboratories after
many
years of experience
and solutions are handled on one side of the room and printing on the other side. Figure 25 shows the view of one side of a room built according to the plan. The Vitrolite ledge represents an alternative material to the wood construction shown in the plan. with various plans.
Note the
All chemicals
The
location of safelights and the illuminator.
turned on with a foot switch.
which blows
air
The drying
downward through a
cabinet
cloth
heating by means of electric coils are possible.
is
filter.
A
latter
be
Several degrees of
vertical
movable
plate has been installed inside in order that the size of the drying
may
may
equipped with a fan
be varied, thereby controlling the velocity of the
baffle
chamber
air current.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
50
Figure 28 shows a view of the bench and cabinets on the opposite side
An exposure box is located at the end of the bench. This equipped with several diaphragms and a rheostat for controlling the
of the room. is
light.
It is
exposures
very convenient, and often important, to be able to duplicate
when
For
printing.
this purpose, the rheostat is included in
Darkroom exposure box, with the
lamp
circuit,
and a voltmeter
is
rheostat and voltmeter.
attached across the lamp terminals.
Fluctuations in line voltage result in serious changes in exposure
from
no
Voltages for printing should be a
The
;
a drop
100 volts will almost cut the intensity of the lamp in half.
to
little
below normal, say, 105 volts. darkroom is an important
installation of suitable safelights in a
Overhead safelights may be either of the direct or indirect style. Bench or sink safelights may be fastened permanently to the wall or arranged to be moved. The degree of safety of a safelight to a specified sensitive material may be determined by exposing the material for vari-
matter.
ous times at a
by covering a
known
distance from the safelight.
strip of film
This
is
accomplished
with a piece of cardboard and moving the card
along an inch or so after each exposure until the material has received several exposures.
The
material should then be developed for a standard
time and temperature, whereupon a record will be obtained from which the time of exposure that
is
safe
may
be determined.
Every darkroom should be well ventilated Refrigerating units of small size are cost,
and
it
now
(see details on
page 48).
available at a reasonable
should be possible to utilize such units for controlling the
temperature of the
air in
darkrooms.
:
CHAPTER
IV
MATERIALS FOR CONSTRUCTION OF PHOTOGRAPHIC PROCESSING APPARATUS* When
selecting a material for the construction of
any particular piece
of photographic processing apparatus, several factors should be con-
namely:
sidered, 1.
The
which
it
resistivity of the material to the
come
will
fairly satisfactory for
most corrosive liquid with
For example, a galvanized tank, while
in contact.
washing purposes,
is
very rapidly corroded and
therefore unsuitable for use with fixing baths. 2.
The
solution.
on the photographic properties of the
effect of the material
For instance, a developer solution
visibly unchanged, but on testing,
it
may
in
a brass tank
may
appear
fog emulsions badly, due to
the copper salts dissolved from the brass. 3.
The time during which
material.
If a
developer
ultimately soften and peel 4. 5.
for
The The
the solution will be in contact with the
stored in a japanned tank, the japan will
off.
cost of the material.
adaptability of the material for construction purposes.
example,
and the
is
is
entirely unsuitable for large tanks because of
difficulty of
Glass,
its fragility,
annealing such tanks.
There are three general classes of materials suitable
for the construc-
tion of photographic apparatus intended for use as containers for or to
be immersed
in
photographic solutions, namely:
coated metals, and non-metallic materials.
These
metallic materials,
may
be subclassified
as follows
A. Metallic materials: Unplated and plated metals; alloys. B. Coated metals:
Enameled
steel,
asphalt-coated metals and lac-
quered metals. C. Non-metallic
materials:
Glass,
impregnated fibrous materials,
wood, paraffined wood, porcelain and glazed earthenware, rubber, rubber composition, nitro-cellulose materials, slate and Alberene stone.
Metallic Materials. will resist corrosion *
â&#x20AC;&#x201D; No metal or
completely in
The experimental work reported
thors in conjunction with H. A. Hartt,
J.
in
all
alloy has yet been found which
photographic solutions, and
this chapter
it
was carried out by the au-
F. Ross, and L. E. Muehler.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
52
is
therefore necessary to restrict their use to specific purposes.
]Metanic
materials possess certain desirable properties, however, such as duc-
and general workability, that render them parthe manufacture of several types of photographic apparatus such as small tanks, racks, film hangers, clips and non-fragility
tility,
suitable
ticularly
for
reels.
In considering the suitability of a particular metal for construction purposes,
it is
very important to
know whether
a single metal or of two or more metals.
the article will be built of
In the former case only the
corrosive effect of the solution itself need be considered, whereas in
the latter case an electrical current flows between the two different metals, and
effect
its
must be considered
in
addition to the chemical
action.
In testing the resistivity of various metallic materials to chemical action,
it
2.
necessary to observe the effects obtained under two sets of
is
conditions:
i.
those in which only a single metal or alloy
those in which two or
more metals or
is
involved and
alloys are in contact with each
other and also with the photographic solutions.
The
Resistivity oÂŁ Single Metals in Photographic Solutions.
â&#x20AC;&#x201D; An extended
has been carried out to determine the
series of tests
tivity of a large
number
of metals
The experimental
solutions.
details of the
materials given in the following
to
are recorded in a paper
list,
resis-
common photographic tests made on most of the
and alloys
by the
authors.^
Metals: Aluminum, iron, lead nickel,
tin, zinc.
Plated Metals: Galvanized iron, tinned iron, lead-coated iron, chro-
mium,
and cadmium-plated brass. Xo. 136 (aluminum-magnesium-copper), Corronil
silver
Alloys: (nickel
Aterite
alloy).
G
Illium
Duralumin
(aluminum-magnesium-copper), Duriron,
(chromium-iron-nickel),
Monel, Niaco
(nickel alloy),
Inconel
(chromium-iron-nickel),
Xichrome (nickel-chromium),
(copper-zinc-nickel-iron), Nicolene
nickel silver
(nickel-copper), phosphor bronze
(copper-tin-phosphorus), solder (both high and low tin content), Rezistal
1
J. I.
steel
" Tlie
(chromium
steel),
Resistivity of Various Materials
Crabtree and G. E. Matthews.
Eng. Chcm.
stainless
steel*
(iS^c
chromium-S^c
Toward Photographic
Solutions " by
Brit. J. Phot. 70, 366, 3S5 (1923)
;
also Iiid.
&
666 (1923). * Stainless steels of 18â&#x20AC;&#x201D;8 composition and containing small percentages of otlier metals are supplied by several manufacturers in the United State under various trade names, such as Allegheny metal, Carpalloy 8, Enduro KA-2, Rezistal KA-2, USS 1
8-8, etc.
15,
MATERIALS FOR CONSTRUCTION
with varying carbon titanium, zirconium, selenium content),
nickel
type metal (lead-tin-antimony),
USS 18-8 Mo
molybdenum) and various stainless steels. Method of Testing Metal Samples. is contemplated, tests should be made of the
—
quantity is
53
is
A
fabricated.
essentially the
(chromium-nickel-iron-
a large scale installation
If
metallic material before
simple but effective test
same as used by the authors
any
the following which
is
studying the materials
in
listed above.
The
strip of the
mouth
a wide
page 286) fixing
A
.
bath
metal or alloy to be tested should be half immersed
bottle containing the developer
sample should also be placed
tests
should be
made both
F-5, Appendix, page 310) and in the
The
latter test is desirable to
to plate out
from a used
fixing bath.
with a clean, new, cork stopper. the severity of the test it
in the acid fixing bath.
in fresh acid fixing
same bath when
determine
there
if
The
in
(Formula D-19 Appendix,
bottle
is
bath
(
The
Formula
partially exhausted.
a tendency for silver
mouth should be
closed
Although a closed container increases
somewhat because
it
gives a stronger vapor phase,
has been found an effective method of measuring the resistivity of two
more materials (such as different samples of 18-8 stainless steel) which very nearly the same resistance to vapor attack. Duplicate tests should be made at room temperatures, 65° to yo'F. (18- to 2i°C.) and at no F. (43°C.) and should be continued for at least i month and or
offer
3 days respectively.
The
results at high temperatures should not be
regarded as conclusive but merely as an indication of the resistivity of the material.
Observations should be made frequently of the appearance of the
samples and the developer should be tested
for its fogging propensity
The
condition
of the metal samples should be noted both above and below the
air line of
by
developing therein a strip of film for a
the solution.
The
normal time.
results of these tests give a fairly reliable indication
of the effective resistivity of the metal or alloy.
The Resistivity of Two or More Metals in When two Towards Photographic Solutions.
—
placed in contact and immersed in a solution, an
formed which causes more or metals. metals,
This electrical action
when some
less
may
Metallic Contact different metals are
electrolytic battery
is
rapid disintegration of one of the
occur
in several
ways; with plated
of the plating wears off; with soldered metals, be-
tween the solder and the metal; and with of the various metals which
compose the
alloys,
between the tiny crystals
alloy.
In making metal containers for photographic solutions,
it
is
often
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
54
necessary to use a second metal or alloy in the form of solder, to render the joints or seams free from leaks. lines for transporting solutions,
or fittings of the
trouble which
same material
may
it is
Also, in the construction of pipe
frequently not possible to use faucets
as the pipe line.
A specific example of
from the metallic contact
arise
in a solution
is
the
as
follows:
Fig. 29
â&#x20AC;&#x201D; Spotted
type of corrosion of copper-nickel
alloy after prolonged
immersion
in acid fixing bath.
In the course of a series of tests on metal tanks of a copper-nickel alloy, soldered if
on the inside with a lead-tin solder,
it
was observed that
a developing solution remained in the tank for a short time the de-
veloper gave very bad fog.
The
solder with which the seams of the tank
were soldered appeared to be etched slightly and the original luster of the metal
The
had disappeared and was replaced by a dark, grainy deposit. was unaffected as far as could be detected from its
alloy itself
physical appearance.
A
series of tests definitely
proved that
this ex-
was a result of the tin constituent of the solder passing into solution, due to the flow of an electric current through the solder, the When the joints were soldered on the outsolution and the alloy. side, no developer fog was produced and corrosion was considerably
cessive fog
less.
-
FOR CONSTRUCTION
:\IATERIALS
55
Corrosion was also observed due to the same cause when a tank
from
and soldered on the
this alloy
inside
was used as a container
made an
for
acid fixing bath, except that the alloy was corroded instead of the solder
The most
(Fig. 29).
above the air-liquid
shown
rapid corrosion of any metal tank usually occurs
An advanced
line.
in Figure 30.^,
case of air-line corrosion
is
which represents a portion of a rack made from
nickel-copper alloy which had been suspended in acid fixing bath for several months. .An extended study of this aspect of corrosion has been results are given completely in
made and
the
two papers.
Value of Various Metallic Materials.
â&#x20AC;&#x201D; Only
the practical ap-
plication of the results of tests on the various metals will be considered in this article; the original
papers should be consulted for more detailed
information.
Metals.
â&#x20AC;&#x201D; Lead
and nickel were the only metals tested which ap-
peared to be of any especial importance for use with photographic solualthough iron
tions,
of value for particular purposes.
is
and wrought iron tanks or piping can be used developing solutions although lead veloper.
Iron
is
attacked more or
form oxides and hydroxides filter
is
most
attacked by strongly alkaline de-
less
by most developers and tends
in the solution so that
Tanks
out such particles before use.
Lead, nickel
satisfactorily for
it
is
to
important to
lined with lead or nickel can
be used for fixing solutions but they are slowly attacked, become coated with silver and must eventually be replaced.
Plated Metals.
â&#x20AC;&#x201D; Galvanized
facture of washing tanks although of apparatus.
Vessels
made
iron has long been used for the it is
manu-
not entirely suitable for this type
of this material
must not be used, however,
mixing developers which contain sodium bisulphite, because the bisulphite attacks the zinc coating, forming sodium hydrosulphite which for
causes fog.^
Xickel-plated brass
is
are used intermittently.
satisfactory for small developing tanks which
Metals plated with
from an exhausted fixing bath or by
by deposition more resistant to
silver, either
electroplating, are
~ " The Effect of Electrolysis on the Rate of Corrosion of Metals in Photographic Eng. Chcm. Solutions " by J. I. Crabtree, H. .\. Hartt, and G. E. Matthews. Ind.
&
16, 13 (1924)
and
" Corrosion of
Crabtree and G. E. Matthews.
Monel Metal in Photographic Solutions" by Ind. & Chcm. i6, 671 (1924).
J.
1.
Contact with 3 " The Fogging Properties of Developing Solutions Stored in Various Metals and Alloys " by J. F. Ross and J. I. Crabtree. Aiucr. Phot. 23. 254 (1929).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
56
developing solutions according to the homogeneity of the silver coating,
but their resistance towards fixing baths that of the unplated metals.
do not satisfactorily
resist
is
only slightly greater than
Aluminum- and cadmium-coated metals
photographic solutions.
metals would probably be satisfactory
if
Chromium-plated
were possible
it
to secure a
continuous nonporous coating over the base metal, but no such coatings are available to date.
washing tanks
if
Lead-coated iron can be used for developing and
the iron base-metal
is
not exposed, but
is
not very
satisfactory.
Plated metals and alloys are always open to the objection that as soon as
some
of the plating wears
electrolytic corrosion sets in,
Alloys.
â&#x20AC;&#x201D; Of
off,
exposing the other metal underneath,
and disintegration takes place rapidly.
numerous known alloys, Monel metal and 18-8 which have been adopted to any great photographic use. ]Monel metal is attacked and coated with the
stainless steel are the only ones
extent for silver
when used
for
storing exhausted fixing solutions.
Inconel, a
nickel-chromium alloy, appears somewhat more promising than Monel because tures.
does not plate out silver except very slowly at high tempera-
it
A
chromium-iron-nickel alloy
known
as Illium
B
also appears
promising.
Most samples
of 18-8 stainless steels are quite resistant to both de-
veloping and fixing solutions but some show a tendency to form corrosion pits above the air-solution line with acid fixing baths (Fig. 30B).
A
stabilized
form of 18-8
of titanium represents
stainless steel containing a small percentage
an improvement over the older 18-8
pecially for tank construction
provement
of the
18-8
where welds are required.
is
4%)
of
steels, es-
further im-
steels relative to their corrosion resistance to
acid fixing baths has been realized (2 to
A
molybdenum.
somewhat higher (25
to
The
by adding
to
them a small percentage
relative cost of such steels, however,
50%)
than regular 18-8 stainless
steel.
Another form that has high corrosion resistance contains a greater chro-
mium and
nickel content
advantage that
The
it
â&#x20AC;&#x201D;
12% nickel) and has the more than the regular 18-8 steel.
(24% chromium
costs only slightly
selection of a stainless steel for a construction material in connection
with photographic equipment depends, therefore, upon the type of use the equipment will receive and the fabrication requirements necessary
when forming the equipment. The welding of stainless rosion
may
chapter.
steels
must be done carefully or
occur at the welded joints.
cor-
See discussion at end of this
MATERIALS FOR CONSTRUCTION
57
An idea of the variation in composition of stainless steels of the 18-8 may be gained from an examination of the following table compiled
type
by
Smith.''
TABLE
I
Percentage Composition Ranges of Various Types of
Enduro Stainless Steel Type
PHOTOGRAPHIC CHEAHCALS AND SOLUTIONS
58
^
r
Fig. 30A line
—
Corrosion above air on section of metal developer
v/.
\^^'
v.*^
M
l-ii:.
iS-S
,,oi;
corro-idii
Pittfii
stainless
steel
above
ot
air-
liquid level after several weeks' ex-
rack.
posure to the vapors of an acid bath at 90°F. (32 °C.).
fixing
Coated Metals.
— The
resistivity
of
metals which readily cor-
rode can be greatly increased by coating them with a more resistant
metal or non-metallic substance.
The
properties and applications of a
few such coated metals are described below.
—
Enameled trays
Steel. Enameled steel is extensively used for small and tanks, and has proven fairly satisfactory. When the under-
coating of steel
is
vitreous enamel,
laid bare
it
by the chipping away
of the relatively brittle
corrodes very rapidly, and the vessel
is
rendered use-
Smooth, hard enamel coatings are resistant to weak acids used in photographic practice, but with developers and alkaline solutions the surface becomes etched, making it difficult to clean. Dye solutions
less.
permanently discolor such roughened surfaces of enamel. Glass Enameled Steel. Equipment having very satisfactory
—
re-
MATERIALS FOR CONSTRUCTION sistance to
velopers)
is
most photographic solutions (except strongly alkaline deavailable in the form of mixing tanks and agitators (5-gallon
upwards) suitable
made by
59
for
motion picture laboratory
use.
Such equipment
is
fusing resistive silicate enamels onto substantial steel shells at a
temperature of 980 ""C. (i8oo°F.).
Advantages claimed are less weight and bulk and greater heat conductivity than with cast metals or earthenware.
The
glass
enamel on the
than ordinary enamel since
steel
is
much more
resistant to breakage
Repairs
actually fused onto the metal.
it is
the event of breakage, however, are difficult to
make without
in
returning
the entire unit to the factory.
Lacquered and Painted Metals.
â&#x20AC;&#x201D;A
satisfactory photographic
lacquer consists of asphalt paint or a mixture of asphalt paint with rub-
ber cement, the latter serving to overcome the slight brittleness of the
Baked japan
asphalt coating.
is
very satisfactory, but none of these
materials will resist developing solutions containing a high percentage of alkali.
Freshly applied asphalt paint will often produce a scum on the
developer.
Kodacoat paint represents a satisfactory material metallic surface from corrosion
when subjected
graphic solutions or their vapors.
A
secure
maximum
tained
by using oxygenated
protection.
for protecting
a
intermittently to photo-
Several coats should be applied to
thicker protective coating
asphalt.
may
be ob-
This material requires melting
and must be applied hot for best results. Halogenated rubber paints such as Tornesit
*
and some other rubber
paints such as Pliolite f are also fairly resistant to the action of developers and fixing baths. Some types of bakelite lacquers, such as Larcoloid, t are quite resistant to the action of corrosive vapors.
As a general
rule,
it is
best to use paints
and lacquers on surfaces that
only receive intermittent exposure to solutions or their vapors because it is
it
very
difficult to treat
a surface with a paint or lacquer so as to render
completely impervious to the penetration of a liquid. It is
important to protect the exterior as well as the interior surfaces of
tanks to prevent corrosion of the base metal.
Consideration should be
given to the possibility of abrasion and pressure to which the exterior
may
A
heavy tank resting on a beam, for example, would soon press through any protective coating and allow surface
*
May
be subjected.
large
Products Co., Newark, N. Y.
Staten Island, N. Y.
& Lambert
t
Pratt
:
Larkin
Co., Buffalo,
Co., Buffalo,
N. Y.
N. Y.
Also Perry-Austen Manufacturing Co.,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
60
corrosion of the base metal to occur.
All surfaces
which are
likely to
be abraded or worn away should be recoated at frequent intervals.
Laminated Metals. als
— About 1931, several types ^
of laminated met-
were introduced, which consisted of thin sheets of a corrosion-resistant
metal on a thicker metal base such as iron. steel, for
terials
Lead, nickel, and stainless
example, have been laminated onto
may
find
some uses
for
Such ma-
steel or iron.
photographic work but are open to the
objection that once the thin upper coating
is
broken through, the base
metal would probably corrode rapidly.
Non-Metallic Materials. in
— Several
satisfactory materials for use
handling photographic solutions on a large scale are to be found
in
the non-metallic group.
Glass.
— Glass
apparatus well annealed, free from
the corners of small trays and tanks rounded is
one of the most resistant materials available.
An
however, glass
is
opal plate glass,
and with
Owing
to its
not suitable for large trays and tanks.
known
as Vitrolite, represents a satisfactory
material for bench or table tops where chemicals are to be used. fairly resistant to it
may
most photographic solutions except strong
be kept clean easily.
Like other glasses,
and, therefore, care must be used that
it is
possibility of breakage of glassware
if
It is
alkalis
this material
and
brittle
is
not struck with a metal object.
A disadvantage common with stoneware or Alberene is the ever may
and
For the storage of
strong alkalis, special, resistant glass should be used. fragility,
ribs,
quite satisfactory
off, is
present
dropped on such surfaces.
This
be avoided by using a sheet of rubber matting on the surface where
glassware
is
to
be placed.
Impregnated Fibrous Materials.
— Trays or tanks prepared from
paper or other fibrous materials impregnated with varnish or lacquer develop cracks with use, thus permitting access of the solutions to the
under layers.
Such trays and tanks are entirely unsatisfactory
for use
with solutions containing strong alkalis, or with fixing baths, because these solutions disintegrate the fibrous materials through crystallization, as explained later under " Porcelain fiber trays carefully
tory for intermittent use
Containers
and Glazed Earthenware."
Small
impregnated with a high melting wax are satisfacif
carefully handled.
made from most laminated
phenolic condensation products
can be used with photographic solutions, with the exception of strong
Some samples of these materials have been found to and warp out of shape when used with strongly alkaline solutions.
oxidizing solutions. swell
INIATERIALS
Wood.
â&#x20AC;&#x201D; Wood
ing purposes,
and
FOR CONSTRUCTION
61
and wash-
fairly satisfactory for developing, fixing
is
cheaper than any other available material.
is
It
has
the disadvantage that, unless strongly braced, the tanks have a tendency
warp out
This tendency is at a minimum with round tanks, which should be well braced with iron rings that are tightened up as to
of shape.
I
Fig. 31
â&#x20AC;&#x201D; Splintering
of
wood
in a
hypo storage tank caused by wood.
crystallization
of the salt in the pores of the
much
as possible after the tank has been soaked thoroughly
with water and allowing If
it
by
filling
stand for several days.
used as containers for fixing baths, the tanks should preferably be
constructed of paraffined crystallize
on the
the tank
filled
many
as
wood
as described below.
sides, will penetrate the
splinter or crack as
In
to
shown
much
localities
in
Figure 31.
wood
in
Hypo,
if
allowed to
time and cause
it
to
This can be avoided by keeping
as possible.
fungus growths accumulate on the outside of the
washing tanks which must be removed frequently, while the inside of wash tanks often become coated with a layer of slime which necessitates frequent cleaning (see Chapter XII, page 265).
Wooden
containers
become permanently discolored if they are used for dye solutions. The most satisfactory varieties of wood for the construction of tanks are cypress, spruce, redwood, maple and teak. also
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
62
Paraffined
Wood.
— Although
woods such
certain
as cypress
and
teak are frequently used for the construction of containers for photo-
graphic solutions, paraffin-impregnated It also possesses the additional
wood
is
much more
advantage that
it
cumulate slimy layers as rapidly as unwaxed wood. advantage of paraffined wood
is
that
it is
satisfactory.
does not tend to ac-
The
chief dis-
too heavy for the construction
equipment which is to be handled manually. It is also quite and breaks easily if dropped. Methods of impregnating wood with paraffin have been investigated by Eberlin and Burgess, who found that the best results were obtained with cypress and spruce by soaking in of large
brittle
•"*
water for twelve hours, and then immersing
two hours at around
The soaking water
2
serves to swell the
in the pores
is
molten paraffin wax
in
for
50°F. (i20°C.).
wood and
in the
hot paraffin bath the
The wood should be wiped
replaced by paraffin.
thoroughly with a cloth on removing from the paraffin bath so as to
remove the excess wax.
made by grooving joint,
Watertight joints with paraffined wood are best
the pieces of
wood
to
be joined together, as for a T-
and inserting tightly a small piece
groove.
When
of unparaffined
caulks the seam.
Porcelain and Glazed Earthenware. ware, and
tile
wood
in the
placed in water the untreated strip swells and completely
— Porcelain, glazed
biscuit
material are usually unsatisfactory because the glaze in-
variably cracks, causing minute fissures into which the solution penetrates
and
The
crystallizes.
crystals then
grow and cause the biscuit Tanks of
ware to disintegrate, incidentally causing the glaze to chip.
high grade, dark brown earthenware, glazed on both sides, are especially
recommended
for storing ordinary developing
and hypo
solutions, but
should not be used with strong alkalis.
During 1933 a new form of hard glazed stoneware was introduced which was claimed to be free of all internal fissures, lighter and thinner than the older types of stoneware, but equally as strong and as chemically resistant.®
Rubber, Rubber Composition, Nitrocellulose and Asphaltum Materials.
— Pure hard
rubber will withstand practically
graphic solutions at normal temperatures.
5
"
Impregnating
Wood
with Paraffin " by L.
W.
all
photo-
Hard rubber thermoplastics Eberlin and A. M. Burgess,
Iiid.
& Eng. 6
40,
Chcm. 19, 87 (1927), Revised 1928. Ind. & Eng. Chcm. 25, Adv. Sec. 35 (Sept. 1933)
270 (May 1933)-
;
also
Chcm.
&
Met. Eng.
MATERIALS FOR CONSTRUCTION
63
(said to be sulphur free) were introduced in 1933/ These appear promising for the construction of small trays and tanks for photographic use.
For certain types of factory because
FiG. 32A
â&#x20AC;&#x201D; Hard
it is
hard rubber piping is very satisand may be threaded easily. Its chief disad-
installations,
light
rubber-lined steel tank showing; seam con-ti uction.
American Hard Rubber Co.,
vantage
is
its
brittleness.
New
Courtesv
York. N. Y.
Iron pipe lined with hard rubber, which
is
firmly cemented in the pipe, represents a very satisfactory type of piping
photographic solutions.
for
hard rubber pipe that
it
It possesses the
advantages over ordinary
does not require support every few feet and
is
not subject to breakage by impact.
Some
so-called hard rubber tanks are
made from a mixture
or rubber composition with an excess of mineral
somewhat
brittle,
warp under
filler.
of asphalt
Such tanks are
and when used as containers for same manner as porous earthenware.
heat,
salt solutions disintegrate in the
Smooth surfaces reduce the tendency
to etching since less strain
is
ex-
erted on the walls during the crystallization process.
Black hard rubber sheet or fabric-backed rubber sheet
may
be used
bench tops or sink ledges where photographic chemicals are to be handled. The sheets should be cemented to a wood table top with for
waterproof cement such as Plastikon cement, supplied by the B. F.
Goodrich Co., Akron, Ohio.
Rubber cements are now "
lud.
&
Eug. Chcm.
26,
available which produce a highly tenacious
123-129 (Feb. 1934)-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
64
bond between hard rubber and metal, wood, porcelain, and other surfaces, and which have fairly high resistance to corrosive attack of acids and
alkalis.
According to Fritz and Hoover
pounded
solutions of salts
Fig. 32B
immersion
to resist actual
and
Above 150'F. (65°C.) the
alkalis.
and
effects of
â&#x20AC;&#x201D; Hard rubber-lined
steel tank showing corner and edge construction. Courtesy American Hard Rubber Co., New York, X. Y.
oxidation, diffusion,
is
vulcanized rubber can be com-
for long periods in organic acids
and absorption become aggravated.
construction of soft and hard rubber it
-
is
described
by
A
three-ply
these authors which
claimed represents an improved type of material for coating the
surface of metal tanks.
The
and corner construction of two hard rubber-lined steel tanks 32A and Fig. 32B. Note method of filling corner with a triangular piece of rubber in Fig. 32 B, to produce a surface, which may is
joint
shown
in Fig.
be cleaned more easily.
These tanks are lined with a two-ply rubber
coating consisting of hard rubber bonded to soft rubber which, in turn, is
bonded
to the steel.
If the
made with overlapped seams
tanks are large enough,
as
all joints
can be
shown in Figure 3 2 A. With deep narmethod of assembly is used. They are
row tanks, however, a different usually formed as two shells with right angle bends at the edges where the joint is to be made. A soft rubber gasket is then set between the faces of the two shell edges as shown in Figure 32C and, when these faces 8
"
The Chemical Resistance
Fritz and J. R. Hoover. terials,
March
9,
of RulDljer as an Engineering Material " by H. E.
Reprint of Symposium on Rubber, Amer. Soc. Testing
1932, p. 79.
Ma-
MATERIALS FOR COXSTRUCTIOX are
drawn together with
occurs on the steel,
no
it is
bolts, the
tank
is
formed.
65
Whenever a corner
important that the weld be smoothed out so that
air pocket is formed when it is covered with rubber. Tanks may be constructed economically from steel
a thin
(^ inch) soft black rubber sheet
rubber
is
is
sheets on which
cemented intimately.
The
permitted to extend over the edges of the steel and " squeezed
joints " are
made
to
form the bottom and walls of the tank by bolting
Z
^^
^///////
t.
STEEL PLATE "^,
d \
SOFT RUBBER CASKET Fig. 32c
â&#x20AC;&#x201D;
Construction detail of joint in a rubber lined steel tank. Courtesy American Hard Rubber Co., New York, N. Y.
two opposite sides together and allowing the rubber sheets at the joint.
When
the bolts are
to protrude
drawn up, the two rubber
sheets are
pressed together and form solution-tight joints.
Rubber sheeting and rubberized cloth are often used for coating the wooden trays and troughs, and are very satisfactory provided
inside of
the surface
is
not subjected to
Cheap rubber sheeting
much
abrasion during use.
or tubing often contains an excess of free sul-
phur which reacts with photographic developers and causes chemical fog.^ Pure gum rubber materials are quite satisfactory. For handling long lengths of wide film (Cirkut film), a rubberized tray
is
e.xcellent.
Since solutions used in a tray or trough are usually in contact with the
rubber for only a relatively short time, more corrosive solutions can be used than 9
"
in the case of a rubber-lined tank.
Chemical Fog
"
by
J. I.
Crabtree.
Amcr. Ann. Phot.
33, 20 (1919)-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
66
A
flocculent precipitate
is
produced when some grades of soft rubber
are placed in a developer solution for several days. will
This precipitate
The use
tend to settle on film and produce scum markings.
of rub-
ber sheeting giving such precipitates should be avoided.
Rubber buckets such as the type made from Flexite) represent useful
FiG. 32D
dling of solutions
32D (which
is
containers for the intermittent han-
â&#x20AC;&#x201D; Rubber
bucket. Courtesy Goodrich Co., Akron, Ohio.
and are
tographic solutions.
illustrated in Figure
most pho-
resistant to the corrosive attack of
The handle should
preferably be
made
of stainless
steel.
Kodacoat paint
as mentioned on page 59 represents a satisfactory
material for coating wood, stone, and metal to protect them against the intermittent attack of acid or alkaline solutions.
A
may be applied with maximum protection.
It
a brush and several coats should be used to give
tarry material called oxygenated asphalt supplied
by the Stand-
ard Oil Co., has been found to be a satisfactory protective coating for use with
all
kinds of photographic solutions.
This material
while hot, as a thick coating over the metal or surface
is
is
if
is
applied,
a smooth
desired the coating can be smoothed out by the use of a blow
torch (Fig. 33).
weather
wood and
will
This coating
adhere to metal
is
normally somewhat tacky and
articles.
Therefore,
if
in
hot
a photofinishing tank
coated with this material, the upper edges of the tank should be pro-
vided with wooden supports for the metal rods carrying the hangers.
MATERIALS FOR CONSTRUCTION
67
Nitrocellulose lacquer (E. K. Lacquer
wooden
articles
No. 5119) is useful for coating such as racks for handling motion picture film, although
several coatings are usually necessary. nitrocellulose sheeting
A
aqueous solution."*
Fig. 33
â&#x20AC;&#x201D; Showing use
such material terial is
is
blow torch
to
Figure 34.
in
smooth out asphalt coating
Wooden
have also proved satisfactory.
that
it is
made from
small film developing reel and tank
of
shown
Small apparatus constructed of
satisfactory for use with almost every type of
is
very inflammable.
Slate and Alberene Stone.
A
in a tank.
tanks lined with this ma-
disadvantage of such sheeting
â&#x20AC;&#x201D; These materials are very
suitable for
For
constructing large tanks for containing developing solutions.
fix-
ing solutions, Alberene stone (a gray, finely crystalline variety of soapstone) splits
is
quite satisfactory, but slate
is
not recommended as
it
along planes of cleavage as a result of crystallization.
varieties of soapstone are not resistant to fixing baths,^^
disintegrate where the
sodium thiosulphate
often
Some
and tend
to
crystallizes out.
Develop-
above the
air-line of
ers also attack these varieties of soapstone chiefly
the solution and produce disintegration as indicated in Figure 35. 10 " Plastic Cellulose in Scientific
man,
Research " by K. Hickman and D. E. Hynd-
Frank. Inst. 207, 231 (1929). 11 " The Action of Hypo Solution on Stone Tanks " by D. Research, Xat. Bur. Standards 16, 161-164 (Feb. 1936). /.
'
'
W.
Kessler.
/.
of
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
68
A
satisfactory
cement
for joining large pieces of soapstone, as in con-
structing a tank, can be prepared from
i
part whiting,
2
parts litharge,
thoroughly mixed and made into a putty with boiled linseed ture of litharge and glycerine
is
recommended
for
oil.
A
mix-
cementing small
fit-
tings into the tanks.
Fig. 34
in
— Small
reel
and tank made from sheet
film base.
Oxygenated asphalt can sometimes be used effectively to repair cracks a soapstone sink. It has the advantage that it expands and contracts
slightly with changes in temperature.
Practical Suggestions Materials suitable for constructing various types of photographic apparatus are as follows:
Small Apparatus. (18-8)
is
—
(Clips,
film
hangers, etc.)
Stainless
one of the most satisfactory materials known, but
ommended
for use in toning solutions.
enced with film hangers made of
this
No
trouble
is
steel
not rec-
usually experi-
metal and having welded
cause such hangers receive only intermittent use.
is
joints, be-
Note: Stainless
steels
(18-8) containing small percentages of molybdenum (2-4%) are more resistant to corrosion than ordinary 18-8 stainless steel. Inconel and, to a less extent, nickel and Monel, have properties somewhat similar to those of 18-8 stainless steel.
Trays, Dishes and Small Tanks.
— Since
these containers are
generally used for a variety of purposes, they should be resistant to most
photographic solutions.
Suitable materials are glass, enameled steel,
hard rubber, teak wood or spruce impregnated with paraffin wax, wood, or metal coated with sheet rubber or rubberized cloth,
wood coated with
â&#x20AC;&#x201D;
MATERIALS FOR CONSTRUCTION
69
oxygenated asphalt, and well-glazed porcelain or stoneware. Plioform,* a rubber product that does not contain sulphur, represents a promising material for the manufacture of small trays and tanks. It is much more resilient than most types of hard rubber. Small amateur trays made of heavy cardboard impregnated with a high melting wax are fairly satis-
Disintegration of soapstonc tank above air-solution
FiG. 35
factory provided they do not receive rough treatment.
Monel, 18-8 stainless
steel (see note,
washing or developing, and
for
line.
Small tanks of
above), or Inconel are satisfactory
for fixing purposes
when
the tanks are
to be used intermittently.
Deep Tanks. finishing.)
â&#x20AC;&#x201D; (For
motion picture work and commercial photo-
Alberene stone, well-glazed stoneware and wood (cypress)
are suitable for developing and fixing baths.
Lead-lined wooden tanks
are fairly satisfactory for developing solutions provided the joints are
lead burned and not soldered.
Glass enameled steel tanks also are sat-
isfactory for use with developing solutions.
Iron tanks lined with hard rubber sheeting or, preferably, with soft rubber sheeting (sulphur-free) represent a useful type of container that *
Goodyear Tire & Rubber
Co.,
Akron, Ohio.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
70
is
resistant to corrosive attack (see Fig.
may
pansion joints
202) and
.
Overlapping ex-
be used with the hard rubber (see Fig. 84, page with soft rubber. The latter are produced
" squeeze joints "
by squeezing together
the rubber that protrudes over the edge of the
steel at the corner of the
An
32A and 32B)
tank by bolting opposite sides together.
economical method of constructing a tank consists in assembling
a rough form with slabs of slate or soapstone, treating these while
warm
with asphalt, and lining the form with sheets of double thickness window
warmed)
glass (also
It
.
is
important to cover the slate surfaces liberally
with asphalt.^-
wooden tanks are usually satisfactory but they tend to accumuStorage and circulating tanks made of cypress wood are used extensively in laboratories in Hollywood and New York (see Fig. 10, page 27). Tanks of paraffined wood can be used if the wood is properly joined together with strips of untreated wood as explained on page 62. Tanks of Portland cement have been found satisfactory for developers of low alkali content. Metal or wooden tanks coated with oxyPlain
late slime.
genated asphalt are excellent provided the base material
from chipping
Deep tanks
of the asphalt.
not exposed
is
of 18-8 stainless steel with
welded
joints have also proved satisfactory as containers for developers and wash water. Tanks for fixing baths should preferably be fabricated from 18-8 stainless steel containing 2-4% molybdenum, to prevent
from the acid vapors above the solution
pitting
page 205).
Covers for Tanks. namely: 2. dirt,
i.
grease,
made
in
for tanks serve several useful purposes,
they prevent too rapid oxidation of the solution by the air;
and other foreign matter are prevented from dropping
into the solution;
be
â&#x20AC;&#x201D; Covers
(see Fig. 85C,
level
and
3.
the rate of evaporation
two ways either
the solution.
;
to
fit
In the latter case, the solution
tection against oxidation.
is
may
Covers
reduced.
over the top of the tank, or to float on is
given the
maximum promay be
For small tanks, satisfactory covers
constructed of hard rubber or cypress
wood
or sheet celluloid.
It is
usually unnecessary to use floating covers for very small tanks since the
by adding
A piece of nitro-
volume can be maintained
easily
cellulose sheeting, in the
form of a shallow tray or boat,
floated
of 100 gallons or larger capacity, covers
wood about
joints (Fig. 36). 12
is
sometimes
on the solution.
For tanks pine
replenisher.
Tech.
News
6 inches wide
One
by | inch
may
be built of
thick and grooved with "
layer should be fitted together tightly
Bull. No. 246, Nat. Bur. Stand.,
T
"
and an-
Washington, D. C, 105 (Oct. 1937).
MATERIALS FOR CONSTRUCTION other cut to
fit
on the
first
layer at right angles.
71
The boards should be
screwed firmly together from one side with Monel or 18-8 stainless screws, counter-sunk below the surface.
The cover should then be
steel
given
No. 5119 is satisfactory), dry thoroughly before the next is ap-
several coats of a nitrocellulose lacquer (E. K.
and each application allowed If desired, the
plied.
cover
together by a shoulder joint.
Fig. 36
â&#x20AC;&#x201D; Large
to
may
be made in two parts which are fitted Most covers built of wood become badly
tank cover showing laminated con^-uucLiuii.
months of use but the degree of warping of the one described will be a minimum. For circulating systems, floating covers may be made of molded sheet celluloid or 18-8 stainless steel with the edges turned up slightly and the seams welded to form a shallow tray or
warped
boat.
may
after a few
A
be
fairly satisfactory cover for
made
tanks of 50 to 100 gallons capacity
of hard surfaced asbestos sheeting or Transite board.
Such
covers should be painted with an acid proof paint such as Kodacoat,
Probus, Tornesit, or Pliolite and the edges protected from chipping by
them with rubber edging as used around automobile windshields. may be held together by attaching a small strip of rubber at the points where the side strips meet. The most satisfactory cover for storage tanks of acid fixing bath and developers is one made from 18-8 fitting
Corners
Mo
stainless steel.
Floating covers
have been used
They
made
of sheet iron
for developer
and coated with oxygenated asphalt
supply tanks for large automatic machines.
are fairly satisfactory for such purposes but should not be used
with fixing baths or other solutions.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
72
Tubes, Sprockets and Idlers for Motion Picture Developing Machines. Hard rubber, lead, 18-8 and 18-8 Mo stainless steel, and Pyrex glass have been found satisfactory for developing tubes. Lead
—
gathers a deposit of silver from the fixing bath, and in time this tends to obstruct the tube, but this deposit can be removed by scraping.
Brass
or copper tubing should not be used since both materials affect devel-
The body
opers and are corroded by fixing baths. sprockets should preferably be
made
structed of Monel, Inconel, or 18-8
part of idlers and
of hard rubber with teeth con-
Mo
stainless steel.
should not be soldered with solders containing
tin.
Metal tubing
Seamless tubing
is
be preferred.
to
Bakelite impregnated fabric represents a useful material for sprock-
and
ets
idlers,
which are exposed
to the action of developers
baths.
Troughs
for Reel Development.
and
fixing
— Glazed stoneware and wooden
troughs lined with sheet rubber or rubberized cloth are satisfactory for practically all ordinary processing solutions.
Mo
stainless
steel,
Leads, nickel, and 18-8
Monel, and Inconel metals are satisfactory
for
use with developing solutions, and although they are slowly attacked
they
may
For acid oxidizing solutions or
be used with fixing solutions.
strong alkalis, hard glazed stoneware troughs are
emergency
if
recommended but the
Metal troughs may be used
troughs should be emptied after use.
the interior of the trough
is
lined with pure
gum
in
an
rubber
This latter lining is applied by coating the heavy canvas cloth and sticking it to the The cloth is then brushed metal with cumar resin (medium hard grade) over with molten hard paraffin wax and the surface finally smoothed off with a hot iron. The wax should be renewed at frequent intervals. Metal troughs may also be coated with oxygenated asphalt but great care should be taken to insure that the metal is covered completely and that the coating is free from bubbles. Japanned metal ware is only satsheeting or paraffined cloth.
interior of the trough with
.
isfactory for intermittent use.
Piping, Pumps, Faucets, Etc. lutions,
hard rubber, iron, Duriron, Inconel, and 18-8
piping and
pumps
steel faucets is
Hard rubber
should be used, especially
necessary.
Mo
For transporting
if
or 18-8
Mo
stainless
continual exposure to the solu-
fixing solutions,
hard rubber piping,
pumps are recommended (see also Chapter IX, page Gear pumps of hard rubber represent a simple and economical
valves and
so-
stainless steel
are satisfactory and should be used in connection
with faucets of similar materials.
tions
— For transporting developing
203). installa-
MATERIALS FOR CONSTRUCTION
73
when a flow not greater than 5 to 6 gallons per minute is required. Such gear pumps require priming and must be kept wet while running.
tion
For a more rapid flow, a centrifugal
pump
Tinned
should be installed.
or tin-lined, copper, or brass faucets or piping should be avoided for
use with developers or
fi,\ing solutions.
however, pipe lines and
fittings of
Pure aluminum piping
are satisfactory.
water
tilled
For conveying
lines.
tin solder
also satisfactory for dis-
is
has the advantage over
It
distilled water,
block tin soldered with pure
tin
and rubber that long
spans do not need supporting.
Lead piping dered.
joints should be "
apparatus
If silver-plated
wiped is
" or
lead-burned, and not sol-
used, the plating should be free
from pinholes or scratches.
A
suitable packing for
the aid of a
pumps consists of asbestos rope twisted with Hard rubber faucets, piping, etc., must
hard grease.
little
be protected from impacts or excessive pressure.
The
and 75 summarizes the above recommendations.
table on pages 74
Precautions to be Taken terials.
â&#x20AC;&#x201D;
I.
come
als to
Do
not permit
in contact
developers, because
When
tin,
Selecting Construction Ma-
copper, or alloys containing these met-
with developing solutions, especially concentrated
more or
less of the tin or
copper
will dissolve
and
cause either serious chemical fog or rapid oxidation of the developer.
Do
not use galvanized iron vessels to mix developing solutions contain-
ing sodium bisulphite because
sodium hydrosulphite
which
Likewise, the zinc in the inner coating
a bad fogging agent.
is
will
be formed,
of galvanized piping will cause developer fog.
Contact of two or more different metals or alloys exposed
to
a devel-
oper will hasten the rate of corrosion of the metal and thus increase the
amount
of fog obtained.
with developers, but
one
free
from
of solder 2.
is
tin
if
Soldered joints are particularly to be avoided
such joints are unavoidable, a low-tin solder or
should be used, and the joints so
made
that a
minimum
exposed to the solution.
^Maximum
corrosion resistance to developers and acid fixing baths
with stainless steel will be secured by using an 18-8 type containing
4%
2
to
or
when
molybdenum.
special fabrication
should be chosen
problem.
in
When maximum is
resistance
is
not required
needed, other types of 18-8 stainless steel
accordance with the individual conditions of the
Stainless steels with low carbon content (below 0.2 ^f)
containing small quantities of
molybdenum should be chosen
and
for con-
struction of tanks, trays, hangers, etc., that will be exposed to acid fixing
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
74
TABLE 3 CONSTRUCTION MATERIALS Solution
Developer
Storage Tanks
Wood
Pipe Lines Iron (ungalvanized)
(cypress)
Stainless steel *
Iron (ungalvanized)
Hard rubber Hard rubber-
Asphalt-coated wood Lead-lined
wood
Hard-glazed stoneGlass-enameled
Rubber-coated con-
Wood
Inconel
Nickel
ware
Hypo not
coated steel Stainless steel *
steel steel
Hard rubber
(cypress)
taining
Lead
Soft rubber
silver
Asphalt-coated wood
Lead
Hard-glazed stone-
Rubber-coated
ware
steel
Rubber-coated
steel
Glass-enameled
Stainless steel *
steel
Stainless steel *
Acid hypo
Wood
(cypress)
Hard rubber
containing
Asphalt-coated wood
Soft rubber
silver
Hard-glazed stoneware
Rubber-coated
Rubber-coated Glass-enameled
18-8
Mo
steel
steel steel
stainless
1
8-8
Mo stainless
steel *
steel *
Water
Same
as under
Developer
Distilled
*
Note
Block
Soft and hard rubber Stainless steel *
Block
tin
Aluminum
water
Galvanized iron
(pure)
tin
Aluminum
(pure)
These materials corrode under certain conditions of use with acid fixing Mo stainless steel is considered to be the most resistant. Refer to the discussion of stainless steels and other alloys on page 56. :
baths but 18-8
MATERIALS FOR CONSTRUCTION
75
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
76
Joints should be welded and heat treated,
baths.
if
necessary, accord-
Occlusions should be ground
ing to the manufacturer's instructions.
away from the back of the weld. The use of steels containing colombium and molybdenum is claimed to decrease corrosion by preventing segregation of carbon near the weld. 3.
For
fixing, toning,
ever possible. cloth 4.
and acid oxidizing solutions, avoid metals when-
Trays lined with pure
may be used for this purpose. When choosing metals for the
gum
rubber sheeting or paraffined
construction of apparatus, a single
metal should be used whenever possible, and
welded or soldered from the outside
Seams
in containers
made
to
it
should be either electro-
avoid electrolytic corrosion.
of sheet lead should be joined together
by
lead burning. 5.
Apparatus constructed
of
aluminum,
zinc, or galvanized iron should
not be used with either developers or fixing baths, since these metals react with such solutions with the formation of precipitates which leave
a deposit on the film and often stain the gelatin. zinc
wash tank
will usually
salts carried over
by the
A
galvanized iron or
corrode rapidly from the action of the silver
film or prints
from the acid
fixing bath.
Plated metals should be avoided whenever possible for use with
6.
photographic solutions and only single metals or alloys used
in prefer-
ence, since electrolytic corrosion sets in as soon as a little of the plating
wears 7.
off.
For fixing baths or strong saline solutions, avoid porous materials
such as incompletely glazed earthenware, impregnated fibrous materials, or rubber compositions, because crystallization of the salts within the
pores of the materials causes disintegration. 8.
Trays or tanks coated with lacquer or baked japan are not
re-
sistant to strongly alkaline developers or fixing baths of high acid con-
centration. 9.
Avoid the use of cheap rubber tubing or other materials contain-
ing free sulphur or metallic sulphides in connection with developing solutions,
because the alkali
in the
developer attacks these, forming alkaline
sulphides which cause chemical fog. 10.
Corrosion of stainless steels and other alloys will be minimized
greatly provided the surface of the alloy
is
cleaned at regular intervals.
â&#x20AC;&#x201D;
In constructing Notes on Welding Stainless Steel Tanks/'' tanks of the 18-8 molybdenum stainless steel, it is important that the * The authors are indebted to Eastman Kodak Co., Rochester, N.
tlie
Engineering and Maintenance Shops of the
Y., for the data supplied in this section.
.
MATERIALS FOR CONSTRUCTION material be furnished with a low carbon content. the carbon content be 0.08'
It
77
is
essential that
or less in order to inhibit the intergranular
,
corrosion which occurs at the joints of welded seams due to deposition of excess carbides
when
the welding heat
is
applied.
It
has been found
that with a carbon content of o.oSS' or under, this characteristic will be
controlled and there will be practically no excess carbides deposited
along the grain boundaries.
For tanks which are large enough to hold 50 to 100 gallons, stainless gauge thickness should be used. Where pos-
steel sheets of at least 16 sible,
corner welds should be avoided, particularly
inside of the tank are to be polished.
formed that the joints
sides should be so
the sheets on the
if
In other words, the bottoms and
come
will
inch or
i
.so
from
the corners so that the seams will be easier to grind and a straight butt
type of seam fully
a
may
be welded.
and where the tanks are
No. 2-B
Stainless steel sheets should be annealed to
be cleaned easily, should have at least
finish.
There are four commonly accepted methods of welding in
stainless steel
These are as follows:
commercial use today. O.xyacetylene method
1
3.
Carbon arc (electric method) Atomic hydrogen arc
4.
Metallic arc
2.
The
first
Use uncoated electrodes
]
Use coated electrodes
two methods are not recommended since there
carbon pick-up
For
this reason,
where the
ance value of the 18-8 molybdenum stainless
method
recommended. The use
is
of distortion and,
corrosion resist-
full
steel is to
arc with uncoated electrode will result in a very
mum
danger of
welded seam by the use of either the oxyacetylene
in the
or carbon arc method.
third or fourth
is
of the flat
on the whole, with very good
be realized, the
atomic hydrogen
seam with a miniresults.
It will
be
found, however, that there are comparatively few skilled operators for the atomic hydrogen arc welding method.
ably not be available
The tric
metallic arc
many
themselves.
That
will is
It
For
this reason,
it
will
prob-
locations.
method makes use
arc welding machines.
welding wire which
The
in
is
of the ordinary
commercial
elec-
well to specify the use of electrodes or
have the same approximate analysis as the sheets
to say, iS^r
chrome,
S'/r
nickel,
3%
electrodes should be coated so that full advantage
the protective gas which
is
released
by the use
molybdenum.
may
be taken of
of this type of electrode,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
78
resulting in a
more
ductile weld
due
to the protection
oxidization of the deposited weld metal.
used with
work
all
types of metallic arc welding of stainless steel, that
or tank sheet should be the negative terminal
positive one.
mately
50%
from the rapid
Reversed polarity should be
The
co-efficient of
expansion of 18-8 alloys
greater than mild steel.
For
job for welding due allowance should be
is
for
the
approxi-
this reason, in setting
made
is,
and the electrode the
up the
expansion and contrac-
That is, greater care should be taken to use proper welding fixand clamps to prevent localized strains and distortion of the tank. After the weld has been made, it will be noticed that there is a discoloration along the sides of the weld seam. This is due to the scale which is formed at the high temperature of the welding arc. This scale and excess weld metal should be removed by grinding. tion.
tures
CHAPTER V
TEMPERATURE MEASUREMENT AND CONTROL The importance graphic solutions
of temperature in the preparation
by an increase
actions are accelerated tion
is
not always desirable since
A
reactions.
it
and use
of photo-
Most chemical
too frequently underestimated.
is
re-
temperature but such accelera-
in
may
result in undesirable
secondary
developer, for example, will require less time to produce
a certain density at 8o°F. (27°C.) than at 65°F. (i8°C.) but the solu-
much more
tion will also oxidize
a resulting increase in to
produce
with
Also,
fog.
film will swell
if
the temperature
and soften
The
difficulty.
rapidly at this higher temperature with
propensity to stain the gelatin of the film and
its
is
sufficiently high, the gelatin
such an extent that
to
it
can be handled only
use of suitable equipment for the control of tem-
perature represents an effective means for minimizing photographic troubles,
and devices
measurement and recording of
for the accurate
temperature constitute indispensable assets in the modern photographic plant.
—
Two thermometer Systems of Temperature Measurement. common use for measuring temperature, namely Centigrade
scales are in
and Fahrenheit.
On
the Centigrade scale (also called the Celsius) water
freezes at zero degrees
and
boils at ioo°,
and on the Fahrenheit
scale,
the corresponding readings are 32° and 212°.
Degrees Centigrade are
" °F."
Conversion of one scale
marked
" °C."
and degrees Fahrenheit
to the other should
be made as follows:
Since ioo°C.
= 2i2°F. — 32°F. or i8o°F.
i°C.=
and
°C. °F.
9/s°F.
X 9/5 + 32 = °F. -32°X 5/9 =°C.
In photographic practice, the Fahrenheit scale
employed, whereas
in research
work
in
is
almost universally
American and British univer-
and industries the Centigrade scale is used almost exclusively. For thermometers having unit scale divisions of equal width, the precision in reading a Fahrenheit scale is usually greater, since an error
sities
of 1° in reading the Centigrade scale
means an
error of nearly
2''
on
the Fahrenheit scale.
On
the continent of Europe, the
though most
thermometers are calibrated
in
Reaumur
scale
is
used extensively
al-
employ the Centigrade scale. Many both scales. The values on the Reaumur
scientific laboratories
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
80
scale differ
from the Centigrade values
scales
is
included in Chapter
50 °r
XIV, page
table
and Reaumur
347.
10°F
HVPROQumoNe Fig. 37
A
proportion 4:5.
in the
of comparative readings for the Fahrenheit, Centigrade,
— Comparative
ELON
rates of
development
of
Elon and hydroquinone de-
velopers at 50° and 7o°F.
Temperature
Effects
on
Photographic
Solutions.
chemical reactions proceed more rapidly as the temperature
and
than when cold.
w^ill
act
— Most
increased,
photography, so that
this is true of all the reactions involved in
developers and fixing baths
is
much more
rapidly
when warm
Different reactions are stimulated to different extents
by rise of temperature, and the effect of temperature can be measured numerically, the result obtained being termed the " temperature coefficient " of the reaction.
As a general
rule, the
temperature coefficient
is
measured
for a
change
of 10 degrees Centigrade, equivalent to 18 degrees Fahrenheit, so that
TEMPERATURE IMEASUREINIENT AND CONTROL if
a reaction, which at 60 degrees Fahrenheit takes 6 minutes,
at 78 degrees Fahrenheit in 3 minutes,
perature coefficient or factor of
we should say
that
is
81
completed
had a tem-
it
the rate of reaction being doubled
2,
for a rise of 18 degrees Fahrenheit.
The temperature
development varies with the develop-
coefficient of
ing agent, being least with the developers of high reduction potential,
such as Elon, and most with developers of low reduction potential, such
There
as hydroquinone.
is
one consequence of this which
is
rather im-
portant, namely, that the behavior of an Elon-hydroquinone developer
depends upon the temperature. is
very
inert,
At low temperature the hydroquinone is not decreased to the same
while the activity of the Elon
if it contained an At high temperatures the activity of the hydroquinone is increased far more than that of the Elon, and the situation is reversed. The difference in rate of development at low temperatures and at normal temperatures is shown in Figure 37. All four strips were given
extent and, consequently, the developer behaves as excess of Elon.
the
same exposure and equal times
It is seen that the lowering of
of development, namely, 4 minutes.
temperature has relatively
little effect
the rate of development of the Elon developer but slows
velopment rate of hydroquinone very greatly. that an Elon-hydroquinone developer will act
developer
A
if
the temperature
is
It is
down
obvious, therefore,
much
like
an all-Elon
lowered considerably.
similar principle applies to the fogging effect produced
opers.
If
development
ers will fog,
by
devel-
continued for a sufficient time, most develop-
but the fog reaction
and apparently has a
much
is
on
the de-
is
different
from that of development,
and one which
different temperature coefficient,
is
higher than the temperature coefficient of the development reac-
tion itself.
Consequently, a developer, which will develop an emulsion
to a satisfactory contrast with
low fog at a normal temperature,
produce very bad fog at the same image contrast
if
may
the temperature
is
high.
From in
the above
photography
is
it
will
be understood that the control of temperature
of great importance.
Whenever
possible,
development
always be carried out at a normal temperature (65째 If the temperature of the developer is too to 7o째F.) (18째 to 21째 C).
and
fixation should
high, then fog, softening,
and
Also, the solution oxidizes gelatin film.
The time
frilling of the
much more
of drying
On
is
material
readily,
may
also increased
by
the other hand,
if
too low, development will be delayed and there
is
cess water in the swollen film.
be encountered.
and tends
to stain the
virtue of the ex-
the temperature
is
danger of under-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
82
development, while the rate of fixation will be slow so that the fixing time must be prolonged to insure thorough fixation.
Acid fixing baths frequently decompose very rapidly with liberation of free sulphur
kept for a few hours to a few days at temperatures
if
over 95°F. (35°C.). temperatures,
it is
Although the rate of fixation
above 75 °F.
rise
for use
being 65° to 70°F. (18° to 2i°C.)-
rately
it
is
(2 4°C.), the
In storing large volumes
hypo and hardener solutions sepathe hypo when the latter is put into the
best to store the
and add the hardener
working tank.
increased at higher
recommended temperature range
bath to
of fixing bath
is
very bad practice to allow the temperature of a fixing
to
made
If cooling coils are used, they should be
of a
metallic material resistant to the corrosive action of these solutions (see
Chapter IV, page 52).
Some strongly oxidizing solutions, when employed at high temperatures
in particular acid
rapidly lose their effectiveness for
photographic use owing to secondary reactions.
work best
at temperatures
permanganate,
Usually these solutions
below 7o°F. (2i°C.).
Some photographic solutions, notably hypo-alum toning baths, are recommended to be used at 120° to 125 °F. (49° to 54°C.), but even these solutions should be watched carefully to see that the temperature
does not rise above that recommended. radation of the tone will result
if
Blistering, staining
and deg-
the temperature rises too high (above
i30°F.).
is
About the best general rule that can be given regarding temperature to mix, store and use the solutions at the temperature recommended
in the instructions of the
Types
of
manufacturer.
Thermometers and Their Application.
scale work, a good-grade glass fairly
— For small
thermometer of the usual type having
wide spaces between the unit divisions and legible figures
Some
satisfactory.
of these are
made
in the
form of a
Mercury
thereby serves a dual purpose (Fig. 38). of the best
known thermometric
liquids.
over a wide range of temperatures,
It
— 40*^^.
is
stirring rod is
quite
which
perhaps one
expands quite uniformly to -)-626°F.
(
— 40°C.
to
-f 330°C.). It is opaque, does not wet the glass, and has a relatively Ethyl alcohol has also large expansion for a given temperature rise.
been used extensively for measuring temperatures and other organic A dark liquids such as toluene have been used to a limited extent.
opaque liquid glass
is
preferable so that
it
may
be seen clearly through the
stem under darkroom illumination.
For the measurement of temperature of solutions automatic machines, the most satisfactory method
is
in
deep tanks or
to place a ther-
TEMPERATURE MEASUREMENT AND CONTROL mometer permanently
The method
in the tank.
of installation
is
83
impor-
tant.
For large storage or feed tanks which are provided with adequate
means
for stirring the solution, the
thermometer may be inserted through
the side, near the base of the tank.
Fic. 38
— Stirring
rod thermometer.
For working tanks or developing machines, practical to use the dial type of thermometer,
more convenient and
it is
which consists essentially
of a bulb, a long flexible stem, a flexible tube,
and an indicating
dial.
The bulb and stem may be placed in the tank from the top and immersed as much as desired, and should be made of a corrosion-resistant material such as 18-8 stainless
any
steel.
By
placing the bulb close to the tank wall
possibility of the bulb interfering with the
tank
is
obviated.
A
pure
gum
movement
used over the flexible tubing connecting the bulb and the
Three common types of thermometers are shown
A
has the scale attached to a short stem but
as type B,
which
is
fitted
of film in the
rubber or lead covered sleeve should be
is
Type
not as convenient to read
with a wall dial which
read at a glance from a distance of several
dial.
in Figure 39.
feet.
if
illuminated can be
Recording instruments
are also available which plot a record of temperature throughout the
day
(Fig. 39C).
For photographic work, an indicating thermometer
should have a large finger tapering sharply to a point.
The
dial figures
should be positioned so that a temperature of i8°C. (65°F.) cated
when the
finger
is
exactly vertical.
Any thermometer
is
indi-
reading less
than 2i2°F. (ioo°C.) which has a stem extending into or fastened to the inside of a tank should be withdrawn
when hot water
is
used to clean
out the tank, so as to avoid damage to the recording mechanism.
Methods
of Heating
Water
for
Mixing Solutions.
— Water
at
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
84
a temperature of
i25^F. (52°C.)
most chemicals, but there the chemicals
if
is
is
quite satisfactory for dissolving
a possible danger of decomposing some of
the temperature of the water
is
too high.
Most photo-
graphic chemicals are only slightly more soluble at i8o° to 2oo°F. (82°
— —
Stem type thermometer. Courtesy Taylor Instrument Co., Rochester, N. Y. Fig. 39B Dial type thermometer. Courtesy Foxboro Co., Foxboro, Mass. Fig. 39A
to
93°C.) than at i25°F. (52 °C.) and the slight saving
solution of the chemicals
is
and the extra time involved
Hot water
is
offset greatly
ture
is
in cooling the solution.
install their
argument against the use of water
own
heaters.
many
In such
at too high a tempera-
it is more economical i25°F. (52°C.) than to 180° to 20o°F. (82° to93°C.).
the increased cost of heating.
to heat water to
in time of dis-
possibility of spoilage
usually available from an independent source for
photographic workers but some must cases, a further
by the
Obviously,
MEASUREMENT AND CONTROL
TEIMPERATl'RE Hot water as follows: heater, 3.
i.
may
mixing solutions
for
85
be supplied from several sources
a water coil in the furnace,
an oil-burner operated heater,
a gas-flame operated water
2.
an
4.
and
electric heater,
5.
a
low pressure steam operated heater.
Fig.
A
â&#x20AC;&#x201D;
Recording thermometer. Courtesy 39c Taylor Instrument Co., Rochester, N. Y.
low pressure steam water heater consists of two essential units,
namely:
a. a
heating chamber and
ing chamber, in turn,
U
ing a group of " 2.
the head, as
is
is
as
fitted into the
chamber
Steam
It
in
The
is
filling
at the bottom.
the length of the
head.
A
The
a thermostatic control.
â&#x20AC;&#x201D;
i.
heat-
a chamber contain-
One end
Figure 40.
open end
sure of 3 to 15 pounds
three sections.
b.
of two parts
exit into
of the cylinder
is
open, and the head, to which are attached the water
the end of the head.
the
made up
shaped pipes having their entrance and
shown
closed, the other
pipes,
''
is
of the
chamber.
A
strong cap
fits
over
chamber under a presthe space around the pipes, and leaving admitted into the
A common
type of head
is
arranged in
incoming cold water enters one section, traverses
chamber twice and flows
into another section of the
then flows out again into the chamber, traverses
its
length
twice again and flows into the third section of the head, from whence flows out into the hot water pipe line.
it
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
86
At the point where the hot water leaves the head, a thermostat bulb This is connected by a capillary line to a valve on a 25- to 30-pound air line which operates the steam valve controlling the steam is
inserted.
pressure entering the heating chamber.
The
largest of the three gauges
STEIKM
Fig. 40
shown
in
— Diagram
Figure 40
is
set
at a desired temperature.
of a
by
low pressure steam water heater.
trial to
The two
operate the valve to deliver water
small gauges,
G^l
and Gg, measure the
pressure of the incoming air and the air which actually operates the
steam
A
line valve, respectively.
by-pass, B, should be provided as
shown
to operate the heater with-
out thermostatic control in the event that repairs are necessary on the
steam
line valve.
—
Control of Temperatures. \'ariations in temperature of plus or minus 2°F. are not usually important photographically except in the machine development of motion picture film or sensitometric control work. Variations of plus or minus 5°F. are usually serious, however, and in development must be compensated for by a change in the time of development or the image contrast will be affected. This is shown quite clearly in Figure 41,
which demonstrates the
effect of
changing the tem-
perature of a developer from 55° to 75° F. (13° to 24° C), on the con-
when developing for a constant time of 12 minutes. same developer (DK-50, page 288) it is interesting to note that equal contrasts at 55°, 65°, and 75°F. (13°, 18°, and 24°C.) are obtained in 14, 10, and 7 minutes, respectively. Therefore, when the trast of a negative
With
this
time of development
is
10 minutes, a change of temperature from 65°
TEMPERATURE MEASUREMENT AND CONTROL to
75°F. (i8° to 24°C.)
as
if
will result in
87
overdevelopment just as much
the time had been doubled at 65 °F.
The above
discussion serves to emphasize the need for temperature
control, especially in the case of large scale processing
55°F.
it is
often
75°F.
6s°F.
— Effect on contrast of varying the temperature
Fig. 41
when
of developer with con-
stant time of development.
difficult
offset
and sometimes impossible
temperature variations.
velopment in
in
many
to
change the time of development to
Furthermore, changing the time of de-
cases does not entirely compensate for the difference
temperature and at higher temperatures stains are apt to be produced. It is
a comparatively simple matter for the small scale worker to con-
trol the
temperature of his solutions by simply placing the bottle, tray,
or tank containing the working solution in a water bath of cold or
water until the solution has attained the desired temperature. scale work, the
problem becomes somewhat more
Water Mixers.
— The simplest type
of cold
warm
For large
difficult.
and hot water mixer
is
commonly used on household sink plumbing. It consists of a single By adjusting the valve on each line, water outlet fed by two lines. that
at
an intermediate temperature can be obtained.
Fluctuations in line
pressure and in the temperature of the water cause variations in tem-
perature of the mixed water, however, and
if
one of the
lines is
turned
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
88
off, it
permits the other to discharge without any mixing.
of this type
If
a mixer
used to control the water temperature flowing into a tray
is
or water bath containing films or prints, there
is
danger of ruining the
materials with extremely hot water.
42A - Water mixer with check valves on hot and cold Courtesy Fulton Sylphon Co., Knoxville, Tenn.
lines.
Several types of mixers are available which can be attached to the
hot and cold lines and which are not open to the above objections.
Some
of these mixers have been designed for shower bath installations in
Such mixers contain thermostatic
schools, hotels, athletic clubs, etc.
valves which contract or expand to maintain a constant delivery tem-
The Sylphon mixer
perature.
* illustrated in Figure 42A, for example,
uses a liquid expansion thermostat to control the cold water valve, and
a differential valve operated by the pressure change to control the hot
water valve.
In the event that either line
delivered
may
be
set
is
cut
off,
the mixer auto-
The temperature of the water to be by moving the hand lever on the side. Water
matically closes off the other
line.
mixers are supplied in several sizes and capacities according to the temperature requirements and the one illustrated will hold the discharged
water temperature within =t:2째F. of the
set point
with a supply water
temperature variation of 35째F. and a pressure variation of 30 pounds.
Another typical installation Valve (Series * Fulton t
R
is
the
Leonard Thermostatic Mixing
and T).t
Sylphon Leonard Rooke
Co., Knoxville,
Tenn.
Co., Inc., Providence, R.
I.
TEMPERATURE IMEASUREIMENT AND CONTROL The standard connections
for
any water mixer
installation are
89
shown
in Figure 42 B.
GAUGE GATE
—
^ 1 ^
VALVE
WOT ~^3ieg
.
1^4-
N
[><|
UNJION
CO\-D
WATER
r^^
^-^
— Standard
Fig. 42B
The mixing
STRAINER
^^^ifi^E*^
WATER TO MACHINE MIXER 65°^ OR TANK
pipe connections for water mixer installation.
valves described above are quite satisfactory for ordinary
use where the operating precision
not greater than
is
±2°F.
rate temperature
maintenance
is
In ex-
usually considered necessary.
treme cases the precision required
may
For
more accu-
processing laboratories using sensitometric control, however,
be as great as ±0.2 °F.
Under
such circumstances, more elaborate temperature control devices must
be installed, which compensate not only for pressure changes
in the lines
but also minimize greatly such factors as valve stem friction and hysteresis (friction
When
and
lost
motion) of diaphragms.
precise temperature control
ing equipment,
it
is
is
engineers of the leading firms
who manufacture temperature
equipment.*
Methods
of Cooling Solutions.
of cooling are
necessary on laboratory process-
suggested that the problem be discussed with the
by means
of
i.
— The
cold water,
regulation
three available
2. ice
and
methods
cooled brine or
3.
a gaseous refrigerant obtainable by mechanical refrigeration. I. Cold water is obtained from a faucet, by adding ice to water, or by mechanical refrigeration, and may be applied to the tanks in the following manner:
a.
Place pipes around the tanks.
b.
Place pipes inside the tanks.
c.
Place water jacket around the tanks.
d.
Flow water down
sides of tanks.
Placing the pipes around the outside of the tanks tory method, provided the tank material
is
as stoneware, Alberene stone, or metal.
With
or other poor conducting material, this
scheme
the rate of heat transfer *
See page 345.
list
is
rather slow and
is
a fairly satisfac-
a fairly good conductor, such insulating tanks of is
is inefficient
wood
In any case,
useless.
by virtue of heat
under water mixers and temperature regulators
in
Appendix
C,
90
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
transfer from the surrounding air, unless the pipes are enclosed with
insulating
medium such
Placing the pipes inside the tanks transfer but the pipes
Fig.
Lead
4,-i
must be
cuil
of a
is
a more efficient method of heat
non-contaminating material such as
un rack lor controlling temperature of a solution in a deep tank.
lead or 18-8 stainless steel for developers, and 18-8 less steel or
molybdenum stainThe dis-
hard rubber for acid rinse baths and fixing baths.
advantages of such a scheme are:
a.
the pipes reduce the available tank
space, h. in case of leakage the baths are ruined, fere with
an
as cork.
and
c.
the pipes inter-
keeping the tanks clean.
In the case of small tanks, the tanks which
may
300 gallon capacity sive floor load.
An
it is
feasible to place a water jacket
With
be of wood or stone.
this is usually impractical,
extremely simple method
around
large tanks of 200 to
on account of the exces-
is
to flow the
water down
the sides of the tanks through perforated pipes, but this will necessitate
frequent cleaning to remove the slime which otherwise accumulates on the tank walls.
In case the developer tanks are of stoneware or Alberene stone, a cooling tank It
may
be placed between the developing and fixing tanks.
should be equipped with a steam
in winter
and a brine
coil for
coil for cooling it in
heating the inflowing water
summer.
The
latter installa-
TEMPERATURE MEASUREISIENT AND CONTROL tion
may
be dispensed with
the temperature of the rinse water does
if
not rise above 65^F. (i8°C.) during the
cedure
is
is
surrounding
Cork
warm
insulation, although rather
The temperature
â&#x20AC;&#x201D; Arrangement
of a
quickly a few degrees
a lead
coil
for cooling solution in ice.
deep tank of solution
by using
the device
may
shown
attached to a wooden frame.
water faucet by means of a hose and the
the correct temperature.
of contamination
A
be raised or lowered
in
Figure 43.
It con-
The pipe is connected frame is moved about in
the tank for 5 or 10 minutes until the solution has
cause, unless the
from the
air to the tank.
deep tank with
to the
This pro-
also effective in preventing the transfer of heat
Fig. 44
sists of
summer months.
used successfully by some motion picture laboratories which
develop by the rack and tank system. expensive,
91
frame of stainless
become adjusted
steel
is
to
preferable be-
wooden rack is well lacquered, there is great danger by chemicals remaining in the rack after insufficient
washing.
With an adequate supply of cool water when using cooling coils, the temperature of the baths can be regulated automatically by means of a thermostat which controls the flow of water through the 2.
Ice can be applied by: a. placing
it
coils.
directly in the solution, h. plac-
PHOTOGRAPHIC CHEi\nCALS AND SOLUTIONS
92
ing it
it
in a
in
a rubber bag or metal tank inside the solutions, and
c.
placing
trough around the tank.
Although
ice is
frequently placed directly in the solutions,
tremely inadvisable because the melting ice dilutes the solution. ter method is to place the ice and move this around in the
in a
it
is
A
ex-
bet-
rubber bag or 18-8 stainless steel tank
solution.
TEMPERATURE MEASUREMENT AND CONTROL when very low temperatures
except is
are required.
93
In any case, dry ice
not recommended for cooling developing solutions because the carbon
dioxide gas converts
some
of the alkali in the developer to bicarbonate
and, therefore, tends to reduce the activity of the developer.
For rapid cooling, the dry placed
in a vessel
Fig. 46
â&#x20AC;&#x201D; Two
which,
ice
should be dissolved in alcohol and
in turn, is
placed
in the solution to
general types of refrigerating units.
be cooled.
Courtesy Frigidaire Corp.,
Dayton, Ohio.
Mechanical Refrigeration Methods. systems are readily applicable to
many
â&#x20AC;&#x201D; Mechanical
refrigeration
types of processing equipment.
Their use should be restricted, however, to the cooling of the actual solu-
because the cost of cooling wash water by this means
tions,
One type
prohibitiv^e.
essing (as described later) since
provides,
it
arrangement
is
usually
of installation designed for x-ray negative proc-
by means
for cooling the
may
be regarded an exception to the rule
of a novel supplementary cooling system,
an
working solutions as well as the wash water.
Fundamentals of Design of Mechanical Refrigerating Units.
â&#x20AC;&#x201D; Mechanical the fact that
pands freely,
it
it
becomes
amount
A a.
is
compressed
liquefied.
it
gives out heat
However,
On
if it is
compressed and cooled
allowing the liquid to evaporate
returns again to the gaseous condition but in doing so the gas
becomes cooled the
a gas
absorbs the heat again.
it
sufficiently,
depend on and when it ex-
refrigerating units of the compression type
if
to a
temperature below the surroundings, depending on
of liquid evaporated
and the rate of evaporation.
mechanical refrigerator consists of four component parts, namely:
the compression
pump
static control device,
and
or compressor, b. the condenser, d.
an expansion or evaporating
c.
a thermo-
coil.
Referring to Figure 45, the gas which may consist of sulphur dioxide, or a volatile organic compound is liquefied by compressing in
ammonia,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
94
the compressor and cooled in the condenser either with an air fan or by
The Hquid
water.
refrigerant
is
then fed into the expansion
coil
through
the expansion valve which must be adjusted for each installation.
operation of the unit the material which coil as
may
On
being cooled.
is
The
be controlled by a thermostat bulb placed
in
evaporating in the expansion
a result of absorption of heat from the surroundings, the liquid
vaporizes and
is
returned to the compressor, thus completing the cycle.
A. Fig. 47
B.
— Direct-Flo cooling unit and section of
pipe showing construction. lor Co.,
Courtesy H.
W. Tay-
Warren, Ohio.
Refrigerating units
may
be obtained either with
cooled condensors as shown in Figure 46.
cooled or water
air
These units are available
in
several sizes which vary in accordance with the requirements of the user.
Refrigerating Equipment for Tanks o£ 40 Liters) Capacity.
made with
of tests
5 to 10
— In 1929 Wilsey described the
Gallons (20 to results of a series
a cooling unit designed for use in conjunction with
x-ray processing solutions
{X-Ray
Bull., E.
K. Co., 5; August 1929,
6: July 1930, page 6). The cooling unit consists essentially of two parts: A. a pre-cooler, and B. a Direct-Flo cooler. The
page
2; also ibid.
coils for
both coolers are made up of two lengths of metal tubing, one
scoped inside the other as shown
in
B
of Figure 47.
tele-
In the pre-cooler
the incoming water flows through the inner tubing and the cooled waste
water from the tank flows through the outer tube.
About two-thirds
the required temperature drop occurs in the pre-cooler.
The
of
partially
cooled water then flows into the outer section of the pipe in the Direct-
Flo cooler.
The
inner section of this pipe constitutes the expansion coil
of the refrigerating unit.
The
efficient
cascade system of washing
is
employed whereby the
water flows from one tank to another and the fresh water flows into the tank in which the films are placed
last.
A
typical installation of such
TEMPERATURE MEASUREMENT AND CONTROL a unit
is
shown
in
fixing tanks is
it is seen that the wash water flows compartment holding the developer and
Figure 48, where
from the wash tanks
fit
95
the
intt)
and then through the pre-cooler
supplied by the Halsey
W. Taylor
to waste.
Co.,
This entire out-
Warren, Ohio, who also
manufacture a compact pre-cooler and Direct-Flo unit illustrated at in
A
Figure 47.
simple thermostat
â&#x20AC;&#x201D; Diagram
\S
cooler.
A
used to control the temperature.
of cooling installation showing pre-cooler and Direct-Flo Courtesy Halsey W. Taylor Co., Warren, Ohio.
In cold weather, provision directly from
is
is
washing tanks
solution compartment.
made
to by-pass the flow of
to the drain
and
The temperature
waste water
to close the outlet
of the solutions
from the
then main-
is
tained by filling the solution compartment with water at the required
temperature.
Refrigerating Equipment for Deep Tanks as Used by PhotoMotion Picture Laboratories, Tanks of 10
â&#x20AC;&#x201D;
finishers or Small to
150 gallon (40 to 600
capacity are generally used
liters)
by photo-
and by motion picture laboratories which employ the rack and tank method of development. Such tanks are usually quite deep in profinishers
portion to their width and are adapted, therefore, to a system of cooling
which involves some scheme of applying a cooling
coil directly
against
the outside or inside of the tank.
A The
refrigerant liquid
may
may
be utilized
in several
ways
as
shown
in
Figure 49.
be circulated through pipes which are placed on the out-
side of the tanks as at
i.
or inside a
narrow tank containing water or a
mixture of w^ater and glycerine or alcohol to prevent freezing which, in turn,
is
placed in contact with the sides of the tank as at
ing tank
may
be immersed
in the
3. are satisfactory and give better heat transfer
2.
or the cool-
Methods 3. than method i.
tank of liquid as at
2.
and
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
96
tank containing the
If a
fixing bath, the
coils
is
actually immersed in the developer or
tank should be constructed of a corrosion resistant metal
preferably 18-8 stainless
and not soldered,
steel,
and should have the seams electro-welded between the solder and
to avoid electrolytic corrosion
the tank.
It is
3
z
I
Fig. 49
— Various methods of applying refrigeration
to deep tanks.
impractical to immerse the compressor coils directly in the tanks
because of the danger of local freezing or crystallization of the constituent chemicals.
An
actual installation on the principle of
The
uses 50 and 51.
30-gallon tank
is
method
i. is
shown
of stoneware | inch thick
in Fig-
and
is
with ^ inch copper coils (22 feet long), front and back, which are bent as indicated and welded or soldered to large copper sheets (20 ounces) held in position tightly against the sides of the tank by small fitted
wooden frames
or metal
bands (Fig. 50).
transfer from the surrounding air, the tank
In order to prevent heat
may
be completely encased
with 2-inch cork board panels or mastic-coated cork board allowing a I
-inch dead air space around the tank.
All exposed
wooden
parts, in-
cluding cork insulation, should be painted with a chemically resistant paint.
The
efficiency of this installation
the user. as follows:
may
be adjusted to
fit
the needs of
In a specific instance, the performance of an installation was
With
a
-^-
horsepower refrigerator unit
in
a room at 8o°F.
(26.5°C.) a freshly mixed developer in a 30-gallon tank at ioo°F. was cooled to 65°F. (i8°C.) in six hours and was easily maintained at this
temperature with a one degree variation. If the room temperature is above 8o°F., a greater time would be required to bring the solution temperature to 65°F. Also, if the initial solution temperature was less
than ioo°F., a proportionally shorter time would be required to adjust The current consumption for three such tanks, each cooled it to 65 °F.
by to
would be around two to room temperatures varying from 75°
refrigerating units of j horsepower capacity
three kilowatt hours per
90° F.
This
is
day
for
considered a satisfactory performance because this
TEINIPERATURE
MEASUREMENT AND CONTROL
97
temperature variation of one degree would not greatly affect the negative
work a more expensive and
contrast although for high precision
precise
thermostat should be installed.
â&#x20AC;&#x201D;
Fig.
50
â&#x20AC;&#x201D; Cooling tank.
installation
51 Cooling installation for Fig. deep tank. Detail showing thermostatic switch and expansion valve with connections to compressor.
for deep
General view.
must necessarily be considered a separate problem by the individual firm working in collaboration with the refrigeration company.* The above method of cooling is applicable only to stoneware or metal tanks which conduct heat fairly well wooden tanks, which have low heat
Each
installation
to be solved
;
conductance, should not be cooled in this way. essary
I
.
to
immerse the cooling
In such cases
it is
nec-
narrow water bath placed
coils in a
in-
and along one wall of the tank as shown in 3 of Figure 49, or 2. to run cool water through coils immersed in the tank, or 3. to circulate the developer as shown in Figure 52. This last named scheme is applicable As shown in the also to large tanks of 100 to 500 gallons capacity.
side
figure, the solution
is
circulated
by means
of a
rounded by a chamber containing refrigerating It is
assumed
in
connection with
all of
pump
through
coils sur-
coils.
these methods of refrigeration
that the solution will receive a normal
amount
* Equipment adapting the above principles Manufacturing Corp., Rochester, N. Y.
is
of agitation during use
supplied by Kellogg Compressor
&
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
98
such as
is
given by moving tilm hangers in and out of the tanks and
agitating the hangers at intervals during processing.
perienced with a temperature gradient, that
is,
If difficulty is ex-
a difference in tempera-
ture between various parts of the solution in the tank,
it
may
sary to install some type of stirrer to agitate the solution.
100 gallons or larger capacity utilized is
by means
is
of square shape
If
be necesa tank of
and external cooling
of coils applied to the tank walls, the use
is
of a stirrer
imperative or uneven temperatures will prevail in different parts of
the tank.
PUMP Fig. 52
REFRIGERATING UNIT
â&#x20AC;&#x201D; Method
of cooling large
tanks by circulating the developer through an external chill box.
Refrigeration Equipment for Use with Large Automatic Large Developing Machines of 100 to 500 Gallons Capacity.
â&#x20AC;&#x201D;
automatic processing machines are essentially of two types, as follows: 1.
machines using the continuous flow system
2.
machines using the recirculation system
for the solution feed,
for the solution feed.*
and
The
problem of temperature control with either type of machine requires some scheme whereby small fluctuations in temperature are quickly corrected.
Machinery
of this t5^e
is
usually installed in rooms which are
equipped with automatic temperature and humidity control of the ventilation system. Solutions are usually fed from the mixing tanks to the circulating or storage tanks *
and then
These systems are discussed more
to the machines.
fully in Chapter
portation of chemicals and solutions, page 210.
IX
The temperature on storage and trans-
TEMPERATURE MEASUREMENT AND CONTROL of the solution in the storage tank
from the temperature required temperature variations
may
is
99
seldom over a few degrees different
in the
machines.
affect negative quality
be given the problem of correcting for fluctuations
Nevertheless, slight
and attention should in
temperature.
In either of the two systems mentioned above, satisfactory cooling
be accomplished in two ways, namely:
may
by flowing cool water through a coil immersed in the storage tank, or />. by passing the solution through a coil surrounded by a refrigerating coil (as shown in Fig. 52) on its a.
passage from the circulating tank to the machine.
Methods of Raising the Temperature of Photographic Solu— The three most common sources of heat for raising the tem-
tions.
-
perature of a solution are:
i.
hot water,
steam, and
2.
3. electricity.
For small scale work, a water bath surrounding the tank or tray Electrical immersion heaters
effective.
schemes described previously
may
quite
is
also be used.
INIany of the
may
be utilized to
for cooling solutions
heat them by using water or steam coils installed in a similar manner.
Although
electric heating jackets
have not been employed to any extent
such heating arrangements should prove satisfactory
in the past,
in
use
providing the jackets are well heat-insulated and protected against the action of the solution. tive
means
ture
is
a
For large processing machines, the most
effec-
of preventing an undesirable drop in the solution tempera-
to recirculate the solution
chamber heated with steam or
and surround the pipe at one point with electrically heated coils.
Wash Water
Importance of
Temperature.
— When
washing
photographic materials, the temperature of the wash water should not
be too high or too low.
If
it is
too high, over i2o°F. (7,8°C.),
it
may
cause blisters to form in the gelatin layer, or softening of the emulsion.
A satisfactory temperature
range is65°to75°F.(i8°to24°C.).
Nega-
on film or plates) do not wash any more rapidly, by hypo elimination, in warm than cold water, but positive materials, coated on paper, wash more rapidly in warm than cold water because the hypo appears to be held less tenaciously by the paper fibers. tive materials (coated
as measured
when washing paper
Therefore, creased
if
prints, the
washing time should be
in-
the water temperature falls below 6s°F. (i8°C.).
Tropical Processing of Photographic Sensitized Materials.
— Where the temperature cannot be
controlled, as
may
be the case in
and plates provided special measures are taken. These involve the use of solutions which have a minimum propensity to swell the gelatin and which act rapidly so the tropics,
it is still
possible to develop films
that the film or plate needs to remain only a comparatively short time in the solutions (see
Chapter VIII, page 180).
:
CHAPTER
VI
EFFECT OF THE WATER SUPPLY ON PHOTOGRAPHIC SOLUTIONS Water
is
the most widely used chemical in the processing of photo-
graphic materials and ties
present in
impurities
it
may
may
important to
it is
know
to
what extent the impuri-
be harmful to the various operations and
how
these
be removed.
Impurities in Water. water from clean, melted
â&#x20AC;&#x201D; Excluding
ice or
distilled water, rain water,
snow, the following impurities
and
may
be
present
Dissolved salts such as bicarbonates, chlorides, and sulphates of
1.
calcium, magnesium, sodium, and potassium.
may
Suspended matter, which
2.
consist of:
a.
Mineral matter such as mud, iron
b.
Vegetable matter such as decayed vegetation, fungus growths,
rust, or free sulphur.
and micro-organisms.
The suspended
particles
may
be of colloidal dimensions
case they are difficult to remove
by
in
which
filtration.
Dissolved extracts, usually colored yellow or brown, from decayed
3.
vegetable matter and the bark of trees.
Dissolved gases such as
4.
air,
carbon dioxide, sulphur dioxide, and
hydrogen sulphide.
EFFECT OF IMPURITIES ON PROCESSING Development.
â&#x20AC;&#x201D;
containing calcium
cium
i.
If a
salts,
sulphite, but with
developing solution
is
prepared with water
a white precipitate consisting largely of cal-
some calcium carbonate,
is
apt to form on mix-
In some cases a precipitate does not form immediately but a
ing.
sludge
^
consisting of fine needle-shaped crystals of calcium sulphite sepa-
rate out on standing (Fig. 53).
Such a sludge or precipitate will settle However, the
out on the emulsion side of the film and cause spots.
harmless
white precipitate or sludge
is
clear supernatant liquid
drawn
is
if
allowed to
off for use.
settle,
Magnesium
and only the salts,
unless
present in excess, are not precipitated.
The
developer, of course,
is
robbed of sulphite and carbonate to the
extent required to form the sludge or precipitate, but except in the case 1
"The Nature
(igi8)
;
B.
J.
of a Developer Sludge" by
Phot. 65, 87 (1918).
J. I.
Crabtree.
Amcr. Phot.
12, 126
EFFECT OF THE WATER SUPPLY ON SOLUTIONS of developers of low alkalinity, this effect
have shown that calcium or magnesium need to be present
is
negligible.
salts
101
Experiments
(chlorides or sulphates)
concentration greater than o.i /c to produce an
in a
appreciable effect on the developing power of developers containing
0.3% sodium
carbonate.
% â&#x20AC;˘".S^iJ^,.... ;.^^ ^.y
W:0
.:.\\
'y^'i^c
â&#x20AC;&#x201D;
Fig. S3 Crystals of calcium sulphite precipitated from a developer pre-
pared with hard water. Artificially
hardened water was used
According
tests.
to
U.
in
preparing developers for the
Geological Survey data
S.
-
on the hardness of
natural waters in different parts of the United States, the hardest water tested
was found
0.04%
to contain only
of
permanent hardness (calcu-
Depression of negative contrast by virtue
lated as calcium carbonate).
of a lowering of the sulphite or carbonate content of a developer
with natural waters found
liable to occur, therefore,
with weakly alkaline developers.
e.xcept, possibly,
in the
is
not
United States
In the case of devel-
opers containing a low concentration of borax, which are very sensitive to slight
changes
of calcium salts
in alkalinity, the presence of
would be
sufficient to
an appreciable quantity
lower the alkali content, and due
allowance for this should be made.
The
precipitation of calcium carbonate can be prevented
sodium metaphosphate (NaPO..) on the hardness, but (30 grains per quart)
fixing
an excessive amount (over
if
apt to form on the film
to the water, in proportion
is
used, a precipitate of
when
bath unless the film
placing in the fixing bath.
is
it is
depending
grams per liter) aluminum phosphate is 2
transferred from the developer to the
rinsed thoroughly in running water before
The
addition of metaphosphate to a fixing
bath containing alum tends to destroy 2
by adding
its
hardening properties.
U. S. Geological Survey Water Supply Paper No. 496.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
102
Salts liable to be present, other than the above, are chlorides
mides of the
alkali metals
carbonate, which
the action of a weakly alkaline developer.
exert
to
any appreciable
With
in the
It is
if
the average developer,
water used for mixing
is
Developers mixed with
effect.
water containing sodium or potassium sulphides fog even
Sodium up
present in certain alkaline waters, tends to speed
is
however, the concentration of the alkali insufficient
and bro-
which exert a restraining action.
bad chemical
will give
the sulphides are present in very small quantities.
customary
to
add copper sulphate
riodic intervals in order to kill vegetable
the presence of
to certain
and
water supplies at pe-
biological growths.
While
part in 10,000 of the copper salt in a developer will
i
cause aerial fog,^ the concentration of the copper salt in the water supply usually 2.
a.
is
much
lower than
this.
Dirt and iron rust suspended in the developer solution often
produce spots and
stains.
In the case of a pyro developer the iron
apt to combine with the pyro, forming an inky
a bluish-red color to the solution although photographically Particles of finely divided sulphur
is
compound which imparts it is
harmless.
which give the characteristic opal-
escence to sulphur waters will cause fog, owing to the formation of
sodium sulphide by interaction with the carbonate present oping solution.
water
whereupon
it
may
is
usually precipitated
developer.
in the devel-
boiled, the colloidal sulphur usually
is
Vegetable matter
coagulates, b.
If the
be separated by settling or
by the
filtration.
salts present in the
Frequently fungus growths and micro-organisms thrive in
a developer and form a slime or scum on the walls of the tank.
Some
types of these growths act on the sulphite in the developer, changing to
sodium sulphide which fogs the emulsion very badly.
is
removed by developing some waste
The
film in the solution or
it
sulphide
by adding
a small quantity of lead acetate to the developer in the proportion of
60 grains per gallon (i gram per
liter)."*
Tanks which show a tend-
ency to accumulate slime should be scrubbed with hot water at regular intervals
and then treated with a
dilute
sodium hypochlorite solution
Chapter XII, page 265). Suspended mineral, vegetable, or animal matter in general has usually no harmful effect on a developer, provided (see
the mixed developing solution
supernatant liquid drawn
wafm 3
off
is
allowed to stand and only the clear
for use.
Preparing the developer with
water tends to hasten the rate of settling of the suspended matter.
"Chemical Fog" by
Pilot. 66,
J.
I.
Crabtree.
Amcr. Ann. Phot.
33, 20
(1920); B.
J.
97 (1919). 4 " Sulphide Fog by Bacteria in Motion Picture Developers " by M. L. Dundon and J. I. Crabtree. Amcr. Phot. 12, 56 (1925).
EFFECT OF THE WATER SUPPLY ON SOLUTIONS
103
Extracts from decayed vegetable matter or the bark of trees usu-
3.
ally discolor developing solutions but are often precipitated
veloper
prepared with
is
warm water and
ing effect of such extracts
Water
4.
is
dissolves about
the de-
if
The
allowed to stand.
stain-
usually negligible. 2""^
of air at yo^F.
developing agent like hydroquinone
is
(2i°C.) and when a
dissolved without the addition of
sulphite the oxygen present in the water combines with the developing
agent, forming an oxidation product which
form of
apt to stain the gelatin and
is
Air in water occasionally collects on the film in the
fog the emulsion.
bubbles or airbells which prevent development and pro-
little
duce characteristic markings ing at high temperatures
causes blisters
'
(see page 188
'^
(see Fig. 70,
(above 8o°F.)
When
page 144).
(26°C.) dissolved
and Fig. 70).
Mineral waters containing carbon dioxide rarely give provided the water dioxide
way
is
boiled
first in
order to drive
off
present in a developer in excessive amounts,
is
as dissolved
air,
developair often
much
the gas. it
trouble,
If
carbon
acts in the
producing bubbles and airbells on the
film.
drogen sulphide gas will cause bad chemical fog in a developer but
same
Hy-
may
be removed by boiling the water or by precipitating with lead acetate before mixing."It is
*
sometimes thought that water treated with chlorine
suitable for mixing photographic solutions.
Any
may
be un-
chlorine present,
how-
would be destroyed immediately by the sulphite or developing
ever,
agents.
The
chlorine content
is
usually so small that the photographic
properties are not appreciably affected
by
virtue of this destruction of
a trace of the constituent chemicals.
— Calcium and magnesuim
Fixation.
sulphites are soluble in acetic
acid and therefore are not precipitated in fresh acid fixing baths. If the
pH
any scum
value or degree of alkalinity of the bath becomes too high,
of calcium sulphite
prints in the developer
is
which
may have formed on
the films or
not dissolved and remains even after washing.
important, therefore, to keep the fixing bath sufficiently acid by
It is
revival or the use of an acid rinse bath. 5
tree 72,
" Rack Marks and Airbell Markings on Motion Picture Film " by J. and C. E. Ives. Trans. Soc. Mot. Pict. Hinj. No. 24. 95 (1925) B. ;
775 (1925) c
tree. '
;
Crab-
J.
Phot.
73, 4 (1926).
The Handling of Motion Picture Film at High Temperatures " by J. I. CrabTrans. Soc. Mot. Pict. Eng. No. 19, 39 (1924); B. J. Phot. 71, 762 (1924). "Chemical Fog" by J. I. Crabtree. Amcr. Ann. Phot. 33, 20 (1920); B. J.
"
Phot. 66, 97 (1919). 8 " Sulphide Fog by Bacteria in Motion Picture Developers " by M. L. J. I.
I.
Crabtree.
Amcr. Phot.
12, 96 (1925)-
Dundon and
104
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
Other dissolved
salts such as bicarbonates, chlorides, and sulphates are Suspended matter such as dirt, iron rust, and certain types of vegetable and animal matter usually will coagulate and settle out on
harmless.
allowing the fixing bath to stand.
(a)
â&#x20AC;&#x201D;
Drying marks on the film emulsion produced by water on the emulsion side; (b) water on the base side.
Fig. 54
Although most suspended substances have practically no
may
photographic properties of fixing baths, the particles film,
locally retarding fixation,
effect
on the
settle
on the
and producing spots and
stains
(see
Chapter XI, pages 248, 255). Extracts from vegetable matter or dissolved gases do not affect the photographic properties of a fixing bath, but are liable to cause stains and
Washing.
â&#x20AC;&#x201D; Dissolved
blisters,
salts often
and
locally retard fixation.
cause trouble by crystallizing on
the film after drying (Fig. 53, p. loi), and although not always visible as crystals to the eye, they detract from
water containing calcium
salts leave a
its
transparency.
Drops
of
white scum after evaporation.
Water which
is
provided
allowed to remain in droplets on either side of the film dur-
it is
free of dissolved salts also will cause
ing drying^ (Fig. 54). all a.
It is
important therefore to remove thoroughly
excess water from the film before drying.
This can be accomplished
by draining thoroughly before applying a current
9 " Moisture Markings on Motion Picture Film " by J. Matthews. Trans. Soc. Mot. Pict. Eng. No. 17, 29 (1923)
IS (1924).
markings on film
of air, h.
I. ;
by swab-
Crabtree and G. E. J. Phot. 71, 6 and
B.
EFFECT OF THE WATER SUPPLY ON SOLUTIONS bing with wet absorbent cotton, viscose sponge, or chamois, and
means
of a
105
c.
by
pneumatic squeegee.'"
Fig. 55
â&#x20AC;&#x201D; Low pressure steam operated water
still.
(Capacity 15 gallons per hour.)
Suspended mineral, vegetable, and animal matter usually produces a
scum on drying. or
film unless the gelatin surface If the
water used
for
filtered before using for
is
washing
wiped carefully previous to run into a large settling tank
is
is
washing purposes, most of the suspended
matter will be removed (see discussion on
filters,
Chapter
III,
page 31).
Dissolved extracts from bark and decayed vegetable matter produce stains
which are very
difficult to
remove.
In
many
cases, however,
it is
by passing it through a filter containing the wash water is warm, dissolved gases
possible to decolorize such water
activated charcoal.
Also,
sometimes produce
will
sufficiently in the fixing
So far as 10
Mot.
"A
Pict.
is
if
blisters, especially
if
the film
is
not hardened
bath (see page 188).
known, any small
Pneumatic Film Squeegee Etig. No. 30, 270 (1927).
"
traces of impurities left in the gelatin by
J. I.
Crabtree and C. E. Ives.
Trans. Soc.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
106
coating of a film after drying, by virtue of the presence of these im-
wash water, are not
purities in the
liable to seriously
impair the keeping
However,
properties of the films over a period of four or five years.
which are
films
be kept for long periods of time should be washed
to
finally in distilled water.
The Preparation
of
Dye
Solutions.
â&#x20AC;&#x201D; Many
dyes are precipi-
by calcium or magnesium salts and alum. The not always immediate and may occur only after standing
tated out of solution precipitation for a
is
The
few days.
properties of dyes with respect to their rate of pene-
tration into gelatin or the rate at
which they are mordanted are affected
considerably by the presence of metallic ions, or acids, or bases, so that in color
photography or when using
desensitizers, impurities in the water
are apt to produce anomalous results.
Dye
solutions should, therefore,
be prepared with distilled water rather than water containing dissolved salts (see
pages 177 and 326).
Distillation.
â&#x20AC;&#x201D;
Distilled water should be used
water by one process only, namely,
which consists
distillation,
verting natural water into steam which, in turn,
The
liquid form.
whenever possible
for
Chemically pure water can be obtained from natural
mixing solutions.
is
condensed
dissolved salts and impurities do not
in con-
to the
over and
distill
are left behind.
Water
stills
are available in sizes ranging from those which deliver
gallons per hour to those of several
to 2
capacity.
Stills
are most
commonly operated with
pressure steam (Fig. 55).
i
hundred gallons per hour low
either gas or
Small units delivering from
i
to 5 gallons
per hour are also supplied with electric heating units but are usually more
expensive to operate unless a cheap source of current
56A). gas
if
It is
not generally considered
the capacity
is
efficient
both small and large capacity
For very large volumes of for
economy.
The
available (Fig. still
with
greater than 10 gallons per hour unless, of course,
a cheap source of gas can be obtained (Fig. 56B). for heating
is
to operate a
Kerosene
is
also used
stills.
distilled water, multiple effect stills are
used
exact type of installation depends on the needs of the
individual photographer, and manufacturers of water
stills
should be
consulted (see Appendix, page 344). Until recent years block tin has been employed extensively as a construction material for pipe lines and fittings to carry distilled water.
In
and storing distilled water. It lends itself to rapid fabrication, threading, and in long pipe Tin-plated lines does not require supporting to the same extent as tin.
some cases aluminum has been used
for piping
EFFECT OF THE WATER SUPPLY ON SOLUTIONS brass or copper as well as of these install if
aluminum
is
used for storage tank linings but
is
an economical precaution to
It is
automatic spring closing faucets on
aluminum piping
num
aluminum
recommended.
is
employed,
107
all distilled
fiber seats
water
lines and,
should be used in the alumi-
faucets.
— Small
capacity water still heated by a storage battery. Courtesy Barnstead Still and Sterilizer Co., Inc., Boston, Mass. Fig. 56A
electrically
Fig. s6b
water
— Small
still.
capacity gas-heated
Courtesy F.
Stokes
J.
Ma-
chine Co., Philadelphia, Pa.
— Unless
Boiling.
solved salts, and it is
if
the water contains an excessive quantity of dis-
the purchase of distillation equipment
usually sufficient to boil the water and allow
natant portion then fine muslin.
Most
may
be siphoned
off or
colloidal vegetable
it
is
to settle.
prohibitive,
The
super-
the solution filtered through
and animal matter, comprising
slimes and scums, coagulates on boiling and certain lime salts are
changed
to
an insoluble condition and
settle out.
not removed but dissolved gases are driven
by
Dissolved extracts are boiling.
—
Various types of water filters are available commerbut these do not remove dissolved salts or colloidal matter unless
Filtration. cially,
off
the water has been treated previously with a coagulant.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
108
The
simplest type of water
filter
consists of several layers of fine
cheesecloth or cotton flannel fitted over the end of a hose attached to the
Another type consists of a small metal receptacle
faucet (Fig. 57).
holding a
felt
pad, sand, or other filtering
medium which may be screwed
on the faucet (Fig. 58).
Simple type of water
Fig.
filter.
â&#x20AC;&#x201D;
Fig. 58 Small water filter attached to faucet. Courtesy
Jones
Manufacturing
Co.,
Boston, Mass.
The tubular
filter
shown
It consists of
filter.
guide rod, a
filter
on a flange.
tube,
The
in
Figure 59 represents a useful type of water
an outer metal cylinder, a combination cap and
and a
cylindrical cover
The
filter
minimum
open
consists of an
helical
Water
ward through the wall of this tube. are made by changing the spacing
A this
against a gasket
in
a
alteration in existing piping.
around a circular wire screen.
filter
fits
which permits installation
straight line on the cylindrical cover,
pipe line with a
which
feed and discharge connections are arranged in a
is
winding of filtered
fluffy cotton
by passing
thread
radially in-
Fillers of various degrees of fineness
of the thread or including a layer of
paper inside the winding. reasonable flow of water for most photographic requirements with
type of
filter will
be obtained with approximately 40 pounds water
pressure per square inch.
The
life
depends
in all cases
on the amount of
material to be removed from the water and on the pressure applied.
use of rotary or gear
pumps
rather than piston
pumps
is
The
recommended.
EFFECT OF THE WATER SUPPLY ON SOLUTIONS
Fig. 59
— Small cylindrical
filter
Commercial
Fig. filter.
using cotton
Filters Corp.,
wound
tubular
filters.
Boston, Mass.
—
Large capacity gravity type water 6o Courtesy Wm. B. Scaife & Sons, Oakmont,
Pa. °f*
Pa.
—
"^jf
Large capacity pressure type water Courtesy Wm. B. Scaife & Sons, Oakmont,
Fig. 6i filter.
SUPPLY
109
Courtesy
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
110
For sand
filtration in plants using
filter
coal, or a
may
25,000 to 500,000 gallons daily, a gravity
be installed (Fig. 60).
Pressure
filters
using sand, char-
composition material are also available of similar capacities to
the gravity type but in general they have not been found to deliver quite as clear water as the gravity type.
much more compact than much floor space Fig. 61 (
a pressure fioors of
filter,
)
Pressure filters
It is often
.
particularly
if
however, are usually
filters,
and, therefore, do not require as
necessary to
the laboratory
pump
the water into
located on the upper
is
a building.
The choice among which 3.
gravity
of a particular type of filter are:
i.
depends on several factors
condition of water supply,
2.
location of laboratory, 4. floor space available, and
For further
tion required.
details, the
capacity needed, 5.
manufacturers of
degree of filters
filtra-
should be
consulted (see Appendix, page 342).
Chemical Treatment. fication * 1.
may be
â&#x20AC;&#x201D; The
following methods of chemical puri-
adopted
Potassium alum
may
be added in the proportion of
grains) to 4 liters (i gallon) of water. carries
down suspended
particles
and
alum introduced
into the water has
2.
A 10%
solution of
and coagulates the
solution.
may 3.
The
no harmful
effect
on the solution
mixing developers and fixing baths.
sodium oxalate may be added
until
no further
slime, although other dissolved salts are left in
Solutions of sodium phosphate and of sodium sulphite also
be used to precipitate calcium and magnesium.
Most
of the
commercial methods of softening water
may
be em-
ployed although such methods do not remove sodium and potassium
One
Dis-
small percentage of
This method removes the calcium and magnesium
precipitate forms. salts
for
gram (15
clears the solution rapidly.
solved salts are not removed by this method.
when subsequently used
i
This coagulates the slime which
salts.
most satisfactory methods consists in passing the water through a tank containing sodium aluminum silicate (zeolite), which possesses the power of exchanging its sodium for the calcium and magof the
nesium present
in the water.
Sodium aluminum
silicate
(zeolite)
+ Calcium sulphate
Sodium sulphate
=
+ Calcium aluminum
silicate
* Water purified by the treatments described is not generally satisfactory for drinking purposes since these treatments are not intended to kill micro-organisms in the water.
EFFECT OF THE WATER SUPPLY ON SOLUTIONS When
the zeolite thus loaded with calcium and
in a strong solution of
common
and magnesium again the chemical
may
for
(about
salt
sodium and
12%)
it
magnesium exchanges
ill
is
washed
its
calcium
thus regenerated, whereupon
is
then be used for further softening.
Calcium aluminum
Sodium aluminum
silicate
silicate
(zeolite)
=
+
+
Sodium chloride
Calcium chloride
â&#x20AC;&#x201D;
62 Portable water softening Courtesy Permutit Co., New York, N. Y. Fig.
unit.
A
compact, portable water softening unit working on the principle
described above
York, N. Y.
It
is
supplied by the Permutit Co., 440 Fourth Ave.,
may
be attached to any household faucet and
of softening 100 gallons of water before
62).
it
is
New
capable
needs to be regenerated (Fig.
Larger water softening units are manufactured by several different
companies, reference to which
may
ing Catalog," published annually
New York, N. Y. A comprehensive
be found in the " Chemical Engineerby the Chemical Catalog Company,
discussion of the relative efficiency of various meth-
ods of water softening has been published by Mills." 11
"
Modern Water Softening
277 (Sept. 1933).
"
by A.
J.
Mills.
/.
Soc.
Dyers and Colorists
41),
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
112
A method exchange
of removal of dissolved mineral solids
removing the ionized dissolved
It consists of
through a bed
from water by organic
has been described by Bird, Kirkpatrick and Melof.^-
filters
in
which the
salts are
by passing the water
solids
converted to acids, and then passing
the acidic water through a second bed in which the acids are removed
from solution
and
to yield a water substantially neutral
free of dissolved
solids.
The Use
of Sea Water.
â&#x20AC;&#x201D; Sea
water contains a relatively large
proportion of soluble salts (about 3.5%) and should not be used for
mixing photographic solutions except other water
is
chlorides, bromides,
last
may
is
and iodides
When
graphic solution. sea water
This
available.
extreme emergencies when no
because the dissolved salts such as
may
retard the action of the photo-
the supply of fresh water available
is
very small,
be used for washing photographic materials provided a
washing or soaking previous
water. ^^
in
Even
to drying
given in distilled or fresh
is
after thorough squeegeeing a considerable quantity of
magnesium
the constituent salts remains and the hygroscopic
chloride
causes " dampness " and tends to accelerate fading of the silver image.
important therefore to wash or soak
It is
treatment, which
is
effective in
Suitability of the
Water Supply.
water supply usually reveals very fulness.
It
may
pure water after the sea water
little
â&#x20AC;&#x201D;A
chemical analysis of the
concerning
its
photographic use-
be of some assistance in indicating the quantity of lime,
oxalate, etc., to be late slimes.
in
removing the hypo.
added
to
The quantity
remove dissolved calcium
of total solids indicates
marks may be anticipated, while the presence
if
of iron,
is
to
The only
prepare a developer with the sample and actually try
compared with the same developer prepared with
coagu-
hydrogen sulphide,
or metallic sulphides should be regarded with suspicion. test
salts or to
trouble from drying
useful it
Also, a large drop of water should be allowed to dry on a film
the
amount
of residual
scum observed.
the trouble to be expected
if
the water
This is
out
distilled water.
and
will indicate the extent of
not removed thoroughly before
drying.
"
of Dissolved Mineral Solids from Water by Organic Exchange by P. G. Bird, W. H. Kirkpatrick and E. Melof. /. Amcr. Water Works Asso. 29, 1526 (Oct. 1937). " Washing Motion Picture Film " by K. C. D. Hickman. Trans. Soc. Mot. Pict. Eng. No. 23> 62 (1925). 12
Filters "
I-''
Removal
EFFECT OF THE WATER SUPPLY ON SOLUTIONS Practical Recommendations. with
warm water
night,
any
If
developing solutions are mixed
(about i2 5°F.) (52'^C.) and allowed to stand over
precipitate or suspended matter will settle out
supernatant liquid
and other
â&#x20AC;&#x201D;
113
may
salts in the
be drawn
water supply
and the clear
The presence
off for use.
sometimes beneficial
is
of calcium
in so far as
they tend to retard the swelling of the gelatin coating of the film during washing.
This
The only
is
advantage
of particular
in
hot weather.
impurities liable to cause serious trouble with developers are
hydrogen sulphide or soluble metallic sulphides.
With such water, about
60 grains of lead acetate per gallon of developer (i gram per should be added before mixing.
phide and any excess lead
is
liter)
This removes the sulphides as lead
sul-
precipitated in the developer and settles
out on standing.
No trouble may be
anticipated with fixing baths prepared with average
samples of impure water provided the bath
is
clarified
by
settling before
use.
In localities where very hard water
mixing photographic solutions, unit.
These are available
in
it is
is
both small, portable
capacity) for amateur or studio use, and
normally require several hundred for
or
100 gallon
sizes (of
in large sizes for plants
more gallons
of water each
which
week
mixing their solutions.
When
washing photographic materials
pated with uncolored water a.
the only source available for
advisable to install a water softening
remove
all
if
little
trouble
may
be antici-
the following precautions are taken:
suspended matter by
filtering, either
by means
of
commer-
by placing two or three layers of cloth over the water outremove thoroughly all excess moisture from the film before drying. Water which is colored brown even after filtering through cloth or
cial filters or let, b.
sand
is
very apt to cause staining of the highlights.
through activated charcoal
is
effective.
Usually
filtering
CHAPTER
VII
TECHNIQUE OF MIXING AND USING PHOTOGRAPHIC SOLUTIONS DEVELOPERS Photographic developers usually contain four solid ingredients as
fol-
lows:
The developing
A.
or reducing agent
(Elon,* hydroquinone, pyro,
para-aminophenol, para-phenylenediamine, B.
The
C.
The
etc.).
preservative (sulphites, bisulphites, and metabisulphites of
sodium and potassium). alkali or activator (carbonates
tassium, and
ammonium;
and hydroxides
of sodium, po-
also borax, borates, amines, etc.).
D. The restrainer (bromides and iodides of sodium and potassium).
The Developing number
or
Reducing Agent.
of different developing agents
photographer from time
â&#x20AC;&#x201D; In
to time, for general use
perior to Elon, hydroquinone,
spite of the large
which have been offered
and pyro.f
to the
none have proved su-
Some photographers
still
use
pyro exclusively, maintaining that a yellow pyro-stained negative
will
give better prints than an Elon-hydroquinone developed negative.
Ex-
tensive tests have shown, however, that
it is
possible to get just as good
prints from negatives developed with Elon-hydroquinone as with pyro.
Of
same contrast as an more contrasty print usually give a
course, a pyro negative which appears to have the
Elon-hydroquinone negative
will
because of the yellow stain image present.
hydroquinone negative
is
If,
however, the Elon-
developed long enough so that
printing contrast as the pyro
it
gives the
same
negative, the quality of the prints for a
given amount of fog on the negative will be identical.
The presence
of the
pyro stain image can readily be revealed by
ducing a pyro-developed negative in Farmer's reducer, which
mixing equal parts of a
5%
solution of hypo.
5%
is
re-
made by
solution of potassium ferricyanide and a
This treatment removes the
silver
image but
leaves the stain image. * The developing agent, mono-methyl para-aminophenol is sold under various Since the experience trade names such as Metol, Elon, Pictol, Photol, Rhodol, etc. of the authors has been largely with Elon, reference will be made to this trade prod-
As supplied to the trade, Elon is a salt of sulphuric acid and methyl para-aminophenol and when dissolved in water it gives an acid reaction. para-aminophenol t Other developing agents which are used less extensively are (amidol), para-oxyphenyl glypara-phenylenediamine, di-aminophenol (p.a.p.), uct throughout this book.
:
cine
The
(glycine),
chlor-hydroquinone, and pyrocatechol (pyrocatechin or catechol). common developing agents are listed in Table 7, page 216
properties of several
MIXING AND USING PHOTOGRAPHIC SOLUTIONS Pyro has one very valuable property which are formed when the developer fog, the
nature of which
is
in so far as its
is
veloper will prevent this fog, which
is
oxidation products,
exposed to the
A
explained later.
115
air,
prevent aerial
trace of pyro in the de-
the reason for using a mixture of
Elon, hydroquinone, and pyro in some formulas.
E
H
E
H
E
Imin.
Imin.
2min.
2min.
4min.
Fig. 63
The
â&#x20AC;&#x201D; Comparative
rates of
development
of
Elon
vs.
H 4min.
hydroquinone.
addition of pyro to an Elon-hydroquinone developer tends to in-
crease the rate of aerial oxidation of the developing agents so that the
quantity of pyro added should be a minimum. In view of the above objections, namely:
poor keeping properties, of
b.
a.
the staining and relatively
the accelerating effect on the aerial oxidation
Elon and hydroquinone, and
c.
the fact that
it
is difficult
to secure
negatives of uniform printing contrast because the quantity of image stain varies with the age of the dev^eloper,
by Elon-hydroquinone is
for the
pyro has been replaced entirely
development of motion picture film and
being discarded rapidly by professional photographers
in
favor of the
more stable Elon-hydroquinone developers. The difference in behavior between Elon and hydroquinone clearly in Figure 63.
The
test
was made with what
are
known
is
shown
as step-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
116
exposed negatives which simply consist of strips of film which have
An
ceived increasing exposures in steps from end to end.
re-
exposed picture
negative likewise consists of a series of patches of irregular shape which
have received increasing exposures so that we
may
consider the lower
density steps in the step negative to correspond to the shadows, and the
higher densities to the highlights of an ordinary negative.
Such step
negatives are to be preferred for testing purposes because they can be
reproduced exactly and can be compared more easily by placing side by side.
Two developers
were prepared, one containing only Elon and the other
only hydroquinone.
Step-exposed strips of film were then developed in
minute, 2 minutes, and 4 minutes, respectively. minute the Elon developer had produced an image of low contrast
each developer for After
I
i
while the hydroquinone had produced only the faintest sign of an image. After
minutes
2
all
the image tones were visible in the case of both de-
velopers but the hydroquinone image was less contrasty than the Elon
After 4 minutes, the two negatives were almost identical.
image.
On
prolonging the development, the hydroquinone image was more contrasty
than the Elon image.
Elon, therefore, brings out the detail quickly but
the hydroquinone builds
The
Preservative.
from oxidizing
sodium sulphite
The
up the
â&#x20AC;&#x201D; In
contrast.
order to prevent the developer solution
in the presence of air, a preservative is or, occasionally,
sodium
added, usually
bisulphite.
sulphite performs a dual function, namely:
i. it
prevents aerial
oxidation of the developing agent, maintaining the solution colorless both
during mixing and storage, and during use.
When
2.
maintains the developer colorless
it
development takes place
sulphite, the developing solution
in the absence of air and becomes colored by the oxidized by-
In the presence of sulphite these oxidation
products of development.
products combine or couple with the sulphite to form colorless sulphonates.
The this
addition of too
for silver halide If
much
chemical in addition to
some
sulphite its
is
and exerts a retarding
silver halide is dissolved
to be avoided, however, because
action as a preservative effect
is
also a solvent
on the rate of development.
from the film as a result of an excess con-
centration of sulphite in the developer, a type of chemical fog called " sulphite fog "
may
be produced (see Chapter XI, page 249).
This
is
caused by the reduction to metallic silver of the silver salts dissolved out
by the sulphite while the emulsion 1
"Chemical Fog" by
J. I.
Crabtree.
is
in the developer.^
Amcr. Ann. Phot.
33, 20 (1919).
MIXING AND USING PHOTOGRAPHIC SOLUTIONS The question
often asked, "
is
sometimes used as preservatives
Why
117
are both sulphite and bisulphite
The
developer?
in a single solution
car-
bonate reacts with the bisulphite to form sodium sulphite and sodium
why
bicarbonate so
answer
is
not use more sulphite in the
place? "
first
The
that developers containing bisulphite tend to give slightly less
fog than those containing only sulphite and
it
has not been possible to
duplicate exactly a developer containing both sulphite and bisulphite
by using a mixture of sulphite and sodium bicarbonate (see further details in Chapter X, page 215). Sodium sulphite is supplied in two forms, namely, the crystalline heptahydrate which has the formula Na.,S0...7HoO, and the desiccated form which contains no water. The water in the crystalline form is united
when it is crystallized and is known as The crystalline form, when pure, requires dry salt when substituting in a formula. The
chemically with the sulphite *'
water of crystallization."
twice the weight of the
desiccated salt as supplied to the photographic market usually contains
96
to
97%
pure sulphite.
Ordinary sodium bisulphite has been shown by analysis chiefly of metabisulphite
which
Sodium bisulphite may be substituted weight
solved in water.
weight for potassium metabisulphite. factory but the former
is
The
and
of three kinds:
The quantity and If
the carbonated
pH
from one-third
alkali if
resulting
is
there
the action of the developer will be retarded. gelatin of the emulsion,
alkalis
present, the developer
is
a deficiency of alkali
Alkalis also soften the
and a strongly alkaline developer in
frilling
or
and the
value of the alkali govern the
an excess of
tend to produce chemical fog, while
over-swelling
costs
available on the American
â&#x20AC;&#x201D;
energy of the developer. will
it
for
equally satis-
Most developing agents will not develop unless in The alkalis most commonly used in development are
the caustic alkalis,
borated alkalis.
is
is
a very pure form.
least, in
Activator.
alkaline solution.
Either chemical
usually preferred since
to one-half the price of the latter
market, at
to consist
converted into bisulphite when dis-
is
blisters,
especially
will
produce
during hot
weather, unless precautions are taken to minimize such tendencies.
The Meaning is
of pH.
â&#x20AC;&#x201D; In comparing the
necessary to understand the meaning of
properties of alkalis,
it
pH values. The acidic proper-
ties of an acid solution are attributable to the presence of free hydrogen ions and, conversely, the properties of an alkaline solution are due
to the presence of free
hydroxyl
ions.
In any aqueous solution, the
product of the concentration of the hydrogen and hydroxyl ions
is
con-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
118
slant so that in a strongly acid solution there
is
an excess of hydrogen
ions in relation to hydroxyl ions and, vice versa, in an alkaline solution
there
is
a relative dearth of hydrogen ions and an excess of hydroxyl
ions.
"
The degree pH," which
of acidity or alkalinity is
usually expressed
is
by
the symbol
equal to the logarithm of the reciprocal of the hydrogen
ion concentration, or
pH
=
Log
^
An
ion concentration.
solution has, therefore, a relatively high
pH
alkaline
value as compared with that
an acid solution.
of
pH
Developer solutions containing caustic soda usually have a
range
of ii.o to 12.0 or higher; those containing carbonate, 9.5 to 10.5; those
containing Kodalk, 9.0 to 10. o; and those containing borax, 8.0 to 9.0,
pH
pure water having a
The
of 7.0.
higher energy developing agents such as Elon which bring up
the image rapidly, require less alkali than the slower developing agents.
Hydroquinone,
for instance,
is
often used with caustic alkalis, while most
other developing agents require only the weaker carbonated alkalis. It
should be remembered, however, that a water solution of Elon
is
acid in character and requires a definite quantity of alkali to neutralize
the acidity before ers
it
will
develop an image.
In weakly alkaline develop-
such as those of the borax type, this neutralizing
much more apparent than with
effect of the
Elon
is
those containing a larger quantity of
carbonate.
The carbonates the carbonate
are salts of a
is split
up
weak
acid, carbonic acid.
carbonate) and caustic alkali.
A
sort of reservoir of alkali
created, only a small quantity of alkali being present at
more
is
generated by dissociation as the alkali
carbonate makes alkali
and
to
keep
it it
In solution,
slightly or dissociated into bicarbonate (or acid
possible to
is
is
thus
any time, but
used up.
The
use of
employ only a small concentration
approximately constant throughout the
life
of
of the
developer.
Sodium carbonate
is
supplied commercially in three varieties, namely,
the decahydrate, which contains ten parts of water to each part of car-
bonate, the monohydrate, which contains one part of water, and the desiccated form, which contains no water.
Very pure grades
of desic-
cated sodium carbonate have been available commercially for years and have found extensive use in
all
many
branches of photographic work.
Within recent years monohydrated sodium carbonate has come into favor with this
some photographers and laboratories because of claims that it is more stable in so
has less tendency to cake on mixing and that
MIXING AND USING PHOTOGRAPHIC SOLUTIONS far as
does not absorb moisture
it
damp weather
in
Experiments have shown that
dry weather.
119
or lose moisture in
desiccated carbonate
if
is
stored with only moderate care in a closed bin, barrel, bottle, or can, the
quantity of water absorbed
is
rarely of sufficient
appreciable photographic effect, while
than that of monohydrated carbonate. crystallization present in the
use
17'^f
The
Na,B^O-.ioH,.0,
to
is
have any
no greater
Also, because of the water of
monohydrated
variety,
more than when the desiccated variety
alkali borax,
magnitude
caking tendency
its
is
is
it
is
necessary to
used.
being used extensively for the
preparation of low contrast developers.
Borax, however, does not ap-
pear to have any specific ability to produce fine grained images but
what
is
known
as a " buffer " alkali, that
is, it
for delivering small quantities of alkali at
is
acts as a large reservoir
any one time
so that during
exhaustion or on the addition of an acid the alkalinity of the solution
does not change appreciably until
Kodalk their
*
â&#x20AC;&#x201D; One
tendency
to
all
the borax has been neutralized.
of the disadvantages of the carbonated alkalis
is
cause blisters within the gelatin layer as a result of the
release of carbon dioxide gas
when
the alkaline developer
is
neutralized
by the acid fixing bath. This trouble is particularly serious in summer months when temperature control of solutions becomes more difficult. Carbonate also tends to precipitate a sludge of aluminum sulphite in a potassium alum acid hardening fixing bath (without boric acid) when the acidity is low by virtue of exhaustion of the bath. The precipitate deposits as an objectionable scum on the surface of films and prints. Both of these difficulties can be avoided by using developers containing borax instead of carbonate but, because of the limited solubility of
borax,
it is
tivity.
By
possible to
compound only developers having
a limited ac-
plotting the concentration of an alkali against the developer
shown in Figure 64, it is seen that in a given formula, 40 grams (ij ounces) of borax are required to give the same activity as 4 grams (60 grains) of desiccated sodium carbonate. activity, as
The shortcomings of both carbonate and borax are avoided by using new alkali known as Kodalk which has properties lying between those With increasing concentrations of the carbonate and borax (Fig. 64.) a
of this alkali, the activity of
idly as
when carbonate
is
an
MQ
developer does not change as rap-
used, so that
it is
possible to control precisely
by varying the concentration of Kodalk. The alkali does not cake when added to water and does not Blister formation is release a gas when added to an acid fixing bath. the activity of a weakly alkaline developer
*
Supplied by Eastman Kodak Co., Rochester, N. Y.
120
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
therefore avoided.
Also, fixing baths containing potassium
alum do not
sludge as readily with developers containing Kodalk as with developers
containing carbonate and trouble from scum formation
mized. in
Formulas containing Kodalk are marked
Appendix A, Chapter XIV, page 279.
0.50
"
is
DK-
"
thereby mini-
and are given
MIXING AND USING PHOTOGRAPHIC SOLUTIONS
121
emulsions, compensation for overexposure by juggling with the bromide
content of the developer
is
no longer necessary.
Moreover, since the
presence of bromide in a developer lowers the effective emulsion speed, it is
if
desirable to maintain the bromide concentration at a
possible, to eliminate
it
Bromide accumulates development so that
if
minimum
and,
entirely.
in the
developer with use as a by-product of
the fresh developer gives a trace of fog, this usu-
ally disappears after the solution has
been used
slightly.
TECHNIQUE OF MIXING Developing Agent and Preservative. like
hydroquinone
velop at
all
brown as a
is
or only very slowly,
quinone with the oxygen present
a developing agent
is
it
will gradually turn
combination of the hydro-
in the air in
This oxidation product
contact with the surface
of the nature of a
dye and
will
dye solution.
stain fabrics or gelatin just like a
On
If
and on standing
result of oxidation or chemical
of the liquid.
—
dissolved in water, the solution will either not de-
adding a solution of an alkali such as sodium carbonate, the hydro-
quinone solution at once becomes a developer, but at the same time the rate of oxidation
is
increased to such an extent that the solution very
rapidly turns dark brown, and
if
a film
is
developed in this solution,
becomes badly stained and sometimes fogged.
The
it
subject of devel-
oper fog has been treated fully in a series of articles to which reference should be made.-If
we add
a
little
tioned above, the solution
is
'
sodium sulphite
brown
obtained.
to the
color or stain
Therefore,
if
is
brown-colored solution menbleached out and a colorless
the preservative
is
added
first to
the
developer, then on adding the accelerator, the solution should remain perfectly clear because the sulphite preserves or protects the developing agent from oxidation
As a general
An
by the
air.
rule, therefore, the preservative
Elon or a similar developing agent stance 2 3
should be dissolved
first.
exception to this rule should be observed with formulas containing
is
readily soluble in
warm
in concentrated solution.
This sub-
water, about i25°F. (52°C.), and
"Chemical Fog" by J. I. Crabtree. Amcr. Ann. Phot. 33, 20 (1919). (a) " The Fogging Properties of Developers " by M. L. Dundon and J. I. Crabtree, Amcr. Phot. 18, 742 (1924) (b) " Sulphide Fog in Motion Picture Developers " by M. L. Dundon and J. I. Crabtree, Amcr. Phot, ig, 96 (1925) (c) " The Staining Properties of Motion Picture Developers " by J. I. Crabtree and M. L. Dundon, Trans. Sac. Mot. Pict. Eng. No. 25, 108 (1926). ;
;
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
122
does not oxidize rapidly.
If the sulphite is dissolved
white precipitate often appears, especially
if
before the Elon, a
the sulphite solution
con-
is
centrated.
This precipitate forms because Elon base with an acid which renders
weak
neutralized by a
also in a solution of
sodium
When
the acid portion
is
sulphite, the insoluble base
is
soluble in an excess of water
is
sodium carbonate with which the base forms a
When
salt.
a combination of an insoluble
sodium
This Elon precipitate
precipitated.
ble
alkali such as
is
soluble.
it
once the Elon
is
dissolved, however,
fairly high concentration of sulphite to bring
though only a low concentration of sulphite
Elon from dissolving.
is
and
solu-
takes a
it
out of solution again,
it
required to prevent the
a precipitate forms on dissolving the Elon and
If
sulphite, this will usually redissolve
on adding the carbonate or alkali
and no harm has been done.
Some
direction sheets
be dissolved
first in
little
that a portion of the sulphite should
and then the remainder
solve the Elon,
add a
recommend
order to prevent the oxidation of the Elon, then dis-
of the solid sulphite to the
This procedure
of the sulphite.
quite satisfactory, though
is
Many
workers
Elon when dissolving the the Elon
if
is
latter.
dissolved
alone in water at a temperature not above i25°F. (52°C.), and the sulphite dissolved immediately afterwards, will
little
or
no oxidation products
be formed, which otherwise might produce chemical stain.*
Activator. 1.
â&#x20AC;&#x201D; The
solution.
There
the alkali
is
2.
alkali
may
be added
in
one of three ways:
Dissolve the alkali separately and add to the cooled Elon-sulphite
Add
is
danger, however, of the Elon precipitating out before
added.
the solid alkali to the Elon-sulphite solution, stirring thor-
oughly until dissolved. 3.
cool,
After dissolving the Elon, dissolve the sulphite and alkali together,
and add
to the
Elon solution.
to the developing agent,
substance
is
even
formed which
in the
If a
hot alkali solution
is
added
presence of the preservative, some
may produce
chemical fog with certain devel-
oper samples.
In the case of some samples of para-aminophenol which are discolored
by by
the presence of oxidation products, these
may
boiling after adding to the sulphite solution.
tion products are reduced again
by the
be partially removed
In this way, the oxida-
sulphite to colorless products
* The quality of chemicals supplied for photographic work has improved greatly since 1920 and they have less propensity to produce fog, colored solutions, etc., if the
above precautions are not observed.
MIXING AND USING PHOTOGRAPHIC SOLUTIONS
123
though the sokition should be cooled again before adding the alkali. If pure chemicals are used, such a procedure is, of course, unnecessary. In the case of desiccated chemicals like sodium carbonate and sodium sulphite,
add the chemical
The
ing will result.
Restrainer.
—
to the
It is
water and not vice versa, otherwise cak-
Kodalk,
alkali,
is
not subject to caking.
immaterial at what stage the bromide
is
added
during the mixing.
GENERAL HINTS ON MIXING DEVELOPERS 1.
Water Temperature.
except 2.
ber. 3.
when
— Use
a higher temperature
is
water at i25°F. (S2°C.) or
less
recommended.
specifically
— Use good enamelled ware, ware, or hard rubwhich cause Avoid copper, or galvanized mixCheck the Formulas. — Arrange the chemicals needed Containers.
glass
fog.
iron
tin,
for
ing at one end of a shelf or bench.
As each one
is
weighed out, place the
Use only
stock can or bottle on the opposite side of the shelf or bench.
chemicals of reliable manufacture. 4.
Water
First.
Caking
chemicals.
— Pour water
results
into the container,
from adding water
to
and then add the
dry chemicals.
Boiling
water should never be used unless specifically recommended. 5.
Avoid Premature Oxidation.
— Add
water before adding the developing agents.
Elon because of 6.
its
This
slow rate of oxidation.
Complete Solution of Each Chemical.
cal completely before
adding the next and
a
little is
sulphite to the
not necessary with
— Dissolve each chemi-
in the order given.
PRACTICAL RULES FOR MIXING DEVELOPERS The
following practical procedures are
recommended
for
mixing de-
velopers, unless definite instructions otherwise are given with the formula.
A. For Mixing Small Volumes of Developer (Less than 5 Gallons).
—
i.
Weigh out
all
of the chemicals, placing each one on a
separate piece of paper on which is
its
name and weight
are written.
It
then possible to check the chemicals before starting to dissolve them,
thus greatly reducing the possibility of error.
Be
sure that the scales
are sufficiently accurate, particularly for the developing agents, potas-
sium bromide, and any other ingredients which are used discussion on scales, page 15).
in
small quan-
tities (see 2.
Into a container large enough to take the
tion place a
volume
of
warm water
full final
volume
of solu-
(not over i25°F.) (52°C.), equal to
one-half to three-quarters of the total volume to be used.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
124
Elon
3. If there is it is
4.
to the
it
water and
stir until
completely dissolved.
Add
the sulphite or other preservative (bisulphite, potassium meta-
and
bisulphite, etc.)
Add and make 5.
6.
add
in the formula,
stir until fully dissolved.
the remaining developing agents (hydroquinone, pyro, etc.) sure that they are completely dissolved.
If the
formula contains an acid material,
in addition to a carbonate,
the acid substance should be dissolved and mixed in with thorough stirring. 7.
Dissolve the alkali (carbonate, Kodalk, borax, etc.) and mix.
the formula contains caustic soda,
it
Then pour
small volume of cold water.
If
should be dissolved separately in a the caustic solution in slowly
while stirring the remainder of the developer. 8.
Dissolve the potassium bromide and any other remaining ingre-
dients. 9.
After
all
the chemicals have been dissolved in turn, add sufficient
cold water to bring the solution
oughly
mix
in order to
up
to the correct
volume, and
stir thor-
the water with the heavier solutions already
present. 10.
Filtering
used, but
if
is
there
unnecessary is
if
clear water
and clean chemicals are
evidence of a sediment or suspension, the solution
Complete directions on
should be filtered before use or storage.
filter-
ing are given in Chapter III, page 31. 11. If the solution in
is
not to be used immediately,
a clean bottle of the proper
An example
of this
method
size,
of mixing
Developer
is
A grains
45
Sodium
Sulphite, desiccated
Hydroquinone
1
'2
2J
ounces grains
135
Sodium Carbonate, desiccated Potassium Bromide Water to make
should be placed
as follows:
Avoirdupois
Elon
it
stoppered, and labeled plainly.
2
ounces
15
grains
32
ounces
Metric 3.1
45.0 9.5 75.0
grams grams grams grams grams
1.1 1.0 liter
Dissolve the Elon in 16 ounces (500 cc.) of water (about I2S째F.) (52째C.), then add the sulphite, and when completely dissolved, add the hydroquinone. Finally add the carbonate and bromide and cold water to make 32 ounces (i liter).
An
above consists in weighing out and Pour the mixture slowly into 90^0 of the water with rapid stirring and then dilute to volume. only satisfactory for small volumes of solution. The
alternative
method
to the
mixing the dry chemicals. total
volume
This method
of is
dry chemicals must also be mixed uniformly and added immediately to the water. If the dry mixture is allowed to stand around for an hour or
MIXING AND USING PHOTOGRAPHIC SOLUTIONS so,
may
it
absorb moisture from the
and produce B. For
125
dissolve with great difficulty,
air,
a colored solution.
Mixing Moderately Large Volumes of Developer
to 500 Gallons).
— The
following procedure
is
safe
and
(5
probably
is
more economical of time. 1. Weigh out the chemicals and check all weights carefully. It facilitates weighing if two pairs of scales are provided, a large one and a small one. 2.
In a tank large enough to take the
volume
final
of solution, place
a volume of water equal to about one-tenth the final volume. 3.
In a separate container (enamelled pail or rubber bucket
Chapter IV, page 68) dissolve each of the chemicals
volume of warm water (not over
—
see
in turn in a small
(52°C.) and add to the
i2 5°F.)
A
tank, stirring after each addition to insure thorough mixing.
small
quantity of the sulphite solution should be saved and added to the water in
With some developing
which the developing agents are dissolved.
agents, hydroquinone for example, the total quantity should be divided into
two or more parts and each part dissolved separately.
Also,
it
is
somewhat by adding a por-
usually desirable to cool the tank solution
tion of cold water before adding the solution of the alkali. 4.
Add
cold water to bring the solution to the correct volume and stir
thoroughly to insure complete mixing of
As an alternative
all
to the above, the filter
ingredients.
bag method may be more
convenient (see Figs. 14A and 14B, page 33).
bag
is
In this method, a cloth
suspended over the tank and each chemical placed
solved in turn by allowing a stream of
Do
bag into the tank.
warm
in
it
and
dis-
water to flow through the
not add the water so rapidly that the final vol-
ume is reached before all the chemicals are dissolved. An example of this second method of mixing is as follows: Developer B Metric
Avoirdupois
Sodium
Sulphite, desiccated
Hydroquinone
Sodium Carbonate, desiccated Potassium Bromide Water to make
4
pounds
13
ounces
4
pounds
3 ounces 10 gallons
1800.0 390.0 1800.0 90.0 40.0
(irams
grams $)rams f^rams liters
Dissolve the sulphite in about i gallon (4 liters) of warm water (not over i25°F.) (52°C.). Pour about three quarts of this solution in the tank and add i gallon of
warm water
to the
solution to the tank.
Then when completely
remaining quart of sulphite solution.
(luinone in this dilute sulphite solution
Now,
and,
dissolve the hydrodissolved,
dissolve the carbonate and the bromide in
i
add
gallon of
this
warm
Add cold water immediately to (40 liters). Stir the entire volume of solution with a paddle or a mechanical stirrer until thorough mixing is assured. water (not over I25''F.) ($2°C.) and add to the tank.
make up
to 10 gallons
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
126
C.
For Mixing Very Large Volumes of Developer (500 or
More
Gallons).
— When mixing very
as 500 or 1000 gallons (2000 or
4000
volumes
large liters)
of solution such
or more, the heating or
an important
cooling effect of chemicals going into solution becomes
temperature of the solution when
It is desirable also that the
factor.
mixed should approximate that required
finally
amount
A minimum
for use.
For mixing most
of handling of chemicals should be necessary.
developers (except very concentrated solutions), the use of
water
may
warm
or hot
be dispensed with, providing the volume of water used
sufficiently large
when
is
use of automatic
than hand stirring (see page 27).
stirrers is preferable rather
The temperature
The
dissolving the chemicals.
of the water in
range from season to season.
most cities varies over a fairly wide good practice, therefore, to install
It is
a tempering or mixing device which delivers water at a temperature
somewhat
suitable for use, say, 70°F. (2i°C.) or
the heat of hydration 88).
when
This device could be used most effectively
to heat the
it is
compensate
in the winter
water up to the temperature specified.
tant to cool the tap water in the unless
less to
for
dissolving desiccated sodas (Fig. 42 A, page
summer months
for
months
not so impor-
It is
mixing purposes
necessary to do so in connection with an installation for cool-
ing the solutions during use (see page 89)
Care must be taken not
to use too
much water
or the total
volume of
Some
the developer as finally mixed will exceed the prescribed volume.
chemicals increase the volume more than others; for example, sulphite increases the
volume about
3%
(for a
concentration of carbonate increases
Example.
— When
it
20%
solution), whereas the
same
only i^/r.
mixing 1000 gallons of an Elon-hydroquinone
developer, the tank should
first
be
filled
about half
water.
full of
About
one-quarter of the total quantity of sulphite should then be added to the tank,
and
Then add the hydroquinone.
After this solution has been stirred for
10 or 15 minutes, add the sodium carbonate.
next be run in to solution.
Elon should be added.
after stirring about 5 minutes, the
fill
Then add
the tank to about
80%
Sufficient
the balance of the sulphite,
other ingredient such as bisulphite and citric acid.
volume.
The
stirrer
water should
volume of the the bromide, and any
of the final
Dilute to the final
should be run for about one-half hour after the
chemicals have been added to insure a uniform solution throughout the
mixing tank.
The
valve
may
then be opened and the solution run into
the feed or storage tank, either directly a
pump.
A
filter
may
be installed
by gravity feed
or
by means
of
between the mixing tank and the
MIXIXG AND USING PHOTOGRAPHIC SOLUTIONS
127
feed tank or between the feed tank
and the developing machine (see Chapter IX, page 209). A convenient scheme for mixing and supplying solutions to automatic developing machines is shown in Figure 19, page 39. The solution should be mixed
tanks located preferably above the storage or feed
in
tanks which permits a gravity flow of the solution as shown
pumped
may
diagram A.
Any
tank as in diagram B.
to the feed
type of stirring device
be utilized in the mixing tank but the portable motor-driven pro-
peller stirrer illustrated will be
"
in
space necessitates mixing in a basement, the solution must be
If floor
Theory
of Stirring,"
found very
efficient (see discussion
on
page 28).
Mixing Concentrated Developers. — The extent to which a demay be concentrated is determined by the solubility of the least
veloper
soluble constituent, because a stock solution should usually withstand
cooling to 40°F. (4°C.) without
Table of
any
of the ingredients crystallizing out
page 338). Usually, the hydroquinone and Elon come out of solution on cooling, but this may be prevented by add(see
ing
wood
alcohol If
Solubilities,
alcohol or methanol in a concentration
may
be used
wood
if
on adding denatured alcohol
denatured alcohol
is
up
to
10%.
Denatured
alcohol has been added as the denaturant. to the developer, a precipitate forms, the
unfit for use.
The
addition of the alcohol does not
prevent the other ingredients such as sodium sulphite from crystallizing
and therefore
out; in fact, the alcohol diminishes their solubility creases the tendency to
A
come out
para-aminophenol-carbonate developer
by adding a
centrated form, though the para-aminophenol
is
in-
of solution. is difficult
to
prepare
in
con-
caustic soda the solubility of
little
increased and a stronger solution can thus be
prepared.
When
preparing concentrated developers,
it
is
important to observe
carefully the rules of mixing, taking care to keep the temperature of the
solution as low as possible but yet high if
a colorless developer
The
is
following formula
oper and
is
enough
to dissolve the chemicals
to be obtained. is
a typical example of a concentrated devel-
prepared by dissolving the ingredients
in the
order given:
Concentrated Elon-Hydroquinone Developer Avoirdupois
Water (about
Wood
125° F.) (52° C.)
Elon
Sodium
ounces
16
4'^ ounces
.\lcohol
grains
7.?
Sulphite, desiccated
2':^
^
Hydroquinone
Sodium Carbonate, desiccated Potassium Bromide Cold water to
make
3'
^7 32
2
ounces ounce ounces
Metric 500.0 cc H5.0 cc .5.0
75.0 22.5 105.0
grams grams grams grams grams
grains
2.5
ounces
1000.0 cc
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
128
When
mixing large volumes of an Elon-hydroquinone developer con-
taining a high concentration of sulphite, there
is
a tendency for precipi-
tation of the insoluble base of Elon as explained on page 122.
tendency
may
example,
in
This
be minimized by using a definite mixing technique.
For
mixing large volumes of the low contrast developer (D-yb)
the procedure should be as follows:
Elon-Hydroquinone-Borax Developer
[D-76]
Metric
Avoirdupois
Elon
2
Sodium
Sulphite, desiccated
100
Hydroquinone
5
Borax, granular
Water
to
Directions. in
2
make
1
— Dissolve about
a small volume of
pounds pounds pounds pounds
5.0 2.0
grams grams grams grams
1 .0
liter
2.0
100.0
20 gallons
pounds (900 grams) of the sulphite water (about i25°F.) (52°C.) in an enameled pail 2
or other suitable mixing vessel and add the Elon slowly with stirring.
When
completely dissolved, pour the solution through a cloth
pended over the large tank.
(This
may
filter sus-
be the tank actually used for
development or a storage tank from which the solution
is
pumped
to
the developing tank.)
Divide the hydroquinone into three or four parts. 4 pounds (1800 grams) of sulphite in
and add one of the fractions
When
of the
Dissolve about
hot water (about i6o°F.) (7i°C.)
hydroquinone slowly with
stirring.
Repeat the procedure
dissolved, filter the solution into the tank.
with each of the other fractions of hydroquinone.
The remainder of the sulphite should then be added to the tank by dissolving as much as possible in separate pails of water (about i2 5°F.) (52°C.), and pouring each pailful of solution into the tank. The volume of the solution should now be about 80% of the total volume (90 gallons or 360 liters) after
all
the sulphite has been dissolved and added
to the tank.
Next
dissolve the borax in a pail of water.
the tank and add cold water to
(480
make
Filter the solution into
the total
volume 120 gallons
liters).
It is
important to
stir
the solution in the large tank thoroughly after
adding each pailful of chemicals {especially the developing agents) and again after the solution has been diluted to volume. This prevents the heavier chemical solutions from remaining at the bottom.
Multiple-solution Developers.
— A two-solution developer
is
sim-
ply a one-solution developer split into two parts, one containing the
developing agent and the preservative, the other containing the alkali
and bromide,
so that the developer will oxidize less readily
and therefore
MIXING AND USING PHOTOGRAPHIC SOLUTIONS keep
well.
The reason
two solutions
is
it is
that pyro
129
customary to keep a developer like pyro in becomes oxidized much more readily than
Elon or para-aminophenol with a given amount of preservative, while keeps well
it
in acid solution.
Developers containing caustic soda as the alkali are usually prepared as two stock solutions.
Sometimes a developer
solution formula in order that the alkali
portions to the solution
when
it is
may
is
prepared as a two-
be added in varying pro-
diluted for use.
Pyro developers are occasionally made up in three stock solutions the pyro, bisulphite, and bromide in one solution, the sulphite in another, ;
and the carbonate
mum
in the third solution.
This scheme insures the maxi-
protection of the pyro against oxidation and permits the user to
vary the proportions of the three solutions
if
desired
when mixing them
for use.
When
developers are quite concentrated, the formulas are sometimes
more parts and arranged to facilitate easy mixing. which have a tendency to oxidize very rapidly (such as Formula D-87, page 300), it is customary to dissolve all the chemicals first except the pyro and the bisulphite. Then, when ready to develop, add the bisulphite-pyro solution, dilute to volume, and published
in three or
\\'hen mixing pyro developers
use the developer immediately.
— In
Two-Bath Developers.
the two-bath process (development
in successive baths), the first solution usually consists of
an Elon-hydro-
quinone developer containing sodium sulphate or sugar
to retard devel-
opment, while the second bath contains the activator, a portion of the sulphite, and the restrainer. One type of developer which was compounded for rapid processing contains formaldehyde and sodium sulphite, which react to form sodium hydroxide.^ This second bath, therefore,
hardens the emulsion and likewise accelerates the developing action
of the developer solution absorbed
by the
film
from the
first
bath.
Compo-
Effect of Varying the Proportion of the Developer nents.
— The question
is
frequently asked, "
What
is
ing the quantity of the ingredients in a developer? "
the effect of vary-
At the
should be stated that normally there should be no reason the ingredients of a manufacturer's formula regular development of a product.
•*
"
when
Much time
Rapid Processing Methods " by H. Parker,
is
Jr.,
it is
to
outset,
for
it
varying
be used for the
spent in the preparation
and
J.
I.
Crabtree.
Anter.
also " Some Properties of Two-Bath Developers Phot. 30, 67 ct scq. (Feb. 1936) for Motion Picture Film " by J. I. Crabtree, H. Parker, Jr., and H. D. Russell. /. Soc. ;
Mot. Pict. Eiig. 21, 2\ (July 1933).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
130
and the quantities
of such formulas
group of ingredients which,
of chemicals represent a balanced
for best results,
should be used as recom-
mended. Occasions
however, when a photographer
arise,
perimental work, or
may have
may
contemplate ex-
a peculiar set of conditions in his
own
studio or laboratory necessitating the adaptation of a special developer.
For such contingencies,
may
of chemicals
which
approximate
effect of
To answer
desirable to
is
it
know
the limiting quantities
be used when compounding a formula and the
each on the performance of the developer.
these questions adequately would require a separate trea-
but briefly, increasing the quantity of developing agents increases
tise,
the activity of the developer up to a certain point beyond which a further increase has
Elon
fact that
little
no
or
effect.
In practice,
we
are limited
by the The
not very soluble in a solution of sodium sulphite.
is
solubility can be increased
by adding alcohol
development.
in turn, restrains
The
to the developer but this,
solubility of developing agents in
a developer depends on the salt concentration (sulphite, carbonate, etc.)
and the degree of alkalinity (pH) of the solution. In general, the lower the salt concentration and the higher the pH value, the greater the solubility of the
developing agents.
The maximum per
liter
per
liter
tion of
useful quantity of Elon
(32 fluid (32 fluid
is
about lo grams (150 grains)
ounces) but for average purposes
ounces)
hydroquinone
is
is
The
adequate.
about 50 grams
(32 fluid ounces) although a strength of
(i
5
5
grams (75 grains)
limiting useful concentra-
ounce 290 grains) per
liter
to 10 grams (73 to 146 grains)
more generally used. With developer formulas of the borax type which usually contain a large quantity of sodium sulphite (approximately 10%) the limiting solubility of Elon is approximately 7.5 grams per liter whfle the maximum permissible concentration of Elon and hydroquinone in the ratio of 2:5 is 3 and 7.5 grams per liter, respectively.
is
Glycin
is
of sulphite
almost insoluble in water but
and
alkalis.
An
is
quite soluble in the presence
average concentration in a developer con-
taining about 20 grams per liter (290 grains per quart) of sulphite 5 to
10 grams (73 to 146 grains).
about 50 grams of glycin per
A per
liter
A
limiting useful concentration
(i oz.
290 grains per 32
is is
fluid oz.).
concentration of 50 grams (i ounce 290 grains) of sodium sulphite liter
(32 fluid ounces)
keeping properties.
ment and
to exert
is
A higher
usually sufficient to provide satisfactory
concentration tends to slow
down
develop-
an appreciable solvent action on the emulsion grains.
MIXING AND USING PHOTOGRAPHIC SOLUTIONS The
limiting useful concentration of sulphite
ounces) per
A of
liter
131
about 150 grams (3^
is
(32 fluid ounces).
strength of about 25 grams (375 grains) per
(32 fluid ounces)
liter
sodium carbonate (desiccated) represents an average concentration of
An
this alkali in developers.
up the development
increase in the quantity of carbonate speeds
to a strength of
about 50 grams
(
i
ounce 290 grains)
Beyond this concennot appreciably speeded up but with over 150
of the desiccated salt per liter (32 fluid ounces).
development
tration,
grams lize
is
(5 ounces) per
liter
(32 fluid ounces) the salt tends to crystal-
out at room temperature.
and carbonate
down
also slows
An
excessive concentration of sulphite
the rate of diffusion of the developer into
the gelatin film and tends to retard development. trated developer, therefore, often speeds
A
up the
useful concentration of the alkali, Kodalk,
grains) per liter (32 ounces).
The
ounces)
is
reached.
grams
is
about 10 grams (145
activity of a given developer in-
creases almost proportionately with the limiting concentration of 40
Dilution of a concenrate of development.
(i
Kodalk concentration ounce 145 grains) per
liter
(32
This property of the almost proportionate change
in developer activity with increased alkali concentration
useful properties of Kodalk, because
it
is
one of the
permits adjustment of the activ-
moderately alkaline developer.
ity of a
Trisodium phosphate concentration
is
activity tends to
The
.
is
used occasionally
in developers.
An
average
about 15 grams (4 ounce) per liter (32 ounces). The increase with increased alkali content to a limiting con-
centration of about
ounces)
until the
100 grams (3 ounces 145 grains) per liter (32 is its propensity to cause
objection to the use of this alkali
the formation of an insoluble precipitate of
aluminum phosphate
in the
fixing bath.
An
average concentration of sodium or potassium hydroxide
10 to 20 grams per
These
liter
is
about
(145 to 290 grains per quart) of developer.
alkalis are extremely soluble
and
their use
is
therefore limited
by
the quantity that can be added without producing excessive fog or
swelling of the emulsion.
borax per
liter
At 6o째F. (i5째C.) a maximum
can be dissolved.
As the proportion
grams
of 20
of borax
is
of
increased
from a zero value, the rate of development increases rapidly up to a liter beyond which the development rate
concentration of 10 grams per increase
A
is
relatively slow.
useful concentration of potassium bromide for the average negative
developer
although
is i
its
to 1.5
grams (15
to 25 grains) per liter (32 fluid
use should be avoided whenever possible.
ounces)
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
132
â&#x20AC;&#x201D;
Testing the Mixed Developer. Every developer solution should be tested before use. As mentioned previously (page 13) the use of a hydrometer a developer.
is
meaningless for determining the satisfactory condition of
The only
or paper) therein for a
reliable test
known time
is
develop an exposed film (plate
to
at a definite
temperature and to com-
pare the resulting image with a standard image which has been exposed
and developed under known conditions
in a similar
Testing a Tank Developer During Use. isfactory
methods
manner.
â&#x20AC;&#x201D; One
of the most sat-
from
of testing a tank developer consists in printing
a standard master positive using controlled exposure and comparing the quality of the developed negative obtained with that of a standard nega-
The developed
good quality.
tive of
negative should match the standard
both with regard to highlight density and shadow
detail.
highlight density (which largely determines the contrast
low)
is
ment
or
If
the
the fog
is
weak, this indicates the need either of a longer time of develop-
more replenisher or both.
standard but there
If the contrast
is
equal to that of the
a considerable loss of shadow detail, this indicates
is
that the developer has accumulated an excess and a fresh developer should be prepared.
A
if
of restraining products
rapid test for determining the degree of exhaustion of developers has
been suggested by Dundon, Brown and taining a sensitometric exposure
is
ing the time accurately to the second.
ment (30 seconds
to
minutes),
2
Capstaff.'^
dipped quickly
it is
A
strip of film con-
in the developer, not-
After a short time of develop-
removed and plunged
hardening stop bath containing potassium iodide.
into an acid
This bath neutralizes
the alkali in the developer and stops development, and the iodide converts the undeveloped silver to
examine the
strip at
once
bromide
to iodide
in the light
which makes
(without fixation).
it
possible
Compari-
son with a standard indicates the degree of development which has taken place in the used developer.
For best results the
test
must be standard-
ized for the developer used.
THE LIFE OF DEVELOPERS A. Without Use. water boiled to free
it
â&#x20AC;&#x201D;
If
a freshly mixed developer (prepared with
from dissolved
air) is stored in a
completely
filled
and stoppered or wax-corked bottle, it will keep almost indefinitely even in the light. Under ordinary conditions of storage, the bottle or vessel contains more or less
cover 5
/.
is
air.
Also,
when an ordinary cork
employed, the surface of the developer
Soc. Mot. Pict. Bug. 14, 389 (April 1930).
is
or non-airtight
continually in contact
MIXING AND USING PHOTOGRAPHIC SOLUTIONS with
air,
133
the oxygen constituent of which oxidizes the developing agent
and sodium sulphite present. This results in a lowering of the developing power in direct proportion to the amount of oxidation of the developing agent, which is accelerated as the preservative or sodium sulphite becomes oxidized
The
also.
oxidation products of developing agents are usually colored so
that the developer on keeping frequently turns dark brown.
presence of sodium
may
quinone
consist of hydroquinone
colorless
is,
The
mono- and di-sulphonates which
an old Elon-hydroquinone developer is therefore, no indication that the original developing power
are colorless."
is
In the
sulphite, however, the oxidation products of hydro-
unimpaired.
An
fact that
oxidized Elon or Elon-hydroquinone developer also
frequently fluoresces strongly.
Developers of low or moderate alkalinity containing Elon and hydroquinone may actually show an increased rate of development on aging which, in the case of a developer containing borax as the alkali, plained by Carlton and Crabtree alkalinity. *
This
effect
may
by the formation
gators
"'
of the
hydroquinone
in the
"
is
ex-
as resulting from an increase in the
be explained according to several investiof caustic soda during the aerial oxidation
presence of sulphite, which reaction also re-
mono- and di-sulphonates of hydroquinone. studied this effect and reported similar results. The
sults in the formation of
Tausch
"
has also
effect of this increased alkalinity rapidly disappears,
as a sufficient quantity of the hydroquinone
is
however, as soon
used up to reduce
effec-
tively its initial concentration.
A will
solution of a developing agent to be stored for a considerable time
keep best
in the presence of
an acid sulphite such as sodium
phite rather than sodium sulphite which
ways
slightly alkaline.
is
bisul-
It is al-
preferable, therefore, to prepare a developer as two solutions: one
containing the developing agent and sodium bisulphite, and the other the carbonate and bromide, and to mix these solutions as required for
Stock solutions containing sodium sulphite alone or in combina-
use.
tion with a developing agent should be prepared so that the concentra-
tion of the sulphite erties/"
Sodium
is
around
io%
to
15%
for
Pinnow.
"
Trans. Soc. Mot. Pict. Eng. No. J*. 406 (1929)Camera (Luzern) 9, 128 (Nov. 1930).
Zeit. wiss, phot, ii,
more
keeping prop-
dilute solutions
289 (1912-13).
c
8
maximum
bisulphite keeps satisfactorily in
Phot. lud. 29, 934 and 1320 (1931). A. & L. Lumiere and A. Seyewetz. Bull. soc. franc, phot. (2) 5. 226 (1904) also L. Lumiere and A. Seyewetz. Bull. soc. chim. (3) 33, 444 (1905)9
10
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
134
and
is
a better preservative than sulphite in the absence of carbonate.
It is usual therefore to
keep readily oxidizable developing agents such
by mixing with sodium bisulphite. On adding sodium carbonate to sodium bisulphite, sodium sulphite and sodium bicarbonate are formed, so that in compounding a two-solution formula as pyro, amidol, etc.,
from a one-solution formula
it is
necessary to take care of this neutraliza-
by using an extra quantity. A more complete dissubject will be given later in Chapter X on " Substitution
tion of the carbonate
cussion of this of Chemicals."
Fig. 65
â&#x20AC;&#x201D; Restraining
effect of
developer reaction products on wet and dry iilm.
Single solution developers containing sodium hydroxide or potassium
hydroxide do not keep well unless the bottle
B.
With
pends on
its
Use.
â&#x20AC;&#x201D; The
life
is
stoppered tightly.
or period of usefulness of a developer de-
particular composition, the surface area exposed to the air,
the temperature, the degree of agitation, and whether the solution
is
used
During development, several reactions the developing agent (s) and sulphite are being
continuously or intermittently. are taking place:
i.
oxidized
by
result of
performing useful work
the air;
2.
each developing agent
is
in reducing the
being destroyed as a
exposed
silver halide
and 3. oxidation products of the developer and the by-products, sodium bromide and sodium iodide, are accumulating. The bromide and iodide and developer oxidation products restrain development while the oxidation products prevent aerial fog. The restraining action of the bromide and iodide is analogous to cutting down the exposure, so that with an old developer it is not possible even on prolonged development to get the ultimate result out of an underexposure. emulsion to metallic
silver;
MIXING AND USING PHOTOGRAPHIC SOLUTIONS The
essential changes going
on
in
135
a developer during use therefore
consist of a depletion of the developing agent (s)
and the accumulation
of restraining products, chiefly developer oxidation products together
with sodium bromide and sodium iodide.
Exhausted
Fresh Fig. 66a
â&#x20AC;&#x201D; Effect
negative quality.
The shown
â&#x20AC;&#x201D; not
replenished
of developer exhaustion without replenishment on
Negatives developed for equal times.
restraining effect of the developer reaction products
Figure 65.
in
of holes
is
clearly
This picture was obtained as follows: a number
were punched in a sheet of black paper which was used as a
negative to expose two sheets of film.
The
were then slightly
films
fogged and afterwards both were developed in a tank while held stationary.
One
of the films
was soaked
in
In
water previous to development.
the case of the dry film the reaction products of development which are
downward and
heavier than the surrounding developer gravitated
re-
strained the development of the fogged area immediately below the black circles,
thus producing white streaks.
reaction products diluted with water
In the case of the wetted film, the
had a lower
specific gravity
than
that of the developer and therefore traveled upward, producing streaks.
A
similar effect occurs during the development of
image at the junction of a shadow and a highlight and in the print as a
white line around a dark object.
"
The
Mackie
line."
effect is
posed negatives developed for full
development.
It is
any photographic is
This
often apparent is
known
as a
more noticeable in the case of fully exa short time and tends to disappear with
Agitation will largely prevent
it.
very important to get a clear conception of the effect of the de-
veloper reaction products on the nature of the developed image as the
developer becomes exhausted.
It is well
known
that potassium bromide
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
136
development and has an
restrains
An
exposure. ucts
maximum
therefore incapable of getting the
is
produced by
effect similar to that
less
old developer contaminated with developer reaction prod-
out of an underex-
posure so that films developed in an old developer appear relatively
The
underexposed.
effect of
exhaustion
is
shown
Figure 66A, which
in
developed for a standard time
illustrates test negatives
in
a fresh devel-
oper and also after exhausting with loo rolls per gallon (i aver,
one 8 by lo-inch film) without replenishment.
roll
=
Both negatives were
given the same time of development.
some extent by shadow detail The loss of shadow
It is possible to offset these effects of exhaustion to
prolonged development but there
even with longer development detail
is
more
serious also
in a
is
always some
loss of
used developer.
when developing
to
low contrast than at higher
contrast.
The
addition of a suitable replenisher solution to
many
developers,
however, will compensate for this loss of shadow detail to a considerable Detailed information has been published on replenishment of
extent.
developers for motion picture work and for photofinishing.^^
Replenishers usually contain an excess of developing agents and alkali over the original formula, and the same sulphite but no bromide.
It is
the additional developing agents and alkali in the replenisher which offset the restraining effects of the
bromide and the developer reaction
products.
The extent of the maintenance of shadow detail by replenishing in way is shown in Figure 66 B, which compares prints made from a
this
negative developed in a fresh developer and from a negative developed for the
same time
in
an exhausted developer which had been replenished.
It is impractical,
definitely unless
accumulates a
it is
however, to exhaust and replenish a developer filtered at
silver sludge
in-
frequent intervals, because the solution
and particles
picked up on the surface of the film.
of gelatin
which are apt
The developer may
to be
also acquire
fogging or staining properties.
The exhaustion products
of
development have a beneficial
effect in
so far as they reduce the fog density of a fresh developer which, in
many
The
fog in
may
cases, 11
"
A
be excessive and
is
apparent as veiled shadows.
Replenishing Solution for a Motion Picture Positive Developer " by
Crabtree and C. E. Ives.
/.
J.
I.
Soc. Mot. Pict. Eng. is, 627 (1930).
" The Maintenance of Negative Quality " by Amcr. Phot. 31, J. I. Crabtree. 874 (November 1937) et seq. " Report of the Committee on Laboratory Practice." /. Soc. Mot. Pict. Eng. 26,
345 (April 1936).
-
AND USING PHOTOGRAPHIC SOLUTIONS
INIIXING
a fresh developer
may
be overcome in three ways:
quantity of potassium bromide (0.5 gram per lon) or potassium iodide (o.oi
gram per
(i
by adding a small
c.
(30 grains per gal-
liter)
liter)
137
dram
of a
10%
solu-
by mixing a definite proold developer with the new; and c. by
tion of potassium iodide per gallon) or both; b.
portion (from 10 to
2 5')t
of
)
developing a few test or waste films in the fresh developer.
Exhausted
Fresh Fig. 66b
â&#x20AC;&#x201D; Comparison
of prints
times in fresh and exhausted (replenished)
shadow
â&#x20AC;&#x201D;
Replenished
from negatives developed
detail in the replenished developer
developers. is
for equal
The
loss in
surprisingly small.
The point at which a developer ceases to be useful depends on what is demanded of it. The time required to produce a definite contrast increases as the developer
when
used, and the developer ceases to be useful
is
the time required for this exceeds the
maximum
This
allotted for the developing operation.
is
of
time which can be
most importance
in
production laboratories where work must be finished according to a definite time schedule.
The by
its
life
of a motion picture developer
staining point.
the developing
life
is
most frequently determined
This frequently occurs long before the limit of
has been reached.^
Developer Troubles.
â&#x20AC;&#x201D; In order
to be able to explain the reason
any particular developer trouble, it is necessary to understand thoroughly what takes place when the ingredients are mixed in the wrong order or if any ingredient is omitted from the formula, and also the effect for
of chemical impurities.
trouble but the 12 "
M.
L.
It
is
unnecessary to indicate every possible
more important ones may be
listed as follows:
The Staining Properties of Motion Picture Developers
Dundon.
"
Trans. Soc. Mot. Pict. Eiig. No. 25, 108 (1926).
by
J. I.
Crahtree and
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
138
A.
The Solution
Is Colored.
when mixed, should be
colorless,
— As and
mixed with bisulphite, which contains to
colored, the developer should
In the case of a pyro developer
be suspected as being likely to give fog.
pyro
a general rule, the developer,
if
to the solution, although photographically If
B
combines with the
iron, the iron
form an inky substance which imparts a dirty bluish-red color
a pyro developer
solution,
is
it is
harmless.
mixed as two separate
solutions,
A
and B, the
which usually contains only carbonate and bromide, should
be perfectly colorless, though
if
carelessly
be colored brown by the presence of a
mixed
little
in dirty vessels
Any
pyro A.
it
may
stock solu-
tion containing pyro, however, usually has a faint pinkish color
when
freshly mixed.
— Either the developing agent or the carbonate was omitted during mixing. a white preC. The Solution Contains a White Sludge. — B.
The Solution Does Not Develop.
If
an AIQ developer on standing,
cipitate settles out of
Elon (or
result of the
precipitate
may
methanol, but too
if
much Elon
this is
probably a
developing agents) precipitating out.
allied
often be redissolved by adding this is not successful, then the
5%
wood
of
This
alcohol or
formula contains either
enough carbonate. If it is known that solution when mixed correctly and should the
or sulphite or not
the formula gives a clear
Elon precipitate out during mixing when the sulphite cipitate will usually redissolve
is
added, the pre-
on adding the carbonate or by heating
(not over i25°F.) (52°C.).
which
—
When a film or plate is immersed in a solution, any demay be lying on the surface is picked up by the gelatin
D. Scum. posit
coating and, unless removed by mechanical means, adheres thereto
throughout the processing and produces an image on the print. surface deposits are termed "
photographic solutions.
minute trace of scum
may
It will
Then
and
may
occur on
be, place a
drop of printer
s
all
Such
types of
how harmful a
ink on the surface
and pass a comb along the surface of the and remove it at once.
lay a sheet of paper on the surface
be seen to be covered entirely with streaky ink markings.
Scum on 1.
"
In order to appreciate fully
of a small tray of developer liquid.
scum
developer solutions
Organic matter
in the
may
be caused by:
water which
is
precipitated
by
the developer
chemicals and then rises to the surface. 2.
The presence
of calcium salts in the water,
which are precipitated
by the alkali in the developer. 3. Drops of oil or grease dropped accidentally onto the surface
of the
MIXING AND USING PHOTOGRAPHIC SOLUTIONS solution.
These are particularly apt
to occur
139
with developing machines
(Fig. 67). 4. Fungus growths or slimes on the sides of the tank, especially with wooden tanks. These become detached and float to the surface. 5.
Small particles of gelatin which are detached from the emulsion
warm
coating due to careless handling especially in
Fig. 67
â&#x20AC;&#x201D; Developer scum markings caused by
Such contaminations may be prevented by for
compounding the
a.
oil
weather.
and
grease.
the use of distilled water
solutions (see Chapter VI, page 106), b. the use of
water softeners (see Chapter \T, page no),
c.
cleaning and brushing the
powder (chloride of lime) followed by scalding so as to prevent slime formations (see Chapter XII, page 265), d. keeping the developer cool so that the gelatin is firm and not subject walls of the tanks with bleaching
to abrasion,
e. filtering,
and
/.
skimming the developer before use. daily rigid routine and may be
The skimming operation should be a accomplished by i. drawing the edge of the surface of the liquid or
skimming device E.
2.
suitable
(see Fig. 20, page 40).
The Developer Gives Fog.
by faulty mixing.
a sheet of blotting paper across
skimming the solution with a
It
may
â&#x20AC;&#x201D; Fog
is
the chief trouble caused
be a result of violation of the rules of mixing,
such as dissolving the carbonate before the sulphite, mixing the solution too hot, omission of the bromide, addition of too much carbonate or too little
sulphite, the use of
Developer fog
may
impure chemicals,
etc.
be defined as the formation of " a
deposited especially on those portions which receive
veil of silver
little
or no expo-
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
140
more or less to the total density Fog may be classified in two ways:
sure and which adds ^^
image."
Fog produced
1.
as a latent
of the developed
image before development and consisting
of the following types:
Emulsion Fog.
a.
— This
may
be a result of the presence of de-
velopable grains in the unexposed emulsion, or in fast emulsions
it
be only an increased susceptibility to chemical development fog.
may
Mod-
ern emulsions exhibit only a very slight tendency to emulsion fog.
Light Fog.
b.
— This
caused by accidental exposure to white
is
by the use of an unsafe light when handling photographic materials. Fog of a similar character may result from accidental exposure X-ray fog is usually distributed uniformly throughout the to x-rays. light or
emulsion layer whereas light fog
may
of the emulsion. c.
Fog from Vapors and
tine, benzol,
ether,
or
and
be confined to the surface layers
— Exposure
Gases.
to gases
to
vapors of turpen-
such as coal gas and hydrogen
sul-
phide renders the silver halide grains developable (see page 192).
Fog produced during development and
2.
types a.
— Several
Chemical Development Fog.
tain dyes, metallic sulphides,
when
and
consisting of the following
substances, notably cer-
strong fogging agents
tin salts, act as
present even in small concentrations in a photographic developer.
For example,
0.5
gram
of developer gives very
phide
is
(7 grains) of stannous chloride in a liter (quart)
bad
fog.
Under
formed by bacteria which
may
certain conditions
sodium
sul-
developer and reduce
live in a
the sulphite to sulphide.^*
The
bacteria seem to thrive in the slime which accumulates on the
sides of a tank so that the tank walls should be scrubbed thoroughly at
intervals (see section
on cleaning tanks. Chapter XII, page 265).
The
sulphide formed by this reaction can be removed by treating the developer with lead acetate in the proportion of
per gallon) of developer.
waste films
in the
It
may
also be
i gram per liter (60 grains removed by placing a few
developer whereby the silver halide emulsion reacts
with the sodium sulphide to form silver sulphide.
Another cause of chemical fog
sodium bisulphite
solution.
If a
is
the presence of zinc
galvanized pail
vessel, the zinc in the galvanized coating reacts
is
when mixing a
used for the mixing
with the bisulphite to
13 " The Fogging Properties of Developers " by M. L. Dundon and J. I. Crabtree. Amer. Phot. 18, 742 (1924). 14 " Sulphide Fog in Motion Picture Developers " by M. L. Dundon and J. I. Crabtree. Amer. Phot. 19, 96 (1925).
MIXING AND USING PHOTOGRAPHIC SOLUTIONS form sodium hydrosulphite, which
a powerful fogging agent.'
is
141
The
â&#x20AC;˘'^'
use of stoneware, hard rubber, stainless steel or enameled steel buckets
completely avoids trouble from this source.
Sometimes a developer may give excessive fog which has a yellowishbrown appearance on examining the film by transmitted light. When a developer gives fog, I
it
is
always desirable to take a portion (about
quart) and add lead acetate in the proportion indicated above and then
test for' fogging
recur
it
known b.
by developing a negative
w^as sulphide fog, but
as yellow stain
Aerial Fog.
if it
it is
and described below under
â&#x20AC;&#x201D;^With
" solvent fog."
certain developers, notably those containing
wet with developing solution
film
does not
a different type of stain
hydroquinone, a form of fog known as aerial fog
when
If the stain
therein.
persists,
is
sometimes produced
exposed to the
is
Such
air.^*^
modern motion picture developing machines, film in a tray, and in many cases where a parremoved from the developer for inspection.
conditions occur with some in the
development of
roll
tially
developed film
is
Traces of certain oxidizing catalysts, such as copper, favor the formation of this type of fog.
Theories as to
its
cause are rather vague but
it
may
be prevented by the addition of a desensitizer to the developer, such as pinakryptol green or phenosafranine in a concentration of one part in
two hundred
fifty
thousand parts of developer (see page 144).
Oxidized developers, particularly pyro, also tend to diminish aerial fog but the
life
MQ developer
of an
is
also shortened appreciably
addition of pyro so that the use of a desensitizing dye It is
is
by the
to be preferred.
somewhat anomalous that aerial fog should be produced while the is being oxidized and that oxidation products, when added to
developer
a fresh developer, should prevent aerial fog. is
Apparently, the aerial fog
produced by an intermediate reaction product which
ducing agent for c.
Solvent Fog.
â&#x20AC;&#x201D; This
type of fog
stain consisting largely of silver.
face
and
is
sulphite or
It
is
is
characterized as a yellowish
usually confined to the film sur-
removed by rubbing with the
absorbent cotton.
a strong re-
is
silver halide.
It
ammonia
is
fingers or a tuft of wetted
primarily a result of the solvent action of the
or hypo, or a combination of these, on the emulsion,
the developing agent reducing the dissolved silver salt back again to
yellow colloidal metallic ^">
J. F.
16
"
Amcr. 1"
M,
L.
Ross and
J. I.
silver.''
Pilot. 18,
J.
I.
Cral)tree.
742 (1924).
The Staining Properties Dundon.
Aincr. Phot. 23, 254 (1929). of Developers " by M. L. Dundon and
Crabtree.
The Fogging Properties
of Motion Picture Developers " by J.
Trans. Soc. Mot, Pict. Hug. No. as> 108 (1926).
I.
Crabtree and
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
142
The
precipitation of the colloidal silver
is
greatly accelerated
by the
presence of the sulphide ion (sodium sulphide) and, possibly, the sul-
phide forms specks of silver sulphide on the emulsion grains which act as nuclei for the silver precipitation.
A
concentration of sodium sulphide as low as
sufficient to
produce excessive stain
i
part in
i
million
is
presence of a sufficient quan-
in the
tity of silver solvent.
Since fine-grained emulsions are more soluble in a given concentration of a solvent than coarse-grained ones, the former are particularly sus-
The presence
ceptible to this type of fog.
of gelatin favors the precipita-
tion in a colloidal condition and, therefore, tends to change the color of
Experiments
the stain toward a dominant hue of longer wavelength.
have shown that the wavelength of the ticles is
absorbed by colloidal par-
equal to one-half the diameter of the particle.
In practice, therefore, yellow stain grained emulsions especially
if
if
is
apt to be encountered with fine-
and hangers are are not hardened in the
the films
the films
This results
dried with excessive heat. gelatin,
light
and sodium sulphide
insufficiently fixing
washed and
bath and are then
accumulation of hypo,
in the
because the unhardened
in the developer
and adheres to the hangers, while some hypo in this gelatin is sulphurized during drying and is sodium sulphide when carried over by the hangers to the
film tends to melt at the edges of the retained
converted to developer.
In some cases, the addition of potassium iodide 0.5
gram per
liter
thorough hardening, ing
in the
proportion of
prevents stain formation but the best preventative fixing,
and washing
of the films,
is
and thorough wash-
and frequent scouring of the hangers and cages.
The scouring
is
readily accomplished
by
boiling in a
10%
solution of
sodium phosphate, brushing, and washing. This development defect shown F. Mottle and Streaks.
tribasic
ure 68
is
â&#x20AC;&#x201D;
in Fig-
invariably caused by a lack of agitation especially in the case
of full exposures developed for only a short time.
form of streaks caused by
aerial oxidation or
It
may
appear in the
by the continuation
of
development locally during transfer of the film from one tank to another. It rarely occurs in automatic developing machines unless the film
and the solution are
insufficiently agitated.
Streaks are occasionally produced on
being retained between the jaws of a film inadequate.
On immersing
pounds flow down the
film
roll
films
by the
clip, especially if
the film in the developer, the
and cause fog (Fig. 69).
If
fixing
bath
washing
is
hypo com-
thorough wash-
MIXING AND USING PHOTOGRAPHIC SOLUTIONS
143
ing with brushing does not eliminate the trouble, the clips should be treated occasionally with a solution containing
ganate and
a
2%
sulphuric acid for
i^/(
solution of
Fig.
68
sodium
bisulphite,
— Developer
i
or
potassium perman-
i''y
minutes, rinsed, immersed in
2
and washed thoroughly.
mottle.
Fig.
69
— Fog
pro-
streaks
•
development by hypo retained between the jaws
duced
during
of film clips.
G. Airbells. film surface
The
— The
when
first
effect of a small
immersed
in the
bubble of
developer
is
trapped at the
air
shown
airbell prevents the access of the developer to the
therefore causes a white spot in the fixed-out
around the white spot of the developer
by
is
Figure 70.
The dark
circle
a result of oxidation fog caused by oxidation
the air bubble.
The dark streamer
result of these fogging oxidation products.
prevented entirely but are minimized into the developer.
fiilm.^*
in
emulsion and
They
if
the film
are rarely encountered
machines.
is
likewise a
Airbells cannot always be is
immersed slowly
when developing by
—
H. Miscellaneous Troubles. Stains on films, plates, and papers be produced in several ways in a developer as discussed in Chapter XI, page 230. Markings consisting of areas of heavier density than
may
the surrounding film are sometimes found on films or plates developed in 18 '
tree
and
Rack Marks and C. E. Ives.
Airbell
Markings on Motion Picture Film
Trans. Soc. Mot. Pict. Eiig. No. 24, 95 (1925).
"
by
J.
I.
Crab-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
144
hangers or on motion picture film developed on racks at the point where the film passes around the top and bottom slats of the rack. These markings are usually caused by retardation of development along the sides of the hangar or rack by the oxidized developer products and so-
dium bromide. They are prevented by thorough
agitation of the holder
or rack during development as well as agitation of the solution at the film surface.
Fig. 70
How
to
Mix
â&#x20AC;&#x201D; Airbell
Desensitizers.
markings on
â&#x20AC;&#x201D; Solutions
film.
of certain dyes
known
as
recommended for the control of developer fog, fog, and to permit development under compara-
desensitizers have been
and especially
aerial
tively brilliant safelight illumination.
The dyes may be used
in
two ways, namely:
before development in a concentration of about or
2.
they
may
I
part in 25,000 for desensitizing purposes or in a con-
part in 250,000 for preventing aerial fog.
I
Very few known Phenosafranine
many
is
desensitizers are stable
i
when added
quite stable but pinakryptol green
developers containing hydroquinone
greater than
as a preliminary bath
part in 5,000 or 10,000,
be added directly to the developer, usually in a concen-
tration of about
centration of
i. i
when used
is
in
to a developer.
precipitated in
a concentration
part in 50,000.
Desensitizing dyes are fairly expensive and for best results must be
used carefully, for with certain developers they are not as satisfactory as with other developers.
undertaken,
it
is
Before any extended use of these solutions
is
suggested that the user familiarize himself with the
characteristic properties of these substances.
A
comprehensive discus-
sion of the use of desensitizing dyes has been given
by M.
L.
Dundon
MIXING AND USING PHOTOGRAPHIC SOLUTIONS and
With modern high speed panchromatic emulsions
J. I. Crabtree.^''
which usually have
145
to be
handled
in
almost complete darkness,
it is
ad-
vantageous to be able to use a desensitizer (see Formula D-89, page 303).
The very
makes
it
dilute concentration in
difficult at first for
which these substances are used
The
an unskilled worker to prepare them.
recommended for their use: The most convenient method of preparing the dye solutions them up as a stock solution. Dissolve i gram (15 grains)
following directions are
to
is
in
make
500 cc
(i6 ounces) or preferably 1000 cc (32 ounces) of warm distilled water (about 125째 F.) (52째C.). The dye dissolves quite slowly and some-
These stock solutions represent
times the solution has to be heated. I
part in 500 and
i
part in 1000, respectively.
The
latter dilution is
most commonly used.
When
adding the stock solution of the desensitizer to a developer,
it
must be added very slowly; otherwise a precipitate may form, especially with developers containing hydroquinone. tion to a developer to
make a
i
To add
the
i
to
to 25,000 concentration of the
1000 solu-
dye
developer, take 40 cc (17 ounces) of the dye solution and pour
it
in the
slowly
with constant stirring into 1000 cc (32 ounces) of the ready to use developer.
If the
I
to
500 dye solution
is
used, take one-half as
much
or
20 cc (5 drams) to 1000 cc (32 ounces) of developer. For a preliminary bath of i to 5000 concentration, take 200 cc (6f ounces) of the i to 1000 dye solution and add water to make 1000 cc (32 ounces).
ACID RINSE BATHS AND ACID HARDENING BATHS During the development
of photographic emulsions, the gelatin
is
ren-
dered alkaline, and on transfer to the fixing bath, the alkali tends to neutralize the acid in the fixing bath.
An
excess of alkali destroys the hard-
ening properties of the usual alum fixing bath and tends to form a precipitate of
readily.
aluminum
Alum-acid
ther use.
It is
sulphite, thus rendering the bath unfit for fur-
fixing baths containing boric acid
important, therefore, to remove as
much
do not sludge so of the alkali as
possible before immersing the film or print in the fixing bath.
The is
simplest type of rinse bath between development and fixation
plain water, but this removes the alkali relatively slowly.
which chemically neutralizes the 19 "
alkali
is
A
bath
preferable, since this reaction
The
Trans. Soc. Mot. Pict. Eng. Effect of Desensitizers in Development." (1926) Amcr. Phot. 20, Xo. 37S, 438 (1926) also " Der Theorie und Praxis dcr Hypersensibilisierung " by K, Jacobsohn, Union Deutsche Verlags., Ber-
No.
z6, III
lin,
2931.
;
;
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
146
stops the progress of development.
With
certain types of automatic
developing machines, the use of an acid rinse cially
the film
if
is
exposed to the
the developer to the fixing bath.
An
very important, espe-
is
seconds in passing from
air for several
acid rinse in such cases introduced
immediately after removal of the film from the developer not only stops
development but also prevents the formation of stain
and insures that sludging does not occur
Two
types of acid rinse baths are in
3%
aerial fog
and developer
in the fixing bath.
common
use,
namely:
i.
2%
a
chrome alum, which might be termed a hardener rinse, since it both hardens the gelatin and neutralizes the alkali in the film or plate, and 2. a 1% or 2% acetic acid solution which is used for prints. In photofinishing work, about 0.5% acetic acid is sometimes added to the chrome alum solution since there is a tendency to carry more alkali There is into the rinse bath than in many other types of processing. or
solution of
greater danger of trouble from blisters, however, with this type of rinse
bath, especially during hot weather.
In case blisters are encountered, of acid, about
add only half the concentration
it is
better to
else
omit the acid entirely.
{Note: Blisters
may
0.25%, or
be avoided by using
An
developers containing Kodalk or borax as the alkali.)
acetic acid
bath containing sodium sulphate has also been suggested for negative materials (Formula SB-5, page 308).
This bath
is
recommended
for
use for photofinishing instead of an acetic acid-chrome alum solution.
An
acetic acid-sulphate bath does not
harden the gelatin but the
sul-
phate prevents swelling and softening while the acid stops development instantly.
The
solution works satisfactorily
up
to
8o°F. (26°C.) but
it
should not be used above that temperature or softening of the gelatin will
The bath keeps
result.
well without use.
It
should be replaced at
bath because the acid
least as often as the fixing
is
rapidly neutralized
and the sulphate concentration may become too low
to suppress the
swelling.
A 2^% bath
is
solution of sodium bisulphite
is
used occasionally for negative
The plain acetic acid rinse often called a " short stop " bath, especially by the photofinish-
materials
when hardening
ing trade.
A
is
unnecessary.
comprehensive discussion of the use of chrome alum rinse
baths has been given by Crabtree and Russell.-"
Hardening Rinse Bath for Films and tion of
chrome alum
retains
its
use, however, sulphite is carried into the bath 20
by
"
J. I.
Plates.
— A plain
solu-
With developer and
hardening properties indefinitely.
from the
—
Part Chrome AUmi Stop Baths and Fixing Baths Crabtree and H. D. Russell. /. Soc. Mot. Pict. Eug. 14, 483 (May 1930).
Some
Properties of
" I
MIXING AND USING PHOTOGRAPHIC SOLUTIONS
147
A
fresh
the presence of the sulphite reduces the hardening properties.
bath should be a blue-violet color by tungsten light when freshly mixed, but
ultimately turns yellowish-green with use.
it
It
then ceases to harden
and should be replaced by a jresh bath. The Importance of Agitation. A chromium scum composed of chromium hydroxide tends to be produced by the reaction between the chrome alum and the alkali in the developer carried over on the surface of the film. If the hardener rinse bath is reasonably fresh and the
â&#x20AC;&#x201D;
films are well agitated
When
when
first
immersed, the scum does not form.
the bath becomes old, however,
tion; the
it
tends to form even with agita-
bath should then be discarded.
Films or plates should always be wiped with wetted cotton after fixing
and washing and previous
to drying to
scum, because once the film thus formed.
Treatment
potassium citrate
is
is
dry
it is
of the film
sometimes
remove any possible traces of the very difficult to remove the stain
by bathing in a 5% solution of removing the stain although
effective in
care must be exercised in handling since this solution softens the gelatin
Chapter XI, page 253).
(see
Acid Rinse Bath for Papers. least 5 seconds in a
tive in checking
i
â&#x20AC;&#x201D; Prints
should be rinsed for at
or ih^^c acetic acid bath in order that
development and
in
be
effec-
preventing spots and stains
when
When
the prints are immersed in the fixing solution.
batches of prints It is
utes.
it is
it
handling large
desirable to extend the rinsing time to
i
or
2
min-
important to move the prints and to keep them separated
while in the acid rinse to insure that the solution has access to
all
parts
The bath should be tested with litmus paper at regular intervals and when it shows an alkaline test (blue litmus remains blue or red litmus turns blue) it should be replaced by a fresh bath. With of every print.
a I- or 8
by
1
2
-second drain after development, the equivalent of about twenty
0-inch prints
acetic acid rinse It is
may
be processed per
liter
(32 fluid ounces) of the
(Formula SB-i, page 307) before
good practice
to use a fresh
the acid rinse bath
is
becomes
it
bath for each batch of prints.
alkaline.
The
life of
determined by the quantity of alkali carried over
from the developer which depends on the quantity of developer retained
by
the print, the time of draining, and the quantity of alkali in the
developer.
Revival of Rinse Baths. a chrome alum rinse bath
is
â&#x20AC;&#x201D; For small
scale processing, revival of
not advisable because
economical to discard the solution and replace processing films on a large scale, however, the
it
life
it is
by a
simpler and more
fresh bath.
When
of the bath can usually
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
148
be extended so as to be twice or three times that of an unrevived solu-
Complete
tion.
details are given in the article referred to previously.-^
Revival of acetic acid or bisulphite baths for use with prints
recommended. alkaline
It is better to
and replace them with fresh ones.
not
is
when they become
discard such solutions
Typical formulas for hard-
ener rinse and acid rinse baths are given in Chapter
XIV, page 307.
FIXING BATHS The primary purpose remaining
of a fixing bath
is
to dissolve the silver salts
any photographic material after deThe chemical most commonly employed for this purpose is
in the gelatin layer of
velopment.
" hypo."
sodium thiosulphate, usually called
This substance has the
property of converting the silver halides to soluble complex thiosulphates of silver
and sodium which are removed from the gelatin
film during
washing.--
Fixing baths
may
be divided into two general classes as follows:
A. Non-hardening fixing baths. 1.
Plain hypo.
2.
Acid hypo.
B. Acid hardening fixing baths.
A. Non-Hardening Fixing Baths.
— A plain solution
quite satisfactory for fixing purposes provided
little
hypo
is
or no developer
is
of
The
carried over on the photographic material being processed.
centration of the hypo
is
con-
important because contrary to some general
impressions, the rate of clearing does not increase uniformly with con-
As shown by the curves
centration. in
Figure 71, which were prepared
in
connection with a motion picture fixing bath, the rate of fixing (meas-
ured in clearing times in minutes) increases as the quantity of
hypo
is
is
quite slow with a
(in the case of a positive emulsion) or of
emulsion), whereupon the rate of fixing tration of
5%
50%
to
concentration.
60%
tion.
40%
and
30%
(in the case of a negative
falls off
For average purposes, a all
difficulty is usually experienced
When
solution,
again until at a concen-
the bath fixes as slowly or even slower than at a
be taken as a rapid working bath for
No
5%
increased to a concentration of
30%
solution of
when mixing
a plain hypo solu-
mixing a quantity of solution in a tank, the filter
should be used (see page 32) and the
hypo may
types of material.
hypo dissolved
in
bag method
warm
water
(about i25°F.) (52°C.), because the temperature drops considerably
—
" Part I Some Properties of Chrome Alum Stop Baths and Fixing Baths Crabtree and H. D. Russell. /, Soc. Mot. Pict. Eng. 14, 483 (May 1930). 22 " Some Properties of Fixing Baths " by Trans, J. I, Crabtree and H. A, Hartt, -1
by
"
J. I.
Soc, Mot, Pict, Eng, No. 3S, 364 (1929).
MIXING AND USING PHOTOGRAPHIC SOLUTIONS while the hypo tion
is
on standing,
dissolving. this
If a
scum forms on
149
the surface of the solu-
should be removed by drawing the edge of a towel
or blotter across the surface, or
by using a skimmer device
(see Fig. 20,
page 40). TIME. TO CL-E^R MOTION PlCTURt
PANCHROMATIC
NEGATIVE. FILM.
TIME TO CLEAR MOTION PICTURE. POSITIVE FILM ^'t^
SO
100
l»0
5!>'f
SOO 600 %00 400 concentration: grams Na.2 SjOj 5HjO /liter solution
£00
700
•
Fig. 71
— Curves showing the time
and negative
films in
hypo
to clear
solutions
of
Eastman motion
picture positive
various concentrations at
different
temperatures.
A
stock solution of plain hypo should preferably be allowed to stand
overnight before use in order that any foreign matter
may
settle
out or
rise to the surface.
A wooden
cover
made
in the
manner described on page
71
(Fig. 36)
and treated with several coats of a nitrocellulose lacquer, such as Eastman Lacquer No. 5119, makes a satisfactory cover for placing on a stock solution hypo tank. A somewhat more expensive but equally satisfactory cover for a hypo tank may be made of 18-8 stainless steel containing about 3% molybdenum.
A plain hypo fixing bath, however, is seldom used because it rapidly becomes alkaline from an accumulation of alkali carried over by prints and films from the developer, and this tends to soften the gelatin, while the image continues to develop in the fixing bath, so that if two prints or films stick together,
more development takes place
contact, causing uneven development.
If the
bath
is
at the point of
acid, however, the
acid neutralizes the alkali in the developer carried over, thus preventing
unevenness.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
150
In order to be able to mix an acid fixing bath intelligently sary to understand a
Hypo can
be
little
made by
boiling together
sulphur until no more sulphur solution, sulphur
is
milk of sulphur.
it is
is
sodium sulphite and flowers of If acid is added to a hypo
dissolved.
again liberated, forming a milky solution
If
neces-
about the chemistry of the acid fixing bath.
sodium sulphite
is
present, however,
known
as
any sulphur
to come out of solution combines with the sulphite to form more hypo and the solution therefore remains clear. This sulphur if precipitated cannot be redissolved by adding sodium sulphite to the milky solution except by boiling, while on standing it is
which tends
All plain acid fixing baths
apt to settle on films or prints as a scum.
by adding an acid salt such as sodium bisulphite or potassium metabisulphite to the hypo solution or by using sodium sulphite and some weak acid which has a much lower tendency to decompose hypo than stronger acids like sulphuric acid. Practical hints therefore are prepared
on mixing acid
Do
1.
hypo
fixing baths are as follows:
not add the bisulphite or acid sulphite solutions to the
solution.
The
(i8°-2i°C.) or the hypo
On
2.
will turn
warm
when mixed (65°-70°F.)
solutions should be cool
milky.
keeping, an acid hypo solution gradually becomes milky. a stock solution of the sodium bisulphite,
To
etc.,
should be
kept and added to the plain hypo stock solution as required.
For gen-
prevent
this,
ounces (45 cc) of a 50% sodium bisulphite solution is added to 32 ounces (1000 cc) of a 35% hypo solution. If any considerable excess over this quantity is added the hypo rapidly turns milky,
eral purposes, i^
especially in
warm
weather, owing to the liberation of sulphur.
Plain acid hypo solutions are not used very tion of
alum because
of the ease with
much without
the addi-
which they sulphurize and their
entire lack of hardening properties. If the
temperature of the processing solutions can be maintained at
65° to 70°F. (18° to 2i°C.) and
if
ample drying time can be allowed so
that relatively cool drying air can be used, a non-hardening fixing bath
containing hypo, sulphite, and bisulphite
The
is
satisfactory.
bisulphite serves to keep the bath acid
the sulphite prevents precipitation of sulphur
vious to use at too high a temperature. acid
and prevent
stains while
the bath
stored pre-
if
is
The bath should be maintained
by reviving with a 25% solution of sodium bisulphite at intervals machine processing, by allowing this reviving solution
or in the case of
to flow into the tank continuously during use.
An
alternative
method
of revival consists in passing sulphur dioxide
MIXING AND USING PHOTOGRAPHIC SOLUTIONS
151
Although this is a fairly efficient procedure, there is danger of accidental escape of the suffocating gas into the atmosphere gas into the bath.
room
of the
so that
practical application
its
of questionable value.
is
A typical non-hardening fixing bath is Formula F-24 page 312. A 2% solution of potassium chrome alum may be used as a hardener rinse bath in conjunction with the
above
fixing bath, although
be desirable to reduce the bisulphite concentration liter
to 10 or 15
it
may
grams per
(150 or 225 grains per quart) because acid would be carried into
the fixing bath from the
chrome alum
rinse bath.
Acid Hardening Fixing Baths.
B.
by adding
are prepared
to
â&#x20AC;&#x201D; Acid hardening
fixing baths
hypo an acid hardening solution which usually
contains the following ingredients: 1.
A
preservative such as sodium sulphite or sodium bisulphite.
latter acts as a preservative in
two ways:
it
The
prevents the formation of
sulphur by the action of the acid on the hypo, while
it
also prevents the
developer carried into the fixing bath from oxidizing and turning brown. 2.
An
acid such as acetic, boric,
3.
A
citric, lactic,
malic, maleic, sulphuric,
which stops development.
tartaric, etc.,
hardening agent such as potassium alum, potassium chrome
alum, or formaldehyde.
A
comprehensive paper on the chemistry of fixing baths has been
published by given herein
J. I. is
Crabtree and H. A. Hartt,-' and '
H. D. Russell which deals with chrome alum 1.
It is
much
taken from this paper and another by
imperative
when compounding an
of the material
J. I.
Crabtree and
fixing baths.-*
acid fixing bath to have a
quantity of free acid present in order to prevent discoloration of the bath
by developer reaction products, and
also to prevent precipitation of the
hardening agents by the alkali of the developer.
Since free acid tends
hypo with liberation which will counteract this substance must be added
of free sulphur,
some
Two
types
to cause decomposition of the
reaction.
of substances are effective, namely: a. the alkaline sulphites, such as
sodium
sulphite,
and
b.
the alkaline salts of organic acids, of which so-
These latter substances tend to is a typical example. " buffer " or reduce the hydrogen ion concentration * or pH of the acid
dium acetate
employed below the 2. 23
Practically "
Some
all
limits at
which sulphur
is
precipitated.
of the commercially available solid organic acids
Properties of Fixing Baths " by
J. I.
Crabtree and H. A. Hartt.
Trans.
Soc. Mot. Pict. Eng. No. 38, 364 (1929). 24 "
by
J. I.
*
Some Properties of Chrome Crabtree and H. D. Russell.
Alum /.
Stop Baths and Fixing
Bathsâ&#x20AC;&#x201D;
Part II
Soc. Mot. Pict. Eng. 14, 667 (June 1930).
For a brief discussion of the meaning of
this term, see
page 117.
"
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
152
yield with tive
aluminum
salts,
hardening agents.
complex aluminum ions which are not
erally efficient acid for use in fixing baths containing potassium
Sulphuric acid, which
the hardening agent.
effec-
Acetic acid has been found to be the most gen-
is
a mineral acid,
is
alum as the most
chrome alum. Of the acid salts, sodium bisulphite and potassium metabisulphite are the best known, but these substances are not suitable for use with acid hardening fixing baths containing alum because the reserve acidity of these salts is insufficient to prevent precipitation of aluminum sulphite
satisfactory for fixing baths containing
on the addition of
alkali.
Hardening agents for use with gelatin consist of two types, temporary and permanent hardeners. The former class, of which sodium sulphate is an example, merely suppress the swelling and raise the melt3.
ing point of the gelatin while
These substances are used essing of materials
when
it is
in contact
with the hardening solution.
chiefly in conjunction with the tropical proc-
it is
necessary to handle them at temperatures
above 75°F. (24°C.) (see Chapter VIII). gelatin, rendering
Permanent hardening usually tans the
it
incapable
washing chromium, and
of swelling except to a very limited degree during subsequent in the
normal manner after
fixing.
The
salts of iron,
aluminum exert the most effective hardening action on gelatin. Salts of aluminum are perhaps the most satisfactory because they are colorless, readily soluble in water, and do not form colored compounds with
common
the
developing agents, while they give satisfactory hardening
provided the wash water temperature tain
aluminum
salts,
aluminum
is
not above 8o°F. (26°C.).
Cer-
chloride, for example, tend to hydrolyze
aluminum hydroxide when dissolved in aluminum and sodium or potassium sulalums form a clear solution and are to be preferred.
and form a white precipitate
of
water, but the double salts of
phate called
Formalin, quinone, and developer oxidation products also tan gelatin
but only is
in alkaline or neutral solution
and
their application therefore
limited.
Acid Hardening Fixing Baths Containing Boric Acid. fixing baths containing acetic acid,
and hypo, the maintained
is
pH
— With
potassium alum, sodium sulphite,
range * throughout which satisfactory hardening is A fresh bath has a pH value of about 4.2
rather limited.
and a used bath, which has precipitated an aluminum sulphite sludge, about 4.8. When the acidity varies much above or below this range, the bath ceases to harden. *
The
pH
of water
is 7.0.
For a discussion of the meaning of the expression
"
pH,"
see p. 117.
MIXING AND USING PHOTOGRAPHIC SOLUTIONS If boric acid is
added
bath of
to a fixing
range over which good hardening exists the sludging tendency
this type,
pH
extended considerably and
is
greatly diminished.-''
is
however, the
153
A
bath of
this
type has
ErrccT or exh«kustion on the: ha.roe.ning. PROPERTIEIS AND pH VA,l_UES OF" VARIOUS riXltSG. BATHS. (0-\a F--Z
FILING
OE-VEI-OPERl
BATH WITHOUT
210
AGIO
REVIVAL
4.5 6.0
ISO u:
6.5
ul
s = si_udg.e:
U 110
I
tf
F-Z
a
I
F-tX\NC»
S.O-
BATH WITH
u o
ACIO RE.V1VA\_
-^N^-.V4^«^N
R R R R R ^ 2 '80 n 160 (J
Z
UO BORIC ACIO FIXING. BATH WITHOUT ACIO RE.VIVAl_
U JZIO
4.6
180 160
liO
100 ZOO 300 400 zoo 300 400 6 MIN. 0-l<i AND FIKEO 10 MIIM.
lOO
Fig. 72
— Hardening
properties and useful
life
60
of
boric acid vs. older type of acid-alum fixing bath.
a a
pH pH
sity
value of about 4.2 value of about 6.0.
fresh and the hardening is maintained to Because of their much lower sludging propen-
when
and excellent hardening
acid are
recommended
characteristics, fixing baths containing boric
and plates
for films
bath which does not contain boric acid.
and the
life in feet of film fixed
Chrome Alum Fixing
sludge in
type of
characteristics
per gallon are shown in Figure 72.
Baths.
— Chrome alum
or
chromium potas-
hardening agents used for tanning it does not readily precipitate a that advantage It has the on the addition of developer baths fixing sulphite acid-sodium
sium sulphate was one of the gelatin.
in place of the older
The hardening
first
baths containing aluminum alum. If the bath once precipitates a sludge of chromium hydroxide, however, the solu-
as
is
the case with
many
tion should be discarded, as there
the film and
producing a stain
is
danger of the precipitate settling on is very difficult to remove.
which
25 " An Improved Potassium Alum Fixing Bath Containing Boric Acid " by H. D. Russell and J. I. Crabtree. /. Soc. Mot. Pict. Eng. zi, 137 (August 1933)-
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
154
Chrome alum
fixing baths are capable of
hardening gelatin to a greater
degree than potassium alum fixing baths but the chrome alum baths,
compounded, lose their hardening powers rapidly either Sodium sulphite, although necessary to prevent
unless properly
with or without use.
decomposition of the hypo, tends to destroy the hardening properties of the
chrome alum.
insures a longer
about
3
:
Usually a concentration of chrome alum of about
life
by weight
5
and the sulphite
to
of chemicals for
alum
maximum
Fixing Baths Containing Potassium Alum. fixing baths containing
The degree
be
keeping properties.
— The
relative merits of
potassium alum as compared with those with
chrome alum may be summarized 1.
3%
ratio should preferably
of hardening
as follows:
may
be adjusted precisely between 120°
and 2i2°F. (49° and ioo°C.). 2.
The hardening
on standing without
properties of the bath do not change appreciably use.
Scum is readily detected and can be removed if dried on the film. There is no danger of staining the film at high temperatures. Fixing Baths Containing Chrome Alum. i. Have great hard3. 4.
—
ening ability when fresh but lose this rapidly on standing with or without use. 2.
The type
of hardening
subsequent treatment and conditions.
It
is
is
very rugged and
useful
is
when
destroy by
not possible to adjust precisely the degree of hardening
obtained between values of 120° and 2i2°F.
alum baths
difficult to
processing film under tropical
either
do not harden at
all
In other words, chrome
or produce a melting point above
2I2°F. 3
Although the scumming tendency
baths, sludge precipitation is
very 4.
difficult to
The
remove
is if
excessive
is
less
than with potassium alum
when once
started and the
scum
allowed to dry on the film.
alkalinity of the film affects the hardening greatly.
in the gelatin if the concentration of the chrome alum is too high. For general use with films and plates at normal temperatures and where it is desired to keep the bath several weeks, an acid fixing bath containing potassium alum and boric acid is preferable. Chrome alum fixing baths are quite satisfactory, however, for use where maximum hardening is required, especially under tropical conditions. Such baths should be discarded every few days if the most effective hardening is to 5.
Green stain forms
be realized.
The
addition of boric acid to chrome alum baths does not extend the
MIXING AND USING PHOTOGRAPHIC SOLUTIONS hardening
life
when
pH
or increase the sludging
pH
bath has a
A
life.
fresh
chrome alum
pH
value of about 3 and hardens well until the
155
fixing is
3.8,
the hardening begins to drop until the bath ceases to harden at a
A
of 4.5.
sludge
is
usually precipitated at a
pH
pH).
for a discussion of the term.
The Useful Properties
of 5 (see page 117
—^A satisfactory acid
of a Fixing Bath.
^
hardening fixing bath should have certain properties, namely: a fairly
minimum tendency
rapid rate of fixation, good hardening, a ing blisters, a long sludging
The time
for fixation
is
and
life,
a long useful
for
produc-
life.
usually taken as twice the time for the milki-
ness or opalescence of the unreduced silver salts to disappear.
depends on the strength of the hypo (30 40% idly), the photographic material tested (portrait films
hypo
to
fixes
fix
This
most rap-
comparatively
slowly, usually requiring 3 to 6 minutes to clear, whereas lantern slides fix
rapidly, clearing in 30 seconds to
solution (65°F.
is
i
minute), the temperature of the
recommended), and the degree of exhaustion
of the
solution.
by a large number of factors. alum is required to give the necessary A certain minimum quantity of may produce too much hardening hardening, while an excess of alum and induce brittleness. Normal potassium alum fixing baths are care-
The hardening
properties are influenced
compounded to give a hardening of 130° to i8o°F. (54° to 82°C.), determined by immersing a strip of the fixed and washed film in water,
fully
heating the water slowly on an electric hot plate (about 5°F. rise per
minute) and reading the temperature at which the gelatin flows away from the support (see apparatus for melting point test. Fig. 73, page 156).
The hardening produced by
the bath depends on
factors such as the emulsion used
and the
and
and the temperature
of all solutions;
factors including the time the film
given in
all
baths,
" certain " fixed
pH of the film, the composipH value of these solutions,
bath and the
tion of the rinse bath
fixing
a.
and upon is
b.
a number of variable
in the fixing bath, the agitation
and the time of washing.
For
maximum
hardening
using a 5-second rinse in water between development and fixation, and
washing 20
to
fixed 15 to 20
40 minutes minutes
in
running water after fixation, film should be
in either fresh or partially
exhausted acid harden-
ing fixing baths.
Since a chrome alum fixing bath loses
veloper better, a
is
carried into the bath,
chrome alum hardener
it is
rinse
its
hardening properties as de-
important to use a water rinse
between development and
or,
fixation.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
156
A
fixing bath should not
produce
page 167).
films or papers (Fig. 75,
blisters in the gelatin coating of
If the acidity of the
bath
is
too high,
the formation of carbon dioxide gas proceeds too rapidly with the addition of a carbonate developer to the fixing bath to
form within the gelatin layer which
finally
and gas pockets are apt blisters. De-
break causing
velopers prepared with borax or with Kodalk do not release any gas
when added
to the fixing
bath and
Apparatus
Fig.
blister
formation
is
eliminated.
for melting point determination.
A
good
life of
fixing
the bath
to 2i°C.).
bath should not sludge or turn milky during the useful at normal temperatures of 65° to 70°F. (18°
when used
There are two
different
ways
in
which a
fixing
bath
may
precipitate a sludge, as will be discussed subsequently under " Trou-
Changes in temperature of the fixing bath affect the rate of fixaand the useful life of the solution. For example, if a film requires 95 seconds to clear at 65°F. (iS^'C.) it would take about 60 seconds to
bles."
tion
clear at 85°F. (29°C.), but
it is
dangerous practice to allow the tempera-
much above 7o°F. (2i°C.) because the solution sulphur. Under tropical conditions when high tem-
ture of the bath to rise is
apt to precipitate
peratures prevail,
it
is
within this limit without
obviously impossible to keep the temperature fixing
bath must
for tropical processing,
where the
artificial refrigeration,
and the
always be replaced oftener.
A
different technique
must be used
MIXING AND USING PHOTOGRAPHIC SOLUTIONS abnormal swelling
secret lies in preventing
swollen,
is
it
almost impossible to reduce
157
of the gelatin, for once
and
it
to
handle the
it is
In-
film.
formation on this subject will be found in Chapter VIII, page 178.
Typical formulas for potassium and chrome alum fixing baths are
found on pages 309-313 of Chapter XIV.
Mixing Fixing Baths and Stock Hardener Solutions.
—
It
is
often convenient to prepare a concentrated hardener for use as required.
The formula
for
such a stock solution for making a fixing bath for papers
(Formula F-i)
as follows:
is
Acid Hardener Stock Solution
[F-la] Metric
Avoirdupois
Water (about
Sodium
125° F.) (52° C.)
ounces ounces ounces
1700.0 cc 240.0 grams 750.0 cc
8
ounces ounces
210.0 cc 240.0 grams
1
gallon
56
Sulphite, desiccated
8
Acetic Acid (28% pure)
24
or Glacial Acetic Acid (pure cone.)
6%
Potassium Alum Cold water to make *
To make 28%
acetic acid
from
4.0 liters
glacial acid, dilute 3 parts of glacial acid with
8 parts of water.
For of a
use,
25%
add i part of cool stock hardener solution slowly with hypo solution.
To make up above.
stirring, to 4 parts
cool
the hardener, dissolve the chemicals in the order given
The sodium
sulphite should be dissolved completely before add-
After the sulphite-acid solution has been mixed thor-
ing the acetic acid.
oughly, add the potassium alum with constant stirring.
If the
hypo
is
not thoroughly dissolved before adding the hardener, a precipitate of
sulphur
is
likely to form,
which
it is
not possible to redissolve, and the
solution will have to be discarded. It is
sometimes recommended
to reverse the order of
hardener, namely: dissolve the alum phite, but the
alum
dissolves
first,
add the
more readily
acid,
mixing of the
and then the
in the acetic
sul-
acid-sodium
sulphite solution.
Another method tions, cool,
is
to dissolve the
add the acid
If the order of
mixing
phite, a white sludge of
is
reversed and the alum added
aluminum
with difficulty when the acid
is
milky after mixing and a sludge sufficiency of acid
;
that
alum and sulphite in separate soluand then add the alum.
to the sulphite solution,
is,
sulphite
added.
is
Therefore,
settles out, this is
the acid used
was
much alum or sulphite was added. Fixing Baths Containing Boric Acid.
or too
cipitation of
an aluminum sulphite sludge
is
first
to the sul-
formed which dissolves if
due
the hardener
is
to a relative in-
either not
up
to strength
— The tendency
greatly minimized
for preif
boric
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
158
acid
is
added
potassium alum acid fixing bath such as the one pre-
to a
pared from the following formula. the bath
is
extended greatly and
film surface
The
much
is
less
Furthermore, the hardening
life of
propensity to deposit a scum on the
its
than for baths which contain no boric
acid.-''
following formula represents a typical bath containing boric acid.
[F-5]
Acid Hardening Fixing Bath for Films and Plates Avoirdupois
Water (about
Metric
13 2
ounces ounces ounce fluid ounces
3}4
drams
125° F.) (52° C.)
20
Sodium Thiosulphate (Hypo) Sodium Sulphite, desiccated *Acetic Acid, 28% pure
8 '2
600.0 cc 240.0 grams 15.0 grams 47.0 cc
or
Glacial Acetic Acid (pure cone.) tBoric Acid, crystals
...
}4 J^
Potassium Alum Cold water to make
32
13.0 cc 7.5 grams 15.0 grams
ounce ounce ounces
1.0 liter
Dissolve chemicals in the order given. *
To make 28%
acetic acid
from
glacial acid, dilute 3 parts of glacial acid with
8 parts of water.
Pow-
t Crystalline boric acid should be used when mixing the above formula. dered boric acid dissolves only with difficulty and its use should be avoided.
—
A Chrome Alum Fixing Bath. Fixing baths containing chrome alum usually have very good hardening properties when freshly prepared but, unless properly compounded, tend to lose their hardening characteristics with or without use after several days. A chrome alum fixing bath having quite satisfactory hardening properties
[F-23]
Chrome Alum Solution
to
Solution
B
make
Water
Sodium
Sulphite, desiccated
*Sulphuric Acid,
pounds
1
96
ounce, 290 grains ounces
20
ounces
600.0 cc
grains
20.0 grams 160.0 cc 128.0 grams
4M 32
ounces ounces ounces
fluid
5 ..
Directions: Solution B by adding the chemicals in
Then add Solution B slowly oughly. If Solutions
A
To prepare 5%
to
Solution
and B are not
cool
sulphviric acid,
A
960.0 50.0
3.0 liters
1.0 liter
and cool the order given and cool
Dissolve the constituents of Solution
Mix
grams grams
2
290
5%
Potassium Chrome Alum. Water to make
*
Metric
Avoirdupois
Sulphite, desiccated
Water
the following:
Fixing Bath for Films and Plates
A
Hypo Sodium
is
A
to 7o°F.
(2i°C).
to 7o°F. (2i°C.).
while stirring the latter solution thor-
when mixed,
the bath will sulphurize.
add one part by volume of pure concentrated
sulphuric acid slowly to 19 parts by volume of cold water, and mix carefully with stirring. The acid must he added to the zvater and not the water to the acid, other-
wise the solution will boil with explosive violence, and or face, will cause serious burns. 26 "
An Improved Potassium Alum
Russell and
J. I.
Crabtree.
/.
if
spattered on the hands
Fixing Bath Containing Boric Acid " by H. D.
Soc. Mot. Pict. Eng. 21, 137 (August 1933)-
MIXING AND USING PHOTOGRAPHIC SOLUTIONS
159
deep tank and the hypo bath is not stirred adequately, the chrome alum solution will tend to float on top of If the solutions are
mixed
in a
hypo solution and sulphurization
the
not be stored as a stock solution as It is possible to revive the
useful
by the addition
life
Fig. 74
it
is
— Lantern
will lose its
— After a
bath has been mixed,
fixing
The
The
be determined as follows:
until the
it
recommended are
tests
rate of fixation
place
bath solution on a strip of film or plate and allow
fixing
its
time of fixation.
slide test of
the rate of fixation and the hardening ability.
may
should
above bath several times and extend
should be tested before being put into use.
to clear
B
hardening properties.
of dilute sulphuric acid.-'
Testing Fixing Baths.
or time
Solution
apt to occur.
some
of the
this to
stand
milky emulsion under the streak becomes clear or dissolved
Then immerse
(Fig. 74).
the strip in the fixing bath and determine the
time required for the streak to disappear, which indicates that silver salts
all
the
The time found should then be commade under standard conditions with a bath known to
have been dissolved.
pared with a
test
be of satisfactory composition.
The degree
of hardening test should be
made
in
a
manner
similar to
the hardening test described previously on page 155.
The time and
I),
of fixing, therefore, depends
upon
a.
the " time to clear,"
the time required to attain the desired degree of hardening.
Ob-
viously, the time for h. should always be greater than the time for a. -'
by
"
J. I.
Some Properties of Chrome Crabtree and H. D. Russell.
Alum Stop /.
Bath.s
and Fixing Baths
— Part
Soc. Mot. Pict. Eiw. 14, 667 (June 1930).
II
"
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
160
Effect of
— With
Time and Temperature on
the Rate of Hardening.
baths containing potassium akim and having a
pH
below
such as the older type of baths without boric acid, the hardening creases rapidly during the
first
few minutes after immersion and then
tends to become almost constant after 10 minutes in the bath.
pH
baths which have a
5,
in-
Fixing
of 5.0 or above, such as a partially exhausted
potassium alum bath containing boric acid, harden more slowly during the
first
few minutes but continue
hardening throughout
to give greater
the time of bathing.
The
rate of hardening increases generally with temperature unless the
swelling of the gelatin, previous to fixation, becomes excessive.
—
Effect of Temperature and Agitation on the Fixing Time. The temperature of a fixing bath, although of less importance than that of the developer, should receive attention.
For instance, with
roll film,
lowering of the temperature from 75°F. to 55°F. (24° to i3°C.) doubles
For
the time of fixation. to
efficient
working, therefore,
it is
very necessary
keep the temperature of the fixing bath approximately the same as Agitation of the film in the fixing bath also speeds
that of the developer.
up
shown
fixation at various temperatures as
in
Table
The data
4.
apply only to a particular emulsion.
TABLE
4
Effect of Agitation and Temperature on the Time of Fixation With Without
...
Temperature
it
•
Agitation
6o°F. (i5°C.)
15 Min.
20 Min.
65°F. (i8°C.)
12
Min.
16 Min.
70°F. (2i°C.)
10 Min.
13
75°F. (24°C.)
Min.
7
The Useful Life used
•
a
Agitation
5
of Fixing
becomes exhausted as a
The
ing out the emulsion. in,
phurization
With
life.
result of
a fixing bath
is
performing useful work
acidity of the bath
although at
developer carried
Baths. — As
Min. Min.
first this
is
being in fix-
being reduced by the
tends to favor a longer sul-
use, however, the usual
potassium alum-acetic
acid-sulphite-hypo solution finally reaches a point where a sludge of
aluminum the
first
sulphite
is
precipitated, rendering the bath useless.
During
stages of use of the usual bath containing potassium alum, the
hardening properties increase slightly, after which they fall off rapidly. As noted previously on page 157, the hardening range is extended and
MIXING AND USING PHOTOGRAPHIC SOLUTIONS the sludging tendency greatly diminished
when
boric acid
added
is
161
to
an
alum-acetic acid bath.
A
bath
fixing
is
usually exhausted
it
if
froths at the surface or
if it
becomes milky or sludges throughout the solution. The bath may also fix so slowly that there is a danger of removing the films or prints be-
When
fore they are completely fixed.
the time of clearing for a fixing
film exceeds lo to 12 minutes, the bath should be discarded.
In order to insure thorough fixation to
remain
in the fixing
customary
it is
to allow the film
bath for twice as long as the time required for
the emulsion to clear.
A
satisfactory acid hardening fixing bath should
fix
completely the
equivalent of eighty to one hundred 8 by lo-inch films or plates per 4
liters (gallon)
before the bath should be discarded.
should be rinsed for at least fixing.
5
All films (plates)
seconds in water between developing and
During hot weather, the use of an acid hardening is recommended.
rinse
(SB-3,
page 307)
A
satisfactory fixing bath for papers should fix the equivalent of
about sixty 8 by lo-inch prints per 4 liters (gallon) provided a thorough rinse (not less than 5 seconds) in water precedes fixation. Or if a twoor three-minute immersion in a suitable acid rinse bath (SB-i, page
307) is given between development and fixation, the equivalent of one hundred and twenty 8 by lo-inch prints may be fixed per 4 liters (gallon).
The chrome alum bath given life
as the potassium
alum
bath
fixing
is
before has about the same useful fixing
alum bath. The hardening
much
life
of the usual
chrome
shorter, however, because the hardening
falls
and the acid two or
off quite rapidly as a result of the reaction between the sulphite
chrome alum, unless the bath
is
three times during
life.
useful
its
revived Its
by
the addition of
hardening power will be main-
tained for only about two weeks regardless of
how
the hardening can be held up for a longer period
For maximum hardening, therefore,
it
is
by thoroughly washing the
by adding
films
used, but
suitable revival.
necessary to maintain the
acidity of the bath close to the original value either
by
little it is
and
this
can be insured
between developing and
fixing, or
further quantities of acetic or sulphuric acid to the bath at
definite intervals.
The
by chemical analysis
add can be determined only by keeping a record of the quantity of films
precise quantity to
or
fixed in the bath.
Attempts
to revive the fixing-out properties of the
baths by further
additions of hypo are not generally to be recommended.
Usually by
162
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
the time the bath
and get the
When
last
is
when
When
excessive.
it
muddy and
it is
â&#x20AC;&#x201D;A
Fixing Bath.
deposits a sludge or
using machines there
economy
false
to try
is
a
fixing
when
bath should be
the time of fixation
maximum
permissible time clear-
equal to one-half the time required for the film to pass through
the fixing bath.
Maximum
at a temperature of 65^ F.
Some workers make
efficiency
is
obtained only when the bath
is
(18-C).
a practice of testing the specific gravity of their
baths, thinking that this 5.
it is
and the baths should therefore be renewed when the
for fixation
ing time
exhausted
to Discard the
discarded either is
is
ounce of work out of the bath.
is
an index of the degree of exhaustion.
Table
however, should convince the most skeptical that the specific gravity
readings of a fixing bath bear very for film to clear.
under actual
A
change
test conditions
gravity of the bath.
Of
little
relation to the time required
in the clearing
time from
2
produced no change whatever
course,
if
to 12
minutes
in the specific
a large quantity of water
is
carried
over by the films, the specific gra\aty will decrease but not necessarily in
proportion to the degree of exhaustion.
MIXING AND USING PHOTOGRAPHIC SOLUTIONS The degree which it
it
of exhaustion of a fixing bath
When
out the emulsion.
fixes
should be discarded.
by a
that required
With papers
Usually,
is
when
difficult to
make
the emulsion has practically the
is
rate at
too slowly,
fix
the time of fixation
fresh bath, the solution
it is
shown by the
best
a bath begins to
163
twice
is
considered exhausted.
a " time of clearing
"'
test
because
color as the paper stock, but
same
it is
possible to determine the fixing efficiency of such baths indirectly.
The Sulphide
Test.
— Cut a number
posed paper for which the fixing bath
of i-inch strips of the unex-
i
the time
it
minute, another
is.
fix
has been fixed, remove them from the fixing bath at the end
of the given time,
merse the strips
Two grams liter
2
these in
one strip 30 seconds, minutes, and so on. Note on each strip
the bath for var\-ing lengths of time; that
another
Immerse
to be used.
is
and wash thoroughly
in a
weak (about 0.2%
)
— about
i
Then im-
hour.
solution of sodium sulphide.*
(30 grains) of sodium sulphide by weight dissolved
(32 ounces) of water will
make up
in
one
a solution of the correct strength.
{Warning: The sulphide solution should be kept away from the develbad chemical jog.)
oper, as a trace of sulphide in the developer will cause
The presence
of very
minute quantities of unfixed
silver in the
emulsion
of these strips will cause a brown or yellowish-brown stain to appear
when
the strip
placed in the sulphide solution.
is
In this way, the rate or speed of fixation of a fixing bath
termined, because a strip treated by this method
is
may
be de-
completely fixed
if
In actual practice, howit does not discolor in the sulphide solution. ever, the time for complete fixation should be longer than that shown
by the
test, since
the test represents ideal conditions.
of prints are being fixed at once, the time should be
The best way make the test as is
of arriving at a
margin of safety
outlined above for a fresh bath.
When
still
for a fixing If a partly
then tested and found to require twice as long to
a
number
longer.
bath
is
to
used bath
fix, it is sufficiently
exhausted to be discarded as unsafe for use.
An fixing
alternative test for detecting
bath has doubled
is
lantern slide in the fresh as
to
when
the
•
time to clear
"'
for a
paper
determine the time to clear for a slow
compared with the used bath
(see page 159
and Fig. 74). The rate of fixation of a lantern slide emulsion is somewhat slower than that of developing-out papers but the ratio of the clearing time of a fresh and exhausted bath is similar in the case of paper and lantern *
The
slide emulsions.
sulphide immersion should be done, preferably, in another room than the that accurate comparison of the strips may be
darkroom and before a window so facilitated.
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
164
Under fix
and with
ideal conditions
agitation, a fresh fixing bath will
a print completely in 30 seconds to
i
minute (as measured by the
sulphide test), and a partially exhausted bath will require from
i
to 3
minutes, depending on the degree of agitation and the quantity of prints
minimum
In practice, however, a
previously fixed therein.
of 10 minutes should be adopted because under practical tions prints
prints
fixing time
working condi-
do not always receive individual treatment, and when the
one on top of another, a stop bath and a fixing bath do not
lie,
The time
have thorough access to the emulsion.
of fixation should be
such that even in the case of prints which stick together the fixing bath has free access to every part of the print for at least 3 minutes. time of 10 minutes for fixation
is
A
set
therefore not excessive.
FIXING BATH TROUBLES A. Sludging of the Fixing Bath.
—A
The
milkiness
ing,
it
b.
in use for
turn milky some time.
of two kinds
pale yellow and settles very slowly on stand-
is
and may be caused by:
consists of sulphur
Too much acid in the hardener. Too little sulphite or the use of impure
a.
is
may be
If the precipitate
1.
may
bath
fixing
immediately on adding the hardener or after being
sulphite, in
which case there
not sufficient present to protect the hypo from the acid.
High temperature. The hardener should only be added to the hypo when at room temperature. If the temperature of the acid fix-
c.
solution
ing bath
is
many
over 85°F. (29°C.),
longer than a few days even
fixing baths will not
when mixed
bath (Formula F-5) given previously 85°F. (2g°C.) due phurizes, the only If a sulphurized
gelatin,
and
later
to its
bath
keep two or three weeks at
high sulphite concentration.
remedy
may
will
is
is
throw
to
used,
it
remain clear
The potassium alum
correctly.
When
away and mix
some sulphur
is
a bath sul-
a fresh solution.
apt to be retained by the
cause fading of the image as a result of the forma-
tion of silver sulphide. If the precipitate is
2.
hours,
consists of basic
it
white and settles out on standing for a few
aluminum
sulphite.'-®
This sludge
may
be
caused by:
Too
a.
calls for less
little
acid in the hardener.
pure glacial acetic acid and
For example, supposing a formula
28%
acid
is
used by mistake, then
than one-third the required amount has been added.
b.
Too
28
S. E.
little
hardener in the fixing bath.
Sheppard and A. Ballard,
/.
When
fixing prints, a rela-
Frank. Inst. 200, 537 (1925)-
MIXING AND USING PHOTOGRAPHIC SOLUTIONS tively large proportion of the developer
is
165
carried over to the fixing bath
which soon neutralizes the acid and, therefore, increases the tendency for precipitation of aluminum sulphite. In the same way, a fixing bath with the correct proportion of hardener, when exhausted,
alum and sulphite but no aluminum sulphite. It is
to
is
and these combine
to
still
contains
form a sludge of
extremely important, therefore, to use only the acid specified and
know
acid
acid,
its
strength, because trouble
used than
is
is
caused
called for in the formula.
It
either
if
more or
less
has been found that the
hardening properties of a potassium alum acid fixing bath bear a
rela-
aluminum sulphite. In other words, a bath containing an excess of acid, and which, therefore, may be used for a relatively long time before the aluminum sulphite precipitates, does not harden as well as a bath which precipitates when a much smaller quantity of developer is added. With such a bath containing a minimum concentration of acid, it is advisable to add a furtion to the tendency of the bath to precipitate
ther quantity of acid as soon as a slight precipitate appears or preferably
when
the acidity begins to
measured by a chemical
as
fall off
test,-''
a
satisfactory quantity being about one-half that originally present in the
A
bath.
bath can usually be revived two or three times
before the fixing power of the
The
hypo
is
in this
way
exhausted.
addition of boric acid to a fixing bath containing potassium alum
which normally requires several revivals with acetic acid during its useful life to prevent sludge formation will greatly minimize this difficulty
and
also extend the hardening life of the bath."*'
With
the potassium
alum stock solution hardener formula given prealuminum sulphite
viously (page 157) the precipitation of a sludge of
may
also be prevented
by the addition
of 25
grams of sodium potassium
tartrate (Rochelle salts) per liter (375 grains per quart) of the solution.
^Mineral acids, such as sulphuric, are generally too strong for use with fixing solutions except with baths containing
sulphuric acid
is
to be preferred.
chrome alum,
Other organic acids than
for
which
acetic,
such
as citric, tartaric, etc., can only be used under certain very limited conditions, since they tend to interfere with hardening.
B.
The Bath Does Not Harden
hardening
may
be a result of
i.
Satisfactorily.
not contain the correct proportion of aluminum or 29 "
Some
Properties of
â&#x20AC;&#x201D;
Insufficient
alum which does chromium sulphate.
the use of inferior
Chrome Alum Stop Baths and Fixing Baths
â&#x20AC;&#x201D; Part
II
"
by J. I. Crabtree and H. D. Russell. /. Soc. Mot. Pict. Eng. 14, 667 (June 1930).. 30 " An Improved Potassium Alum Fixing Bath Containing Boric Acid " by H. D. Russell and J. I. Crabtree. /. Soc. Mot. Pict. Eng. 21, 137 (August 1933)-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
166
2.
The presence
On
of alum.
much
of too
acid or sulphite or an insufficient quantity
varying the proportions of acid, alum, and sulphite in a
potassium alum fixing bath,
it
has been found that the hardening
creases as the quantity of potassium
alum
increases.
With
in-
increasing
quantities of acetic acid with a given quantity of potassium alum, the
maximum beyond which the hardening deminimum quantity of acetic acid, however, is neces-
hardening increases to a creases.
A
certain
sary to give the fixing bath a fairly long, useful sulphite precipitates, but this quantity tity
which produces
maximum
life
With
hardening.
maximum
87 °C.) beyond which the hardening
The hardening boric acid
is
aluminum
use, therefore, the hard-
ening ability of most potassium alum fixing baths at the addition of developer to a
before
usually greater than the quan-
is
first
increases with
(170° to i90°F.)
(76° to
falls off rapidly.
potassium alum acid fixing baths containing
life of
from three to four times greater than the same type of bath
A
without boric acid.
fixing bath containing boric acid also does not
sludge until the bath has become quite alkaline sible, therefore, to
(pH
= 7.0).
It
is
pos-
use baths containing boric acid equally as long or
longer than the older type of potassium
alum
fixing baths,
and without
the necessity of revival.
Fixing baths containing chrome alum usually have high
properties rapidly either tion of
chrome alum,
many
2%
or over, the hardening properties are mainlife is
life.
With a
fixed proportion of
decreased.
An
in-
and increases the chrome alum and sul-
crease in the sulphite content lowers the hardening
sulphurization
hard-
of
tained better on storage but the sulphurization
phite, the hardening
initial
them lose their hardening with or without use. With a high cencentra-
ening (over 2i2°F.) (ioo°C.) but
life
produced with alkaline film increases with the acid
concentration within certain limits.
C. Blisters.
— When a
film or print
is
transferred directly
and with-
out agitation from a developer containing a fairly high concentration of
an alkaline carbonate
to a strongly acid rinse or stop bath, or to
a
strongly acid fixing bath, small bubbles of carbon dioxide gas are apt to
form within the gelatin the carbonate.
film layer as a result of the action of the acid
If the gelatin film
a small pocket of this gas gelatin film blisters
and leaves a
is
created which bursts through the tender
spot, called a blister.
On
dry film or prints
appear as tiny crater-like depressions when examined by
flected light
(Fig. 75).
weather, and especially
This trouble
when
on
has become softened for any reason,
is
more
re-
likely to occur in hot
the rinse bath or fixing bath
is
not hard-
.
MIXING AND USING PHOTOGRAPHIC SOLUTIONS ening sufficiently.
and
is
maintained
If the gelatin is
not allowed to swell,
it
167
hardened condition
in a
can withstand the disruptive force of
the gas.
Concentrated developers containing a high percentage of carbonate
have a greater tendency carbonate concentration. in
to
produce
blisters
than developers having low
obvious that prolonged development
It is also
to become swollen exceswarmer than 70° F. (2i°C.).
an exhausted developer allows the gelatin
sively, especially
if
Fig. 75
the developer solution
—
Blisters
is
on a film emulsion (enlarged greatly)
by observing
Blisters can be prevented entirely
the following precau-
tions: a.
Keep
the
temperature of
working solutions around 65 °F,
all
(i8°C.) for films or plates, and around 70°F. (2i°C.) for papers. b.
Agitate the films or prints
when
first
immersed
in the acid rinse or
fixing bath. c.
Whenever
possible, use a cool water rinse previous to or instead of
the acid rinse bath. d.
Use a non-blistering
alkali
in
the developer such as borax or
Kodalk. If the
wash water temperature
low)
it is
ture
and a chrome alum
ough
is
below 65°F. (i8°C.) (but not too
usually possible to maintain the solutions around this tempera-
rinse
is
rinse bath
can be eliminated, provided a thor-
given in running water previous to immersion in an acid
hardening fixing bath.
If
the
ever, 75°F. (24°C.) or above,
wash water temperature
and the temperature
is
high,
how-
of the processing so-
168
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
lutions can be maintained at 65°F. (i8°C.), a rinse should be used to avoid possible trouble
chrome alum hardener
from
blisters.
When
the
temperature of the processing solutions cannot be held around 65 °F. (i8°C.) and
if it
sodium sulphate
75°F. (24°C.) or above,
rises to
to the developer
Chapter VIII.
and hardener
it is
necessary to add
rinse as discussed in
—
D. Dichroic Fog. If the fixing bath does not contain acid or if old and exhausted and contains an excess of dissolved silver salts,
it is
a stain called dichroic fog
sometimes produced on the
is
flected light, film stained in this
mitted light
it
fresh acid fixing bath or
ject of dichroic fog
Scum on
is is
the film
if
is
by
In retrans-
Dichroic fog never occurs in a rinsed before fixing
and the tem-
kept at 65° to 7o°F. (18° to 2i°C.).
The sub-
discussed fully under Chapter XI, page 249.
the Surface of Fixing Baths.
exhausted fixing bath
film.
looks yellowish-green and
appears reddish-pink.
perature of the bath
E.
way
— When a
hydrogen sulphide gas usually present
in the air reacts
with the silver
thiosulphate in the bath and forms a metallic appearing surface of the solution.
partially
allowed to stand several days without use, the
is
scum on the
This scum consists of silver sulphide and should
be removed by drawing the edge of a sheet of blotting paper across the surface of the bath, or
by using a skimmer made
of several strips of
cheesecloth stretched over a wire frame (Fig. 20, page 40).
A white
scum
consisting of
the films or prints.
velopment;
2.
This
is
aluminum
caused by:
i.
is
found sometimes on
insufficient rinsing after de-
too low a concentration of acid in the fixing bath; 3. in-
sufficient agitation of the film
Since
sulphite
aluminum
sulphite
is
on
first
immersing
soluble in alkali the
in the fixing bath.
scum may be removed
by swabbing the film or print with a 10% solution of sodium carbonate and then washing thoroughly. When using a chrome alum hardener rinse or fixing bath containing chrome alum, a greenish white scum consisting of chromium hydroxide
chromium sulphite is sometimes precipitated on the surface of when an excess of alkaline developer is added to the solution containing the chrome alum. The precipitate may also form on the film locally if it is not agitated sufficiently when first immersed in the hardener or fixing bath. It is readily removed from the wet film by swabbing with moist absorbent cotton but it is very difficult to remove when or basic
the film
once dried on the film surface.
sium
citrate
is
effective
Treatment with a
sometimes
in
5%
solution of potas-
removing the dried scum deposit
MIXING AND USING PHOTOGRAPHIC SOLUTIONS but care must be used since Rinsing
quickly.
in
treatment softens the emulsion very
this
water previous to immersion
when
or fixing bath and thorough agitation
first
in the
XI
film in
scum
Chap-
(see
for further details).
— When processing
F. Mottle.
image
hardener rinse
immersing the
either bath will usually prevent the formation of the ter
169
is
when
occasionally found
tated enough on ficiently rinsed
first
immersing
films or plates in hangers, a mottled
the hanger or rack has not been agi-
in the fixing
between development and
bath or
fixation.
if
the film
insuf-
is
In the absence of
thorough rinsing and agitation, development continues locally during the few minutes of
first
density.
and
fixing,
INIottle is also
in these spots the
produced
image has greater
the ends of the hanger protrude
if
above the surface of the fixing bath especially during the
first
stages of
fixation.
A roll
is
encountered when processing
films which have a dye-coated backing
for reducing halation effects.
mottled pattern of color sometimes
This coating
is
normally removed during processing, but
come off if the solutions do not have as when two films adhere back to back.
free access to the
5%
the film in a
It is easily
it
does not
removed by bathing
by re-immersing
solution of sodium sulphite or
all
back of the film in the
developer for a few minutes and tlien washing thoroughly.
G. Stains.
num
— Several
different types of stains such as white alumi-
sulphite stain (see E. above), sulphur stains, and yellow silver
For a complete discussion of stains
stains are occasionally produced.
caused by fixing baths, reference should be made to Chapter XI, page 230.
MISCELLANEOUS SOLUTIONS The number
of miscellaneous solutions used in
ening, intensifying, reducing, toning, etc.,
is
photography
so large that
it
for hardis
beyond
the scope of this book to deal with other than outstanding cases.
procedure
is
in general
much
the
same
ing baths, and the order of mixing
is
as
when mixing developers
The or fix-
usually stated very specifically.
—
This solution is recA. Superhardener for Bromide Papers. ommended for use after fixation and washing previous to drying on a heated belt dryer, in order to overcome the tendency of glossy prints to stick
on the
belt.
It
be sepia toned because tone.
should not be used it
if
the prints are later to
sometimes has a detrimental
effect
on the
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
170
Supplementary Hardener
[SH-2] Solution
Water Sodium Sulphite, desiccated. *Acetic Acid, 28% pure
F.) (71° C.)
to *
ounces
4^2 drams 4Jo ounces
18.0 135.0
ounces
2.0
16 1
ounces ounce
500.0 30.0
64
ounces
2.0
liter
grams cc cc
grams liters
cc
grams
add cold water
make
To make 28%
fluid
64
.
Borax
dissolved,
1.0
45.0 64.0
2
Potassium Alum Water to make Solution B Hot water (about 160°
ounces
IM ounces
32 ...
or Glacial Acetic Acid, pure cone.
When
Metric
Avoirdupois
A
acetic acid
from
liters
glacial acetic, take 3 parts of glacial acid
and add
8 parts of water.
Solution
A
should be dissolved in the same
the acid hardener given on page 157.
Then
way
as
recommended
water as recommended and add cold water to make up to volume. cool borax solution should then be
for
dissolve the borax in hot
added slowly
The
to the cool Solution
A
while stirring the latter rapidly.
If these directions are followed, a clear
solution will be obtained, but
the
if
warm borax
solution
is
added too
rapidly to Solution A, a white precipitate will form which does not re-dissolve.
Prints should be fixed in the regular fixing bath,
and placed
in the
hardener for
5 or
10 minutes.
washed thoroughly,
Then wash thoroughly
and remove surplus water before drying. Ammonium persulphate is the B. The Persulphate Reducer. only photographic reducing substance known which acts very much more on the heavy deposits than on the light deposits of the negative. It must
—
be used in acid solution as given in the following formula, and is somewhat uncertain in its behavior, occasionally refusing to act, and always acting more rapidly as the reduction progresses. This type of reducer is known as a super-proportional reducer and is described in a comprehensive paper on the subject of reducers and intensifiers by Crabtree and Muehler.^i
Persulphate Reducer
[R-l]
Water
Ammonium
Persulphate
Stock Solution Avoirdupois ounces 32 ounces 2
Sulphuric Acid, C. P. (concentrated)
For
use, take
When
i
%
dram
Metric 1.0 liter
60.0
grams
3.0 cc
part of stock solution and add 2 parts of water.
reduction
is
complete, immerse in an acid fixing bath for a few minutes,
then wash. " Reducing and Intensifying Solutions for Motion Picture Film and L. E. Muehler. /. Soc. Mot. Pict. Eng. 17, looi (1931).
31
tree
"
by
J. I.
Crab-
MIXING AND USING PHOTOGRAPHIC SOLUTIONS According to is
due largely
S.
E. Sheppard
the capricious behavior of persulphate
In preparing this solu-
to variations in the iron content.
tion, therefore, only tested
C.
â&#x20AC;˘'-
171
samples of persulphate should be used.
The Permanganate Reducer,
reducer, a typical formula of which
is
â&#x20AC;&#x201D; In
mixing the permanganate
given below,
is
it
sometimes
diffi-
cult to get all the salt to dissolve, for although fairly soluble the crystals
are quite hard and therefore dissolve slowly, especially in cold water.
The
method
best
is
to dissolve the crystals in
very hot water (about
i8o"F.) (82 °C.) with shaking and then dilute with cold water.
A
mixing procedure should be used when preparing
slightly different
large volumes (several
manganate base
is
hundred gallons) of
level
Add
this reducer.
crystals to a small shallow tank or
the per-
box supported so that
with the top of the large storage tank.
its
the small tank
Fill
with water and arrange an open outlet at a point near the top of the tank.
A
small stream of water should be arranged to run into the small
tank at a rate
sufficient to
keep the tank
full.
The
inflow
must not be
up the crystals and cause them to float. After all the crystals have been dissolved, add sufficient water to the large tank to bring the solution up to 90% of the total volume. Then add the sulphuric acid slowly while stirring the large volume of permanganate solution. This method of mixing has the advantage that it insures comso great as to stir
plete solution of all the
permanganate before the solution
is
A
used.
lead-lined iron tank or preferably an iron tank lined with acid proof
brick represents a suitable construction material for holding acid per-
manganate.
Permanganate Reducer
[R-2]
Stock Solution Avoirdupois ounces 32 A. Water Potassium Permanganate IH ounces B.
Cold water Sulphuric Acid, C. P. (concen-
32
trated)
1
Metric 1.0 liter
52.5
ounces fluid
1
ounce
grams
.0 liter
32.0 cc
For use, take i part A, 2 parts B, and 64 parts of water. When the negative has become reduced sufficiently, immerse in a plain hypo solution, or in a fresh acid fixing bath for a
few minutes,
In addition to
employed as a
its
to
remove yellow
stain, after
which wash thoroughly.
use for reduction and bleaching, permanganate
test for
hypo, since
it is
at once reduced
colored solution of the permanganate, therefore, loses 32 "
The
Effect of the Iron Content of
graphic Reducing Brit. J. Phot. 6s,
Power" by 314 (191 8).
S. E.
Ammonium
Sheppard.
is
by hypo, and the its
color in the
Persulphate on
Its
Photo-
Phot. J. Amcr. 55, 29" (1918)
;
also
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
172
presence of any hypo.
It
may
test the extent
consequently be used to
hypo from negatives or prints in washing (see Formula HT-ia, page 313). When permanganate is reduced, a brownish precipitate of manganese dioxide is obtained and sometimes negatives or prints which have been treated with permanganate are stained brown by Fortunately, manganese dioxide is removed by sodium this material. bisulphite which reduces it still further, forming a soluble manganese The brown stain can, therefore, be removed by immersion of the salt.
of the elimination of
stained material in a
5%
solution of bisulphite.
D. Farmer's Reducer. sists of a
â&#x20AC;&#x201D; This subtractive
or cutting reducer con-
mixture of potassium ferricyanide and hypo.
composes very rapidly as soon as the ferricyanide For
this reason, the
is
The
solution de-
added
to the
hypo.
reducer components should never be added together
until just before using.
prepared by mixing a strong solution and adding the required volume (accord-
It is best
of ferricyanide (about 20^'^
),
ing to the strength desired) to a lo^c solution of plain hypo.
Details have been worked out
by A. ^Murray
for using
Farmer's
re-
ducer in a controlled manner for the peripheral reduction of half-tone dots on photographic negatives to be used for lithographic work.^'^
Crabtree and iMuehler
-^^
have published directions
for the
use of
Farmer's reducer in two solutions as well as for the usual single soluThe material is treated first in the ferricyanide and then in the tion. This method has the advantage that the potassium
h)T)o solution.
ricyanide solution will keep indefinitely provided strong daylight.
E. Ferric
it
fer-
shielded from
is
(See Formula R-4b, page 322.)
Alum
Proportional Reducer.
â&#x20AC;&#x201D; The only known pro-
portional reducer which will keep satisfactorily consists of an acid solution of ferric alum, the formula for
Ferric
[R-7]
Alum
which
is
as follows:
Proportional Reducer Avoirdupois
Water Sulphuric Acid, C. P. (concentrated) Ferric Ammonium Sulphate (Ferric
ounces 16 2J^ fluid drams
Ammonium Alum)
Water
to
make
Vi
32
ounce ounces
Metric 500.0 cc 10.0 cc 15.0 1 .0
grams liter
be careful to add the acid to the water solution and not vice versa or the water will boil with explosive violence (see Section J on Sulphuric Acid, page 175). The negative should be hardened with
When mixing,
33 "
New
Control Methods in Chemical Retouching " by A. Murray.
77, 121 (1930). 34 " Reducing
tree
and Intensifying Solutions for Motion Picture Film and L. E. Muehler. /. Soc. Mot. Pict. Eng. 17, looi (1931).
"
Brit. J. Phot.
by
J. I.
Crab-
MIXING AND USING PHOTOGRAPHIC SOLUTIONS
173
an alkaline solution of formalin before treatment as the reducer has a strong tendency to soften the gelatin (see Formula SH-i, page 314).
Important.
â&#x20AC;&#x201D;
It is
very important when using this reducer to keep
the film thoroughly immersed while in contact
eral
remains in the solution.
it
brown
stain will also form
if
the negative contains traces of
or silver salts.
The Iodine-Cyanide Reducer.
F.
ducer
made from
is
during reduction.
Iodine
tion of potassium iodide,
is
â&#x20AC;&#x201D; A very powerful cutting
i
re-
and
to
make up
is
the reducer,
10%
formed
soluble in a solu-
parts of iodine
5
solution of potassium iodide.
part of sodium or potassium cyanide in 10 parts of the
iodine-iodide solution
The
silver iodide
not soluble in water but
crystals are dissolved in 100 parts of a
dissolve
Genhypo
a solution of iodine in potassium iodide, to which
potassium cyanide has been added to dissolve the
Then
If left
with the air for any appreciable time, stains will result.
and make up
activity of the reducer
may
100 parts with water for use.
to
be decreased by diluting with water.
This reducer can be used effectively for bleaching out the silver image after inking over certain parts of a print or
has the advantage that
When
it
bromide enlargement.
using the reducer, the usual precautions should be observed
relative to the use of the poisonous chemical,
page 271).
G.
It
does not leave any residual stain.
The Monckhoven
potassium cyanide (see
â&#x20AC;&#x201D; Solution B
Intensifier.
Monckhoven's
of
intensifier (formula given below), containing silver nitrate and potassium cyanide, often proves a stumbling block when mixed the first few
times.
secret of mixing this solution correctly consists in having
The
excess of silver present, which
is
to the cyanide solution so that a
on standing. If there is
Then
filter off
assured
by adding enough
permanent precipitate
is
an
silver nitrate
obtained even
the precipitate before using the solution.
not an excess of silver present, after bleaching in the Solu-
tion A, the
image
will
be dissolved by the cyanide.
Mercury
Intensifier
[Ii^-l] Metric
Avoirdupois 24
Vl'ater
Potassium Bromide Mercuric Chloride Water to make
Bleach the negative
in the
J^
%
32
ounces ounce ounce ounces
above solution until
750.0 cc 22.5 grams 22.o ftrams 1.0 liter
it is
white, then
wash
thoroughly.
The
negative can be blackened with lo^o sulphite solution or a de-
veloper such as
Formula D-72 diluted
1:3, or with
10% ammonia
174
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
(cone.
28% ammonia
diluted 1:9), these giving progressively greater
To
density in the order given.
increase contrast greatly without in-
shadow portions blacken
creasing the density in the
in:
A
Solution
Avoirdupois
Water
16
Sodium
or Potassium Cyanide ....
}4,
500.0 cc
ounces ounce
500.0 cc 22.5 grams
16
Silver Nitrate, crystals
M
* The usual precautions regarding the use of cyanide which should be observed (see Chapter XIII, page 271).
To prepare
the intensifier, add the silver nitrate Solution
A
cyanide Solution
until a
to stand a short time
and
permanent precipitate
filter.
H. Silver Intensifier. that
it
This
is
a deadly poison
is
B
the potassium
to
just produced; allow the
is
mixture
called Monckliovcn's intensifier.
â&#x20AC;&#x201D; The following formula has the advantage
image of neutral
yields an
grams
15.0
B
Solution Water
Metric
ounces ounce
color,
whereas most
intensifiers
change
the original color of the image giving an image which varies in hue from
a bluish-black to a reddish-brown or yellow."'^
motion picture projection prints, lantern
The
a very useful formula.
and the degree of
resulting
the standpoint of
solution gives proportional intensification
intensification
The
of treatment.
From
slides, or transparencies, it is
is
by varying the time
easily controlled
image
is
permanent.
Silver Intensifier
[In-5]
(Store in a
Stock Solution No.
brown
bottle)
Silver Nitrate Water to make
Stock Solution No.
Sodium Water
2
32
ounces ounces
60.0
ounces ounces
60.0
ounces ounces
105.0
grams
1.0 liter
2
Sulphite, desiccated
2
make
to
Metric
Avoirdupois
1
32
grams
1.0 liter
Stock Solution No. 3
Sodium
Tiiiosulpliate (Hypo) (crys-
tals)
33^2
Water
make
to
32
grams
1.0 liter
Stock Solution No. 4
Sodium
Sulphite, desiccated
J4
Elon
Water
Directions to
I
to
for
Mixing.
part of Solution No.
mixing.
The white
addition of
i
345 96
make
â&#x20AC;&#x201D; Slowly i,
i
grains
ounces
part
of
Solution
precipitate which appears
part of Solution No. 3.
2
is
then dissolved by the
Allow the resulting solution to
Then add, with
stirring, 3 parts of
" Reducing and Intensifying Solutions for Motion Picture Film and L. E. Muehler. /. Soc. Mot. Pict. Eng. 17, looi (1931).
35
No.
shaking or stirring to obtain thorough
stand a few minutes until clear.
tree
add
15.0 grams 24.0 grams 3.0 liters
ounce
"
by
J. I.
Crab-
MIXING AND USING PHOTOGRAPHIC SOLUTIONS The
Solution No. 4.
intensifier
is
now ready
175
and the negative
for use
(or transparency) should be treated immediately.
The degree of intensification depends upon the time of treatment which should not exceed 25 minutes; normal intensification should be obtained usually in 10 to 20 minutes. Then immerse the negative for 2
minutes
The
in a plain
solution
is
30% hypo
and wash thoroughly.
solution
stable for about 30 to 45 minutes before a precipitate
of silver forms in the bath.
If
used after this time limit, a precipitate
appears which will deposit on the highlights and produce fog.
The Caustic
I.
Alkalis.
— When
dissolving
either
sodium hy-
droxide (caustic soda), or potassium hydroxide (caustic potash), never use hot wafer because the heat of solution evolved solution
and
stir
is
apt to boil with explosive violence.
frequently to prevent local heating of the solution.
of these solutions
is
heavy caustic solution
Sulphuric Acid. acid or when adding the J.
is
— When
bottom on account
making
higher
its
dilute solutions of sulphuric
In the latter case, excessive heat
may
meets the acid and the acid
Hypo-Alum Toning
Baths.
add
the water to
produced when the water
— Occasionally when a hypo-alum
mixed, the solution turns a
The
formation of silver sulphide.
is
and never
spatter on the hands or face causing
serious burns.
is
of
acid to a developer or a fixing bath, always
the concentrated acid to the water with stirring
toning bath
either
stirred thoroughly, otherwise the
will sink to the
specific gravity.
the acid.
When
added as a component part of another solution,
care should be taken that the bath
K.
so great that the
is
Always use cold water
murky black
as a result of the
usual hypo-alum bath consists of a
mixture of hypo and potassium alum, with or without the addition of silver chloride or silver iodide.
toning bath given below or
hypo-alum bath cipitate, the
is
bath
not stirred will
If boiling
water
is
the order of mixing
if
when adding
used for mixing the is
changed or
if
the
the white silver chloride pre-
turn a dirty gray or black.
Once the
solution
cannot be cleared immediately except by a tedious filtration process, but it will settle out almost completely if allowed to stand overnight when the clear supernatant liquid may be poured or
becomes black,
siphoned
it
off for use.
Hypo- Alum Bath
for Sepia
Toning
Avoirdupois
Cold water
90 ounces
Hypo
It
ounces
(Formula continued on next page)
Metric 2800.0 cc 480.0 f^rams
[T-la]
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
176
Dissolve thoroughly, and add the following solution: Hot water (about Potassium Alum
Then add
160° F.) (71° C.)
20
ounces
640.0 cc 120.0 grams
4 ounces
the following solution (including precipitate) slowly to the
h)^o-alum solution while
stirring the latter rapidly.
Cold water
2
ounces
60 grains 60 grains
Silver Nitrate Crystals Sodium Chloride (table salt)
64.0 cc 4.2 grams 4.2 grams
After combining above solutions
Add water Note
The
to
make
1
gallon
4.0 liters
adding the sodium and immediately afterward the solution containing the milky white precipishould be added to the hypo-alum solution as directed above. :
silver nitrate should be dissolved completely before
chloride, tate
For
pour into a tray standing
use,
(49°C.).
water bath and heat to i20°F.
in a
Prints will tone in 12 to 15 minutes.
The bath should never be heated above i25°F. (52°C.), otherwise blistering, staining,
and non-uniform toning
Toning Bath.
L. Sulphide
— When
will result.
by the redevelopment process, a solution of sodium sulphide is used for redeveloping. Sodium sulphide is supplied commercially in two forms, crystalline and fused sulphide. The latter is to be preferred for photographic work, sepia toning
since the crystalline form deliquesces or absorbs moisture from the air
very quickly and
is
The crystals often contain One part by weight of fused (approximately) by weight of the
troublesome to handle.
impurities and do not yield a clear solution.
sulphide
equivalent to three parts
is
Both
crystals.
varieties contain iron as
an impurity.
In preparing a
sulphide solution, the chemical should be dissolved in hot water and
allowed to stand about 24 hours before use.
The
iron sulphide settles
out as a sludge and the clear yellow solution should be decanted off before use.
Sodium sulphide
crystals
sometimes contain hypo as an
impurity, which will attack the highlights of the print and give a
bleached out effect in the
final tone.
Toning baths containing sulphide
should not be used near developer solutions or fog will result.
M. Iron Toning Bath, tive
—-Lantern
motion picture film are often toned
and posiby treatment in
slides, transparencies,
to a blue color
a bath containing iron (ferric) ferricyanide, the silver image being partly
converted to a mixture of silver ferrocyanide and ferric ferrocyanide by the process.
Unless instructions are followed carefully when preparing
the toning bath, a certain degradation of tone will result.
formula
is
as follows:
A
typical
MIXING AND USING PHOTOGRAPHIC SOLUTIONS Iron Toning Bath
[T-11] Avoirdupois
Ammonium Persulphate Ferric Ammonium Sulphate (Ferric Alum)
7 20
Oxalic Acid
45
Potassium Ferricyanide
15
Ammonium Alum
75
Hydrochloric Acid, 10% Water to make
32
Dissolve chemicals *
A 10%
solution of hydrochloric acid
trated hydrochloric acid and adding
Directions for Mixing.
it
in is
grains grains grains grains grains
Metric 0.5 ftram 1.4 3.0 1.0 5.0
^ dram
grams grams gram grams
1.0 cc 1.0 liter
ounces
order given.
prepared by taking
i
part of concen-
to g parts of water.
— Dissolve each
of the solid chemicals sepa-
(preferably in a glass or enamelled ware container, free of
rately
cracks) in a small volume of water, and
The
177
filter
into the tank or crock.
solutions should be mixed strictly in the order given,
luted to volume with cool water.
and then
di-
If these instructions are followed, the
bath will be pale yellow in color and perfectly clear.
When
preparing a uranium toning bath, or a uranium mordanting
bath, similar precautions should be followed (see page 327).
N.
Dye
tern slides
Solutions,
— Dyes
and motion picture
the mixing vessels should be
are used for tinting and toning of lan-
films.
made
When
preparing solutions of dyes,
of hard glazed earthenware, stone-
If enamelled ware is used, it should have a high glaze any cracks which would expose the metal underneath and tend to contaminate the dye solutions. The solid dye should be dissolved in as small a volume of hot distilled water as possible, and filtered
ware, or glassware.
and be
free of
through fine muslin or a suitable mechanical
that
all
be diluted to the required
volume with cool
distilled
Chapter
(see
filter
Hot water should be poured over any the dye will be dissolved. The solution in
page 32).
III,
residue remaining so the tank should then
water (about 65°F.)
(i8°C.).
Very
dilute solutions of certain dyes are also used for optical sensitiz-
ing of films or plates
by bathing.
Dundon
has described the special
technique involved for such work and reference should be original paper for
working
details."'
Dyes
made
to the
are also used in a preliminary
bath before development or added to the developer to desensitize the emulsion and permit development in brighter
The technique
light.
for
mixing desensitizers has been described on page 144. 36 " Color
Amer. Phot.
Sensitizing
Photographic
20, 670 (1926).
Plates
by
Bathing
"
by
M.
L.
Dundon.
CHAPTER
VIII
HANDLING SOLUTIONS AT HIGH TEMPERATURES Photographic solutions give the most satisfactory and uniform results
when used
normal temperatures of 65°F. (i8°C.)
at the
materials and 70° F. (2i°C.) for positive materials.
degrees above or below these temperatures sions arise
except by
when
it
extremely
is
difficult
not significant but occa-
is
control the temperature
to
artificial refrigeration or heating.
for negative
Variation of a few
Several methods of tem-
perature control have been discussed under Chapter V.
When
a gelatin film
is
placed in an alkaline developer solution,
ally starts to swell immediately.
high, 75° to 90° F.
and becomes very is
usuis
(24° to 32 -C), the gelatin swells more rapidly soft
and
difficult
ers containing carbonate, the
tion
it
temperature of the developer
If the
increased greatly
when
the film
blister
formation and reticula-
placed subsequently in the acid
is
The developer
rinse or in the acid fixing bath.
Also, with develop-
to handle.
danger of
solution,
on the other
hand, oxidizes more rapidly and tends to fog and stain at a much earlier stage of exhaustion than at normal temperatures.
The
extent of these swelling and shrinking effects mentioned above
has been measured by Sheppard
and the
^
results of a typical case with
motion picture positive film at normal temperatures are shown ure 76.
At higher temperatures
or
when
the temperature
is
in Fig-
different for
the various operations, the expansion and contraction effects are
worse.
In
fact, the strains set
up
may
much
be so great as to distort the gela-
produce reticulation (see Fig. 77). It is important, maintain all photographic solutions at a temperature as
tin sufficiently to
therefore, to
nearly normal as possible (65° to 70° F.)
(18° to 2i°C.), but
if
this
cannot be done, the various solutions should be maintained at equal temperatures.
At high temperatures, the useful shortened because the tendency
life
of
an acid
is
bath
is
usually
increased.
Films
fixing
for sulphurization
which are swollen by processing at high temperatures also require longer to
dry and are more subject to drying troubles than films on which the
gelatin coating
Nearly
all
is
not excessively swollen.
solid chemicals
used
enough melting point so that there
in
photographic work have a high
is little
danger of the solids melting
while stored in bottles or other containers, but
it is
good practice to keep
1 " Behavior of Gelatin in the Processing of Motion Picture Fihn Sheppard. Trans. Soc. Mot. Pict. Bug. No. 32, 707-727 (1927).
"
by S. E.
.
SOLUTIONS AT HIGH TEMPERATURES chemicals as dry and cool as possible during storage. for instance,
17Q
Bottles or cans,
should not be placed on shelves or in cupboards near a
source of heat such as a radiator, an electric light, or a stove, or where direct sunlight can shine
When
in solution
upon them
must be taken Chapter \').
greater and tion (see
(see C'hapter IX, page 195
)
the effect of temperature on chemicals
is
much
into account with every photographic solu-
50
^ 40 30 20
10
ALKAUNE
ACID FIXING BATH
DCVeLOPE.R 5 MIN
S MIN
Swelling of Eastman motion picture positive film during processing
Fig. 76
65°F. (i8°C.)
at
The is
secret of processing films or plates under hot weather conditions
to prevent
and some
abnormal swelling of the gelatin coating. Most papers and plates are hardened during manufacture and no
films
trouble from e.xcessive swelling rials.
]\Iost films
and
is
manufacture and the gelatin layer to 43 °C.)
perature
when
is
will
a strip of the material
raised gradually.
melting point of gelatin films sists of
usually encountered with these mate-
however, are not super-hardened during
plates,
A is
melt around 95° to iio°F. (35° is
placed in water and the tem-
suitable apparatus for determining the
shown
in
Figure 73, page 156, and con-
The wooden frame which is
a beaker of water heated by means of an electric hot plate.
strips of material to
be tested are pinned
to the
immersed in the beaker of water. With unhardened materials, care must be exercised when handling if the temperature of the processing solutions or the wash water is above 75°F. (24°C.). A few materials such as x-ray film and some motion picture films are coated with emulsion on both sides
and require
special precautions
when handling
at
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
180
high temperatures. is
With
roll films
and cut
films, the
back of the film
coated with a layer of gelatin which serves to prevent curling and the
degree of hardness (melting point) of this layer
is
usually greater than
Motion picture films (except double coated do not have a gelatin coating on the side opposite to the
that of the emulsion layer. positive)
emulsion.
Fig. 77
— Reticulation of a gelatin
Special Technique for is
film.
High Temperature Processing.
—
If
it
impossible to install a cooling system, a special technique must be
adopted in order to process films or plates satisfactorily at temperatures above 75°F. (24°C.). This technique consists in i. using developers containing a high concentration of sodium sulphite and an alkali or an inert salt, such as
and
2.
sodium sulphate,
hardening the film in a
dium sulphate (anhydrous) the unswollen condition.-
An
chrome alum plus 5% soand while the gelatin is in hardened in this manner, it will then
after developing
When
withstand immersion in very ing.
3%
to prevent swelling of the gelatin,
solution of
warm water
without swelling or reticulat-
exception to the technique described above should be
made
with double coated films which are hardened excessively by this procedure. terials at
A
modified technique will be described for handling these ma-
high temperatures.
Development of Films or Plates at Temperatures of 75° to Any good developer may be used which de-
90°F. (24° to 32°C.).
—
velops fully in 6 to 7 minutes at 75°F. (24°C.).
The developer should
2 " Handling Motion Picture Film at High Temperatures " by Trans. Soc. Mot. Pict. Eng. No. 19, 39-47 (1924).
J.
I.
Crabtree.
SOLUTIONS AT HIGH TEMPERATURES
181
preferably contain developing agents which oxidize slowly, such as Elon, hydroqiiinone, or para-aminophenol and should have a saline content of
not
less
added
An
than io%.
inert salt such as
to the developer to
sodium sulphate should be
supplement the anti-swelling action of the
salts in the developer.
Usually a concentration of lo to
sulphate crystals (4.3 to
6.5% desiccated sulphate)
is
15% sodium
satisfactory.
addition of sodium sulphate retards the development about
30%.
The If
a
developer requires normally about 9 minutes at 8o°F. ( 26. 5°C.), it should be compounded twice as strong so as to diminish the swelling tendency,
when
it
develop in approximately
will
developer at high temperatures
is
dizes rapidly at high temperatures
5
minutes.
The
use of a pyro
not recommended because pyro oxi-
and
Typical
stains the gelatin film.
developers which are satisfactory for high temperature work are given in the
Appendix, page 283.
The Use
of
Sodium Sulphate.
perature control equipment,
70°F. (2i°C.) for temperature
is
all
it is
— In
solutions rather than 65°F. (i8°C.), because this
closest to the average
much and
day emulsions have
The
there
little
is
less
The advantage
room temperature.
of the lower temperature of 65°F. (i8°C.)
not swell as
the absence of precise tem-
better to adopt a basic temperature of
is
that the gelatin film does
tendency to
fog,
although present
propensity to fog when used correctly.
increase in activity of a developer resulting from rise in tempera-
ture can be offset
by adding sodium
When
sulphate.
sulphate has been
added, the developer does not penetrate the gelatin film as rapidly and its
developing activity
is
lowered.
For example, with Formulas correct
gamma
(i.i)
is
DK-50
and DK-60, assuming that the
obtained at 65°F. (i8°C.), the quantities of
desiccated sodium sulphate to add at the various temperatures to
and
DK-60 are given
in the following Table.
If
DK-50
sodium sulphate crystals
are used, double the quantities indicated should be used.
TABLE
6
Total Content of Sodium Sulphate (Desiccated)
DK-60
DK-50 Temperature 70°F.
75°F.
8o°F.
7
2.0% ( 2| 8.5% (12 13.0% (18
Min. oz./gal.) oz./gal.) oz./gal.)
10 Min.
8.5% (12 13.0% (18 16.5% (24
oz./gal.) oz./gal.) oz./gal.)
7 Min.
8.5% 13.0% Not recommended
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
182
Thus, assuming that the developer activity
is
satisfactory at 65 °F.
(i8°C.) withDK-5o,at7o°F. (2i°C.) 8.5% of sodium sulphate should be added and, if the temperature then rises to 75°F. (24°C.), a further
4-5% (13% minus 8.5%) should be added. directly to the tank provided
it is
The
salt
stirred to insure that
may
be added
thoroughly
it is
Similar tables can be prepared for other developers.
dissolved.
Of course, once the sulphate is added, if the temperature drops again, the time of development must be prolonged so that it would appear desirable to maintain the temperature of the developer, if necessary, by means of steam or hot water coils of plain black wrought iron (not galvanized) immersed in the developer tanks.
When
replenishing such developers containing sulphate,
is
it
neces-
sary to add, likewise, an equivalent amount of sulphate to the replenisher.
The
new
introduction of the
Kodalk,
alkali,
in
1934
is
of special
Formula
interest because of its adaptability for tropical development.
DK-15
(page 284) containing Kodalk has been compounded particu-
weather processing and has the following advantages:
larly for hot is
non-blistering because no gas
to the acid
formed when the developer
is
hardener rinse or the acid fixing bath,
2.
i.
It
added the development is
rate changes slowly with time so that on slight overdevelopment, the
negatives will not be too dense, and 3.
tendency veloper
in conjunction
is
hands
minimum scumming The de-
and plates are more conveniently handled
films
when working
in direct contact
The
has a
equally satisfactory for tray or tank use.
Both sheet or racks
it
with the average acid fixing bath.
at high temperatures,
in
hangers
which avoids bringing the
with the materials while wet.
addition of the hardening agent, formalin, directly to a developer
has also been recommended and gives satisfaction in certain cases but in
many
tity of
instances
it
sulphite in the developer.
hyde
For
causes fog.
maximum
hardening, the quan-
formalin must be adjusted carefully to the quantity of alkali and
According to Crabtree and Ross
formalin
is
tion for this reaction
Note on
J.
many
quite objectionable to
in small or poorly ventilated
3
formalde-
reacts with the sulphite constituent of the developer to produce
a formaldehyde-bisulphite complex and sodium hydroxide.
and
^
F. Ross.
"
Use
of
is
The odor
persons and, therefore,
its
of
use
The equa-
darkrooms should be avoided.
as follows:
Formaldehyde
in
Brit. J. Phot. 77, 71, 1930.
Developing Solutions " by
J.
I.
Crabtree
SOLUTIONS AT HIGH TEMPERATURES
183
HCHO + Na,S03 + H.,0 ^ HCHO-NaHSO, + NaOH Sodium
Formalin
Water
Sodium Hydroxide
Formo-Siilpliite
Sulpliite
Although the use of formalin ers,
very limited in single bath develop-
is
presents certain advantages for use with two bath developers for
it
rapid processing, for example, in news photography.'
Bath No.
first in is
in
i
absorbed but very
Bath No.
2
little
development takes place.
film
is
placed
then placed
It is
containing sulphite, formalin, and bromide (plus a de-
Formula SD-6
sensitizer for control of aerial fog), see
Appendix A, page 306. first
The
low alkalinity where a certain volume of solution
of
Development
in Solution 2
in
Chapter XIV,
proceeds rapidly at
but practically stops after a short time when the developing agents
have had time to
diffuse out of the film.
The formalin hardens
the film
and also reacts with the sulphite to form sodium hydroxide which turn activates the developer.
in
Satisfactory results are obtainable at tem-
This method of development avoids the troublesome reactions that otherwise occur between many developing agents and formalin when used in a single bath deperatures from 65° to 85°F. (18° to 29.5°C.).
veloper.
Developer Fog.
—
If a
developer tends to give excessive fog
when
used at 85°F. (29.5°C.) a small quantity of potassium bromide (30 grains per gallon) (0.5
gram per
liter) or
potassium iodide
dram
(i
of a
lO/r solution of iodide per gallon) (o.oi gram per liter) should be added. If
streaked aerial oxidation fog
produced, add one part in 250,000 of
is
pinakryptol green which will usually eliminate this type of fog (see
method
of mixing desensitizers,
The Rinse over
2
page 144).
— After development,
Bath.
or 3 seconds in water
rinse the material for not
and then immerse
minutes
for at least j
in
chrome alum solution containing s^/c sodium sulphate, anhydrous* (12% crystal sulphate) (Formula SB-4, page 308). Agitate a
3%
the material for 30 or 40 seconds to
when
first
placed in this bath, in order
minimize the tendency for the formation of
chrome alum
stains.
If the film or plate is
tated, the alkali in the developer
mium 4
is
hydroxide on the film which
" Rapid Processing
Methods
30, 67, 142 (1936). * With some negative
" by
blisters, streakiness
apt to precipitate a sludge of chrois
difficult to
H. Parker and
J.
remove.
I.
Crabtree.
materials and providing the temperature
than 85°F. (29.5°C.) the sodium sulphate
and
not rinsed slightly and agi-
may be
Amer. Phot. is
not higher
omitted from the hardener formula.
PHOTOGRAPHIC CHE^HCALS AXD SOLUTIONS
184
The chrome akim
in the
hardener
sufficiently acid to neutralize a
is
considerable quantity of alkali carried over from the developer. addition of acetic acid to the bath
is
not recommended because
creases the tendency for blister formation.
ener rinse bath sometimes
recommended
For
temperatures.
maximum
The
plain
must be maintained between
tion
pH
phuric acid
is
3.8
is
is
and 3.0
for alkaline film.
Sul-
the most satisfactory indicator (see discussion on
Acid should be
by lo-inch films or plates (or per gallon of 3% chrome alum hardener
after processing ten to fifteen 8
their equivalent in other sizes)
The
acid revival
Although
it is
may
usually be repeated several times.
not essential, a rinse of
development and before immersion the
For
value of the chrome alum solu-
preparation and use of an indicator, pages 144-145).
bath.
at high
to be preferred.
the most suitable acid for maintaining the acidity and
brom phenol blue added
which con-
when developing
chrome alum solution
hardening, the acidity or
this reason, the hard-
for photofinishing,
tains acetic acid, should preferably not be used
The
this in-
life of
the chrome
for blister formation.
i
in the
or
2
alum bath and minimize
A
seconds in water after
hardener rinse will prolong still
more the tendency
prolonged water rinse should be avoided, how-
and effective hardmore the gelatin is swollen. Furthermore, the gelatin may be tanned most effectively when it is slightly alkaline and it is, therefore, undesirable to wash all the developer out of the film. Space and time requirements will usually determine whether a water rinse can be used in addition to a hardener rinse. Above 85 °F. (29.5^0.) the water rinse should be omitted if any signs of softening of
ever, as the film continues to swell while in the water
ening becomes more
difficult the
the gelatin are observed.
however, by using a
Softening of the gelatin
10% sodium
may
be avoided,
sulphate solution instead of a water
film for 10 or 15 seconds after
development and
previous to treatment in the chrome alum rinse bath.
This procedure
rinse
and immersing the
remove much of the alkaline developer from the film before it reaches the chrome alum acid rinse bath. When the developer solution is Life of Hardener Rinse Bath.
also
seems
to
â&#x20AC;&#x201D;
carried over in the gelatin layer of the film into the hardening rinse bath,
the
chrome alum solution gradually
loses its hardening properties.
sulphite in the developer reacts with the
chrome alum causing
The it
to
change from a violet-blue colored solution to yellowish-green in which state it ceases to harden. It should then be replaced by a fresh bath.
A
plain
chrome alum solution
definitely,
will retain its
but as soon as sulphite
is
added
hardening properties
to the
in-
bath the solution gradu-
SOLUTIONS AT HIGH TEMPERATURES ally loses its hardening properties
whether used or not, and
185
in the course
of several days will cease to harden gelatin unless the acidity of the bath
has been adjusted as mentioned on page 147. With average use, the hardener rinse bath should be replaced four or five times as often as the fixing bath.
The Fixing in conjunction
Bath.
rinse bath the film should be so
gelatin will not dissolve in boiling water.
the chrome alum bath loses its
is
is
This
may
bath
be used
it
turns green and
Care should be exercised
when
discarded
hardened that the
only true providing
is
not allowed to be used after
hardening properties.
hardener bath
fixing
with the chrome alum hardening bath, because on leav-
chrome alum
ing the
— Any acid hardening
it
loses its
to see that the
hardening powers and
is
replaced by a fresh bath.
Although
is
it
possible to revive fixing baths
when they reach
a cer-
by the addition of a measured quantity of acid, not recommended when working at high temperatures
tain stage of exhaustion this
procedure
is
because of the increased danger of precipitating sulphur.
attempt revival, revival
which
is
is
it
is
safer practice to discard the bath.
Rather than Furthermore,
unnecessary when using the fixing bath containing boric acid
described on page 157.
— After
Washing.
rials for 10 to 15
fixing
minutes.
thoroughly for
If
running water
5
minutes, wash the mateis
not available three suc-
remove most
of the hypo, but a
thorough washing at a later date should be given
in order to insure
cessive soakings of 5 minutes each will
permanency. Warning.
— Films
alum hardener or
or plates which have been treated in a
in a
chrome alum
fixing
chrome
bath should always be wiped
and before drying to remove any possible traces chromium scum which might be on the film surface. Such scum, if
carefully after washing of
is very difficult and often impossible to remove. Processing of Double Coated Films Under Hot Weather
allowed to dry,
Conditions.
— Success
in
high
temperature
processing
of
double
coated films (emulsion coated on both sides) such as x-ray and certain types of motion picture film depends on the observance of the following precautions:
i.
short time of development,
development and
onds after immersion fixing bath,
5.
2.
thorough rinsing between
fixation, 3. agitation of the film for at least 15 secin the fixing bath, 4. use of
a special hardening
limitation of the time of washing to 15 minutes.
Many chrome alum effectively while the
fixing baths are capable of
bath
is
hardening gelatin very
fresh but they lose their hardening proper-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
186
in a
ties
searches
fixing baths
by Crabtree and
have been compounded as a
Russell
A
'
result of re-
which maintain good hardening char-
two weeks unless previously exhausted by
acteristics over a period of
use.
Within recent years,
few days either with or without use.
chrome alum
formula suitable for use with double coated films
is
given in the
Appendix, page 311.
The hardening power of this special chrome alum fixing bath Formula F— 23, page 311) will permit about twenty 8 by lo-inch films or their (
equivalent to be processed per 4
The
processing procedure
is
liters (gallon).
Develop
as follows:
concentrated
in a
developer for times varying from 3 minutes at 7S°F. (24°C.) to 2 minutes at 85 °F. (29.5°C.). Then rinse the films in water for not over 3 seconds or
from 10 to 15 seconds
10% sodium
in a plain
sulphate
bath, immerse in the fixing bath, and agitate for at least 15 seconds.
Fix for at least 15 minutes with occasional agitation.
Wash
for a time
not exceeding 15 minutes in a tank where the hourly flow of water
should be at least twelve times the volume of the tank.
When
hardening
is
the chief consideration, then the chrome alum
fix-
non-scumming properties are also of importance, the special potassium alum acid fixing bath containing Kodalk (Formula F-io, page 311) is recommended. ing bath should be used, but
Although
it is
if
anti-sludging or
possible to handle double coated films at temperatures
above 85°F. (2g.5°C.) by using able to do so
if
this processing technique,
the temperature can be brought
or lower, since the danger of blisters, stains, is
much
down
it is
inadvis-
to 85 ^F. (29.5°C.)
and softening
of the gelatin
greater at higher temperatures.
Relative Temperatures of the Various Solutions.
—
can-
It
not be emphasized too strongly that high temperature processing should
Whenever
only be regarded as an emergency measure. tions should be handled at
do
so,
then
it is
normal temperatures.
If
possible, solu-
it is
impossible to
important that the temperature of the various solutions
should be maintained as nearly equal as possible.
If a swollen film
subjected to a sudden change of temperature, as, for example, transferring from a cool developer to a
warm
fixing bath, the gelatin
tends to pucker up and assume a leather-like appearance reticulation,
The
which
effect of a
the film
is
it is
not possible to remedy.
sudden temperature change
is
a
is
when
known
as
(See Fig. 77, page 180.)
minimum, however, when
unswollen and hardened.
5 " Some Properties of Chrome Alum Stop Baths and Fixing Baths " by Crabtree and H. D. Russell. /. Soc. Mot. Pict. Eiig. 14, 667 (June 1930).
J.
I.
SOLUTIONS AT HIGH TEMPERATURES The temperature
187
wash water is the governing factor in deterunder any particular conditions. a. If the temperature of the solutions is 90'^F. (32 °C.) and that of the wash water near 65°F. (i8°C.), it is only necessary to cool the tanks with the wash water as described in Chapter V, page 89, and of the
mining the procedure
to follow
use a water rinse between the developer and fixing bath.
temperature after adjustment visable to
add
and
the rinse bath
if
it is
ad-
sulphate crj^stals to the developer.
the solutions are at 90°F. (32 °C.), artificially
If the solution
70° to 75°F. (21° to 24°C.)
temperature of the wash water
If the
b.
10% sodium
is
it is
is
above 75°F. (24°C.), and
necessary to cool the solutions
kept in good condition, the film will
is
be hardened sufficiently to withstand the wash water at temperatures
from
it is
ioo°F. (24° to 38°C.).
75^" to
If the
c.
temperature of the wash water
is
above 75°F. (24°C.), and
not desired to add sodium sulphate to the developer and rinse bath
(assuming that a concentrated developer
above 80' F.) (26.5°C.), then this is an expensive procedure.
it is
is
used at a temperature not
necessary to cool the wash water, but
HOT WEATHER TROUBLES 1.
Fog and Stain During Development.
— Stock developing
so-
As the temperature rises, developers tend to fog photographic emulsions more readily, the solutions oxidize more rapidly, and trouble from stain may be expected. The rate of formation of aerial fog also increases as the temperature rises but this can be retarded by the addition of either pyro or a desen-
lutions should always be stored in a cool place.
Chapter XI, page 249). A pyro developer gives little or even at relatively high temperatures. Most photographic papers are hardened sufficiently in manufacture so that no trouble from softening may be anticipated, but stains and
sitizer
no
(see
aerial fog
fog are likely to be formed on prints controlled carefully.
10%
If the
the developer temperature
if
is
not
developer gives fog, add a few drops of a
solution of potassium bromide to the tray containing 8 ounces of
developer.
It
is
advisable to rinse a few seconds in a
2%
or
3%
acetic
acid stop bath between development and fixation, and to use the regular acid
hardening fixing bath recommended for papers. A more comis given in Chapter XI, page 230.
plete discussion of developer stains 2.
Dichroic Fog.
page 249.
— This trouble
is
discussed fully in Chapter XI,
In reflected light, film stained with dichroic fog looks yel-
lowish-green, and
by transmitted
light,
it
appears reddish-pink.
The
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
188
tendency for the formation of dichroic fog temperature of the bath the fixing bath
by
rises, since
the swollen film.
increased greatly as the
is
more developer is carried over The remedy for dichroic fog is
to to
keep the temperature of the solution down, rinse between development
and
fixation, agitate
thoroughly on
first
immersing the films
ing bath, and renew the fixing bath as soon as 3.
Reticulation.
sively,
is
it
— When
allowed to swell exces-
warm wash
occurs, there
is
may
cause
it
to
Sudden changes
or reticulated (Fig. 77, page 180).
in temperature, such as
removal of the film from a cool fixing bath to
water or vice versa, will produce
this effect.
no way of removing the reticulation.
therefore, to prevent swelling either
by
of all solutions as near 65° to 70°F. b.
is
very sensitive to physical strains, which
become puckered very
a gelatin film
in the fix-
shows signs of aging.
it
a.
It
is
Once
it
important,
maintaining the temperature
(18° to 2i°C.) as possible, or
using a chrome alum hardening bath between development and fixa-
tion, or c.
adding sodium sulphate to the developer and the hardener
rinse bath. 4.
Blisters.
—
Blisters are
formed
in
carbonate developers usually
during hot weather and as a result of insufficient rinsing. saturated with a carbonate developer
is
When
a film
placed in an acid rinse or fixing
bath, carbon dioxide gas bubbles are released within the gelatin layer of the film.
If this layer
is
not hardened sufficiently to withstand the
disruptive action of the gas, the carbon dioxide crater-like depression
is
left
in the gelatin
rinse thoroughly after developing, to
the use of the
keep
all
is
layer.
released and a tiny
The remedy
is
to
harden the film well (either by
chrome alum hardener or a fresh acid
fixing bath)
solutions as near normal temperature (65° to 7o°F.)
and
to
(18° to
2i°C.) as possible (for further details see page 166 of Chapter VII). Blister formation
may
be avoided entirely, however, by using devel-
opers containing alkalis, such as borax and Kodalk, because neither of
when added to an acid solution. In the case of certain Sulphur Sludge in the Fixing Bath. baths, when adding acid hardener to the hypo solution, it is im-
these substances release a gas 5.
acid
—
portant that both solutions should be cool (below 85°F.)
(29.5°C.);
otherwise a precipitate of sulphur will form immediately or within a
few hours.
In case the bath precipitates sulphur the only remedy
discard the solution and prepare a fresh one.
Sulphur
will also
is
to
be pre-
if stock solutions of an acid fixing bath are stored for several daysathightemperatures, above 85° F. (29.5°C.). If a fixing bath containing sulphur is used for fixing papers, there is danger of subsequent
cipitated
SOLUTIONS AT HIGH TEMPERATURES
189
fading of the image, resulting from interaction between fine particles of sulphur (held within the pores of the paper) and the silver image,
which
converted to a yellow modification of silver sulphide that
is
The presence
constitutes the faded image.
phur dioxide
of carbon dioxide or of sul-
moist atmosphere accelerates greatly the tendency for
in a
fading.*' 6.
—^A
Green Stain from Chrome Alum Rinse or Fixing Baths. gelatin film
of the stain to
is
usually stained a pale green color after immer-
chrome alum hardener
sion in a
35°C.).
intensity
increased at high temperatures, 80° to 95°F.
It
is
(26.5°
decreased by increasing the sulphite concentration
The
developer and increased by increasing the alkali content.
in the
formation of this stain
the chief reason that
is
baths are unsuitable for use with papers.
formly over the entire
The a.
if
it
is
fixing is
not
distributed uni-
film.
stain can usually be s^'c
chrome alum
Ordinarily, the stain
objectionable from a photographic standpoint
with
The
rinse or fixing bath.
is
removed from
solution of potassium
films or plates
citrate although
by
by treatment
virtue of this treat-
ment the hardening is destroyed. It is desirable, therefore, to harden the film by treatment in an alkaline formaldehyde bath before the stain
A
removal treatment.
suitable hardener formula
is
given on page 314
of the Appendix. 7. is
Scum.
— When a
film saturated with a strongly alkaline developer
placed in a chrome alum rinse or in a fixing bath containing either
chrome alum or potassium alum, there is a tendency to decomposition of the alum with resulting precipitation of a gelatinous sludge which deposits as a scum on the film surface. This tendency is greatest providing the acidity of the rinse or fixing bath is low and the film is not agitated
when
first
immersed
in either bath.
temperature of the processing solutions to flocculate
more readily
is
It is also increased
if
the
high, since the sludge tends
at higher temperatures.
when first immersed in all processremoved to the next bath, and to keep the rinse and fixing baths acid. The scum can be removed while the film is still wet by wiping the surface with a cotton pad or a chamois,
The remedy
ing baths
but
it is
on the 6 "
and
is
to agitate the film
at intervals until
removed only with great
difficulty after being allowed to
dry
film.
A
Method of Testing
Picture Films" by (April 1930).
J.
I.
for the
Crabtree and
Presence of Sodium Thiosulfate in Motion /. Soc. Mot. Ptct. Eng. 14, 419 F. Ross.
J.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
190
Drying o£ Photographic Materials The
usual difficulties encountered
at
High Temperatures.
when drying
—
films or plates at high
temperatures when high humidities prevail are a result of excessive swelling of the gelatin.
more water
the
it
It is
obvious that the more the gelatin
is
swollen,
contains, and the longer the time required for dry-
ing or evaporation of this water.
The
use of a concentrated developer
necessary containing sodium sulphate) and of a chrome alum hard-
(if
ener rinse bath assists greatly in preventing abnormal swelling of the film
and
in
avoiding a prolonged time of drying.
of the image,
which
is
often produced
high temperatures, does not occur
Excessive graininess
by slow drying
if
the gelatin
of swollen film at
prevented from
is
swelling.
The drying power
of air increases rapidly with the temperature
but
the air entering the drying cabinet should be at a temperature which
is
no higher than that necessary to dry the film in the time permitted. The maximum safe temperature depends on the degree of swelling and
As the temperature
hardening of the emulsion. tive
humidity
is
lowered so that
its
greater the higher the temperature of the to the extent to safely.
and
air.
There
is
is
a limit, however,
which the temperature of the drying air can be raised a. the degree of hardening and swelling of the
This depends on
gelatin, b. the " air,
of air is raised, its rela-
capacity for water absorption
c.
dry bulb
"
the air velocity.
temperature and relative humidity of the LTsually the temperature of the air should
not be raised to such an extent that the " wet bulb " temperature exceeds 95°F. (35°C.).
In order to insure rapid drying,
it is
most important
renewal of the air in contact with the film surface.
A
to obtain rapid
small volume of
high pressures striking directly on the surface is much more effecthan a large volume of air moving slowly past the film. tive on handling amateur and professional films at high information Useful
air at
temperatures
is
and " Handling Motion Picture Film in Eastman Kodak Co., Rochester, N. Y.
—
Development " the Tropics," published by the
contained in the booklets
" Tropical
CH.XPTER IX
STORAGE AND TRANSPORTATION OF CHEMICALS AND SOLUTIONS The
selection of suitable storage conditions for solids
and liquids con-
cerns primarily the large user of photographic chemicals and not the
amateur who
is
accustomed
many
Nevertheless,
to
buying chemicals
in small quantities.
of the criteria for storage apply to both classes of
consumers. Storage conditions for dry chemicals are determined
b)^
two
factors,
namely, the relative humidity of the atmosphere and the temperature.
Certain chemicals tend to absorb moisture from the air and are
said to be deliquescent, while others lose moisture
The
efflorescent.
and are classed as
extent of the absorption or loss of moisture
is
de-
termined by the relative humidity and the temperature.
much unknown composition and many powa damp atmosphere.
very important that chemicals should not absorb or lose
It is
water, otherwise they have an
dered chemicals tend to cake in
The temperature of the storage compartment should be moderate. Most solid chemicals are unaffected by temperatures varying from 32 °F. (o°C.) to iio°F. (43 °C.), but liquids tend to expand when heated and freeze when cooled and it is important, therefore, to use greater care in For winter storage, liquids should not
choosing their place of storage.
be placed too near steam pipes or radiators or other sources of heat, and in summer they should not be placed where direct sunlight may fall on
them.
Chemical Storage Room.
— The
space chosen for the storage of
chemicals should be located in or preferably adjoining the chemical mixing room.
It
should be situated some distance from rooms containing
sensitive films or plates
and
also
from the developing room
in order to
avoid contamination of the sensitive materials with fumes or gases given
off
by
liquid chemicals
and solutions, and the formation
or stains arising from chemical dust settling
during processing
(see
discussion
of spots
on the sensitive materials
on page
18
and Figure
5,
page
23)It is
good practice
used for chemicals.
to separate the storage
The
room
following substances are
for film
known
to
from that
have a harm-
ful effect on dry undeveloped films or plates and usually produce fog on subsequent development of the sensitive materials:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
192
Hydrogen peroxide Volatile oils and solvents
1.
2.
a.
Turpentine
b.
Benzol
c.
Oil of cloves
d. Oil of e.
Some
lavender
used in paints
oils
3.
Ether
4.
Ethyl acetate (used
5.
Coal gas and illuminating gas
in varnishes
and lacquers)
Hydrogen sulphide Ammonia.
6. 7.
Adequate ventilation and the chemical storage
exit facilities
and mixing rooms.
should be provided for both
Their
air
systems should be
designed so that the fresh air tends to enter (rather than leave) the
mixing room from the other processing rooms. provided in the mixing room to carry the
Exhaust fans should be
There
air directly outdoors.
is
always a danger of some employee breaking a carboy of acid while handling
and
of being
of the room. to
them kept
A
overcome by poisonous fumes before he can get out
Exits should be
marked
plainly
and passage ways leading
clear.
shower operated by a quick acting valve should be provided
quantities of acid are being used.
This scheme
is
if
large
utilized in all large
manufacturing plants and technical laboratories as the quickest and most effective
means
of first-aid to prevent acid burns.
rooms should be provided with a good
All chemical storage if
possible, to permit
floor drain,
accumulated (see Figure 23, page 43). Chemicals should be marked carefully and stored only places in the room.
Employees should be cautioned
labels carefully before mixing, because
casual inspection. result
may have
washing away any chemical dust which
many
to
chemicals look alike on
Trouble from incorrect mixing and
from mistakes made when selecting the chemicals
developer or fixing bath.
A
little
in definite
examine the
lost
may
batch of
time spent in insuring cleanliness and
order in the chemical storage and mixing rooms will be repaid
hours of time saved
time
for a
in the processing
by many
room.
THE STORAGE OF CHEMICALS AND SOLUTIONS Chemical Storage.
â&#x20AC;&#x201D; As noted
previously, chemicals for amateurs
They are
usually purchased in small packages
are seldom stored in bulk.
STORAGE AND TRANSPORTATION which contain the exact weight of chemicals necessary definite
mon
volume
The types
of water for use.
193
for dissolving in
of containers in
a
most com-
use are: small glass tubes, cartons, metal cans, and cans with metal
Waxed paper
top and base and cardboard paper tube sides.
liners or
bags are often used for the cartons and waxed corks for the glass tubes.
When
very corrosive materials are placed
in glass tubes, as in the case
some reducer chemicals, an asbestos or glass wool plug is usually In recent years, molded placed between the chemical and the cork. of
phenolic condensation products such as bakelite are being used for caps
and cans. Advanced amateurs, camera
for tubes, bottles,
and professional
clubs, photofinishers,
photographers who use larger quantities of chemicals usually buy bulk chemicals from which they can prepare their stock solutions.
consumers, chemicals are packed
in quantities
up
For such
pounds (2^
to 5
kilo-
grams).
Larger quantities for use by professional photographers, photo-
finishers,
motion picture and x-ray laboratories,
etc.,
laminated fiber drums (25 to 100 pounds capacity)
grams).
Hypo
is
packed
in several
(45 kilograms), in wooden
ways:
in
are supplied in
(ir to 45 kilo-
wooden kegs (100 pounds)
barrels (about 350 pounds) (160 kilograms),
bags (100 and 200 pounds capacity) (45 to 90 kilograms). This system of packing a definite weight in a bag, barrel, or drum sim-
and
in cloth
plifies
the mixing considerably, as
number
of such units
definite volume.
and add
it is
only necessary to count out the
their contents to the
tank when mixing a
Thus, the time required for weighing
For many types of work, chemicals in their original
is
avoided.
more convenient to leave the containers and to use a scoop when removing
small quantities for mixing.
is
it
A
usually
tilting bin represents a useful storage
pounds (45 kilograms) or less. It is not satisfactory for large quantities because the heavy bin becomes strained and broken if allowed to fall back into place by gravity. A
compartment
for quantities of 100
wooden box with
may
and castors which ride on metal tracks Such a storage compartment may be slid under
a hinged cover
be used (Fig. 78).
a bench when not in use. ]Most chemicals are affected
by
air
which contains oxygen, carbon
dioxide gas, and moisture.
A. Oxygen readily attacks such substances
as
cially in the presence of moisture, converting
it
which
is
useless as a preservative.
With
sodium into
crystallized
sulphite, espe-
sodium sulphate, sodium sulphite,
the sodium sulphate forms on the outside of the crystals as a
which
may
be washed
off
and the crystals
dried.
It
is
less
powder easy to
PHOTOGRAPHIC CHEIVHCALS AND SOLUTIONS
194
detect sodium sulphate in desiccated sulphite except
by chemical
tests.
Other substances which combine with oxygen and are therefore said to
be oxidized are sodium bisulphite and potassium metabisulphite,
and all developing agents such more or less brown, the extent
as pyro, hydroquinone, etc., of the color
which turn
change roughly indicating
the degree of oxidation.
Storage compartment for solid
Fig.
chemicals
B. Carbon dioxide gas combines with substances
like caustic
soda
and caustic potash, converting them into the corresponding carbonated alkalis which are less reactive. If caustic soda is kept in a glass stoppered bottle, the stopper usually becomes cemented fast by the sodium carbonate formed, so that cork.
Owing
it
should be kept
with a waxed
in a bottle fitted
to the solvent action of the caustic alkalis
on
glass, the
inside of the glass bottle containing caustic or strongly carbonated solutions
becomes
will usually
C.
When
frosted,
though the amount of glass thus dissolved away
do no harm. exposed to a
damp
atmosphere, the
alkali,
Kodalk, tends
STORAGE AND TRANSPORTATION carbon dioxide gas with a corresponding
to absorb
With reasonable difficulty
cals
due
care,
by storage
in the original
to loss of activity will
have a strong attraction or
atmosphere and gradually dissolve This phenomenon
a solution.
is
loss of alkalinity.
covered containers, no
in the
moisture present in the
water thus absorbed, forming
termed deliquescence and the chemi-
Familiar examples are
cals are said to deliquesce.
Certain chemi-
be encountered.
affinity for the
195
ammonium
thio-
cyanate, potassium carbonate, sodium hydroxide, potassium hydroxide,
sodium sulphide, uranyl be stored
in
It is possible to
a chemical
hydrometer readings
book
by N. A. Lange or the
edited
in
etc.,
which should
melted paraffin wax.
prepare a solution of definite percentage strength from
typical good reference
Journal
sodium bichromate,
which has deliquesced, by the use of a hydrometer, referring
to a table giving the
A
nitrate,
corked bottles and the neck dipped
is
in
the "
terms of percentage strength.
Handbook
Chemistry
of
" *
tables given in every issue of the British
Almanac^
D. While some chemicals absorb moisture as above, others give up water of crystallization to the atmosphere and therefore lose their
their
and fall to a powder and are then said to effloresce, phenomenon being termed efflorescence. Some crystals do not contain any water and therefore cannot effloresce. Typical efflorescent
crystalline shape
the
salt.s
A
are sodium carbonate .loH.O, sodium sulphate .loH.O, and hypo.
very dry atmosphere
but not for efflorescent
idly
The only
for storing deliquescent salts
satisfactory
way
to store chemi-
to isolate
is
when made up
Silver nitrate
darken is
most favorable
them from the air by sealing in a suitable manner. E. There are some chemicals which are decomposed by long exposure Such chemicals usually change more raplight, especially sunlight.
cals
to
is
salts.
in light
to store
or else
The
is
as a solution than
when
stored in the solid form.
probably the outstanding e.xample.
and
a solution will
both the solid and
Crystals of this salt
darken quite rapidly.
liquid in a
The remedy
cupboard away from the
light,
cover the bottle with black paper or opaque paint. use of brown bottles, as often recommended,
is
not necessarily
a protection of the liquid or solid from the action of light unless the absorption properties of the glass are such as to stop all harmful rays reaching the solution.
Publishers, Inc., Sandusky, Ohio, 2nd edition, 1938. Almanac are printed on the British imperial quart
*
Handbook
t
All formulas in the Brit. J.
or gallon basis and re<iuire conversion
The metric values
(see page 7)
given, however, are universal.
for use in the United States.
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
196
Solution Storage.
â&#x20AC;&#x201D; Most
in glass bottles or in carboys.
liquids used for
photography are shipped
Solvents for cleaning film and for splicing
are usually supplied in metal (tin) cans and in metal (galvanized iron)
When emptying
barrels or drums.
should be used.
liquid
from a carboy, a carboy rocker
There are several types of these rockers but the gen-
â&#x20AC;&#x201D;
FiG. 79 Hard-glazed stoneware crocks for solution storage. Note stainless steel drip tray and
type of outlets on crocks and storage tank (right) eral principle of each
is
similar,
namely, a cradle holds the carboy crate
and permits gradual, smooth tipping liquid contents.
It
is
when removing the empty Most industrial acids.
of the carboy
dangerous practice to use
carboys containing corrosive liquids, such as
air pressure to
plants prohibit such practice in their safety code.
Small volumes of solution
may
be stored in tanks
earthenware, hard rubber, enamelled
32A and 32B, pages tainer
is
steel,
made
of glazed
rubber lined steel (see Figs.
A
63 and 64), or glass.*
a crock of hard glazed stoneware as
convenient storage con-
shown
in
Figure 79.
All
stock solutions should be mixed in a separate container and then added to *
See Appendix, Part
materials and equipment.
III,
page 341, for a
list
of manufacturers of construction
STORAGE AND TRANSPORTATION A
the storage crock or bottle. of 18-8 stainless steel are
satisfactory mixing tank
shown
in
Figure
4,
page
welding the joints when constructing stainless
and
is
discussed in Chapter
page 64.
I\',
A
steel
197 stirrer made The method of
and
22.
tanks
is
important
suitable outlet should be
provided near the base of a stoneware container but a little space should be left below the outlet to allow any foreign matter to settle to the bot-
tom
of the container rather than run out through the outlet.
Fig. So
The method
â&#x20AC;&#x201D; Battery
of stoneware tanks.
of attaching the outlet
is
important.
If
not supplied
with a hole slightly above the base, the crock should be drilled. A soft rubber stopper with straight rather than beveled sides and having a center hole should be fitted snugly into the outlet.
A
hard rubber tube
and hard rubber faucet should be fitted tightly into the hole in the soft rubber stopper (see right hand crock in Fig. 79). The diameter of the hole in the soft stopper should be slightly smaller than the diameter of the hard rubber tube to assure a tight
sometimes advisable
to attach a
fit.
clamp
As a double precaution,
it is
to the outlet so designed as to
extend over the edge of the outlet and the top of the stopper. This type of outlet has several advantages, namely: it is i. non-corrodible, 2. resistant to breakage,
An
and
3. easily
removed
for cleaning.
alternative outlet consists of a right angled lead tube inserted
through a rubber stopper.
An
18-8 stainless
steel or a
should be fastened around the jar as shown on the
Monel metal band
left
crock in Figure
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
198
79 to hold the stopper securely in place. A short length of pure gum rubber tubing may be fastened over the lead tube and closed by means of a screw
clamp or a pinch clamp.
Large storage tanks of lOo gallon capacity or over should have a hole
bottom
in the
fitted
ing of the tank.
with a tapered wooden plug to facilitate easy clean-
This outlet
may
If a strongly caustic developer
also serve as the delivery pipe.
is
to be stored in a crock, a glass tube
or a hard rubber faucet should be used rather than a lead one, since the alkali
may
and form a
react with the lead
Glass outlets
precipitate.
should be avoided whenever possible because of the danger of breakage
and
of cutting the
It is
hands when
on the surface of a solution so as cedure
is
to protect
not recommended, however, as
may
material into the developer which it
tube into the rubber stopper.
fitting the
sometimes suggested that a layer of refined mineral
empty crock
leaves an
scheme
it is
it
from the
This pro-
apt to introduce a foreign
lead to trouble from spots, while
A much more
in a dirty condition.
Kodapak to lit the container and float made of 18-8 stainless steel.
A
on the surface.
it
practical
Kodaloid or
to construct a shallow boat of thin sheets of
is
be poured
oil
air.
boat
may
also be
When
a battery of stock solution crocks or bottles
18-8 stainless
table, a small
arranged on a
is
Monel metal trough should be
steel or
tached to the table edge to catch the drippings (Fig. 79).
good practice
to provide a floor sink
because an entire building
example,
if
under the table holding the crocks,
may become
inoculated with hypo dust, for
a large crock or bottle containing
and the contents allowed
to seep
stock solution bottles or crocks
with sheet lead or white
may
be
made
vitrolite.
by prolonged exposure
hypo were
through the
Action of Sunlight on Stock Solutions. are affected
at-
It is also
of
to
be broken
Table tops for
floor.
hard maple covered
â&#x20AC;&#x201D; Some stock
to direct sunlight.
solutions
Potassium iodide
solutions, for example, often turn a deep yellow color because of the
liberation of free iodine.
on standing
in
Nitric acid sometimes turns yellowish-brown
white glass bottles for long periods of time.
Potassium
ferricyanide also turns blue due to the formation of Prussian blue. lutions of this type are best stored in dark cupboards located direct sunlight.
Storage of Large Volumes of Solutions.
So-
away from
â&#x20AC;&#x201D; Deep tanks
of
hard
glazed stoneware are very satisfactory for storage of large volumes of solution.
B
is
A
typical battery of such tanks
a smaller stone tank, and
C shows
is
shown
at
A
in
Figure 80.
the slatted platform on which the
STORAGE AND TRANSPORTATION tanks rest above the mastic a hypo tank
made
A solution Figure 8i.
lloor,
mixing room
in a
is
shown
in
mixing the chemicals
is
Each
barrel
is
The
with a dust-proof cover.
modern photofinishing plant
of barrels used for
equipped with power driven
Fig. 81
D
thus permitting easy washing.
of cypress.
The upper row
storage units.
The lower row
stirrers.
made
mixing room on a larger scale
represents the solution mixing
tanks on
The
the floor below.
A
schematic diagram
moderate
size
is
shown
is
fitted
is
room
shown in
Note
in
Courtesy
Calif.
Figure 82.
This picture
a motion picture laboratory in
by gravity
to the circulating
Every tank wooden cover being
the portable mixers in use.
should be covered, whenever possible, a laminated in
and
in a photofinishing plant.
solutions are fed
very effective as illustrated
represents the
of oak, holds 48 gallons,
â&#x20AC;&#x201D; Solution mixing and storage room
Hollywood, Calif.
is
large tanks are of 250 gallon capacity.
Bear Photo Service, San Francisco,
A
199
Figure 36, page 71. room for a photographic plant of
of a mixing
in Figure 83.
The
fixing
bath tank
is
located on
one side of the chemical storage room, which permits the hypo to be handled and mixed in a separate room from that where the developers are prepared. Developer chemicals are moved on a small elevator from
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
200
the chemical storage
room on
the upper left into the mixing room.
The
weighing bench, sink, and mixing and settling tanks are located on an
A
elevated platform, approximately 3 feet above the floor of the room.
runway extends
room from
across part of the
tween two rows of mixing tanks.
the weighing bench be-
Portable mechanical stirrers
used to mix the solution (see Fig. 10, page 27).
Sulution mixing
room
in a large
Metro-Goldwyn-Mayer,
been mixed and allowed to
clear,
motion picture laboratory Hollywood, Calif.
either side
is
it is
by gravity
fed
into the adjoining
Another sink with a bench on
located at the opposite side of the mixing
venience of mixing smaller volumes of chemicals.
adequate ventilation
facilities
Courtesy
Inc.,
storage or feed tanks on the floor level.
be provided
in the
It
is
room
for con-
important that
mixing room.
very satisfactory material for protecting the outlet of large stone-
ware tanks
is
called " superflexite." *
It is
a hard semi-flexible lami-
nated rubber compound that gives a tightly sealed
When
washing down the
to see that the
wooden
tanks.
false floor of a
slats receive
cals tend to crystallize out
solutions
is
it is
important
spilled over the sides of the
picked up on the shoes and
room where
and produce spots on the
joint.
mixing room,
a thorough flushing because chemi-
from solution
Later this chemical dust
carried into the developing
*
be
Ww
R
A
may
After the solution has
it
will tend to
film.
Supplied by B. F. Goodrich Co., Akron, Ohio.
may
be
contaminate the
.
STORAGE AND TRANSPORTATION
201
Another useful type of storage or mixing tank is a glass-enameled tank which is made by fusing a resistive silicate enamel on to steel
steel
shells.
Such tanks can also be obtained with either
vertical or hori-
zontal agitators installed (see Chapter IV, page 58).
OFFICE OR
TESTING
Fig. 83
—
LABORATORY
Diagram of chemical storage and mixing laboratory.
Quite satisfactory tanks for moderately large volumes of solution can
be built of a cheaper wood than cypress, such as pine, and coated on the inside and partly on the outside with a layer of oxygenated asphalt (see Chapter IV, page 66)
Black iron has also been used with satisfaction for use with developmoderate alkalinity. Iron or steel tanks may also be lined with
ers of
hard rubber.
The
coefficient of linear
expansion of hard rubber within
a temperature range of 32° to i40°F. (0° to 6o°C.) according to Fritz
and Hoover
^
is
from three
to five times that of steel.
temperature changes are encountered, the rubber
Therefore,
may
crack.
if
rapid
To
offset
1 " The Chemical Resistance of Rubber as an Engineering Material " by H. D. " Symposium on Rubber " published by Amer. Soc. for Fritz and J. R. Hoover. Testing Materials, Philadelphia, Pa., page 113, 1932.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
202
this disadvantage, a three-ply rubl^er material has
consists of a layer of hard rubber cushioned
new type to
which
immune
soft
84 make
this
Overlapping expansion joints as shown
rubber.
been built up which
between two layers of in Figure
of construction material a very practical lining for steel tanks it
can be bonded with suitable cements so that
to physical
it is
remarkably
damage.
Two-ply rubber coatings on iron or steel are and trays. Soft rubber
linings of tanks, pipings,
also satisfactory
bonded
is first
for
to the
metal and then a layer of hard rubber laid over the soft rubber.
MM Soft Rubbe.r Hard Rubber SX3 M£TAL Cxp/\N5ioN Joint :r
Fig. 84
— Diagram of an
expansion joint lor a laminated rubber sheet.
Soft rubber sheeting should
first
be tested to insure that a precipitate
does not tend to form on prolonged contact with developing solutions (see
Chapter IV, page 66).
Storage tanks for strong oxidizing solutions such as acid permanganate or acid bichromate used in photographic reducer formulas require the use of glazed earthenware or acid-proof brick linings in iron tanks or rubber-lined steel tanks.
Alberene stone
may
be used effectively for building moderately large
tanks to hold developers but hard glazed stoneware or wood tanks should
be used for fixing baths.
For a general summary of the most
tory materials for tank construction, reference should be 3,
Chapter IV on pages
made
satisfac-
to
Table
74, 75.
TRANSPORTATION OF CHEMICALS AND CIRCULATION OF PHOTOGRAPHIC SOLUTIONS Conveyances for Moving Chemicals in Bulk. moved with small handtrucks, which
chemicals can be
— Most
bulk
should be of
sturdy construction, fitted with smooth running wheels
(preferably
equipped with
a
roller bearings)
tendency for crates, barrels,
and
so designed that there
etc., to tip off the truck.
is
minimum
It is especially
important when handling carboys of acid to use trucks which move
smoothly and hold the carboy rigidly
in place
during transit, as serious
STORAGE AND TR.\NSPORTATION burns often result trouble of
may
hypo
and
a strong acid
if
is
spilled
also occur, for example,
if
on the body or
Where
on the
film.
several units of chemicals are to be
This consists of
effective.
moved, a dual system
may
platform
is
is
a low, sturdy platform, usually called a
i.
"skid," on which the boxes or barrels are piled, and
a
2.
truck
lift
be run under the platform and then raised until the entire lifted clear of the floor.
mix
cals necessary to
unit from the storage
With such a
device,
a batch of developer can be
room
all
the chemi-
moved quickly
as a
into the mixing room.
often necessary to raise barrels or
It is
INIuch
feet.
the dust from a broken barrel
gets into the air circulation system of a processing laboratory
settles
which
203
drums containing chemicals
several feet from the floor to a platform surrounding the mixing tanks. If the elevation
is
only one or two
feet,
an inclined runway
With
and the containers wheeled up on a truck.
is
A
however, some sort of hoist must be installed.
feet,
it
hoist
also
is
is
quite slow in operation.
very effective; while
hoist operated
When
air
may
if
time
is
may
be used
a factor, an electric
a source of compressed air
is
available, a
be utilized.
handling chemicals on a large scale, a portable elevator more
commonly Stackers
by
If
be built
block and tackle
perhaps the simplest and most economical hoist which
but
may
elevations of several
called
may
" stacker
a
be obtained
in
""
represents an
many
styles
and
efficient
sizes
type of hoist.
from simple types
which are manually operated by means of a winch to the more complex types which are electrically operated and have large lifting capacities.
Methods oÂŁ Conveying Solutions. veying solutions
is
by gravity with
â&#x20AC;&#x201D; The simplest method
of con-
A
the aid of suitable piping.
good
grade of rubber tubing represents, perhaps, one of the cheapest types of installation, but care
insure that
it
must be exercised
encountered when using is
it
more satisfactory than
to
soft
cation in chemical industries.
convey developers.Its chief
ported by a trough or brackets pipe line which
iron pipe which
mum
is
is
Hard rubber piping
rubber tubing, and has found wide appli-
and may break under the impact
A
in selecting tubing in order to
does not contain free sulphur or trouble from fog will be
of a
if
disadvantage
heavy blow.
is
that
It also
it
is
brittle
must be sup-
long lengths of pipe need to be used.
not subject to this trouble
is
hard rubber lined
supplied in standard lengths and diameters (mini-
^ inch) and with
all
types of fittings.*
The connections
are de-
Chemical Fog " by J. I. Crabtree. Amcr. Aim. Phot. 33, 20 (1919)by such firms as B. F. Goodrich Co., Akron, Ohio, and U. S. Rubber Co., New York, N. Y. -
"
* Supplied
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
204
signed so that the solution never comes in contact with the iron at any
point during transit.
Wooden
troughs built of untreated cypress or of a cheaper
coated with Kodacoat paint or with oxygenated asphalt for
wood and
may
be used
conveying solutions down a slight incline from one point to another
on the same
floor.
to collect dust or
These are subject to leakage occasionally and tend any other foreign matter accidentally dropped in the
trough.
Fig. 85A
— Air
lift
solutions.
for photographic
Tank
Fig. 85B
Use of Compressed
Air.
— Air
lift
solutions.
closed.
— As a general
for photographic
Tank
open.
practice, air under high
pressure should not be used for conveying solutions through pipe lines. It
should never be used for the movement of strong acids or alkalis, as
very serious accidents have resulted from the spraying of corrosive acid
on workers as a
when
ever,
ume
result of a
of solution quickly
tance
is
break in the
air pressure offers a simple,
not too great.
from one
line.
There are occasions, how-
convenient means of moving a vol-
level to a higher level providing the dis-
For example,
it
may
be necessary to locate the
circulating or feed tanks for a small motion picture
machine as high as
STORAGE AND TRANSPORTATION
205
possible from the floor in order to create
enough head to provide adeMixing should then be carried out on the floor and the solutions blown by air pressure from the mixing crock to the
quate flow of solution. level
tanks.
A
An
installation of this type
hard-glazed stoneware crock
keted stoneware cover
Fig.
is
85c
fitted
raised.
shown
fitted
in Figures
85A and 85B.
on when the solutions are ready to be
of
molybdenum
with an to the floor above. is
is
used for a mixing vessel and a gas-
â&#x20AC;&#x201D; Installation
structed of 18-8
tank
is
mixing tanks constainless steel.
Each
air lift for raising the solution
Air pressure of 6 to 10 pounds per square inch
is
applied through
a good grade rubber hose connected to the orifice in the cover. tion outlet
is
near the base indicates the level of the solution. to use air pressures
A
The
solu-
located near the base of the crock and a small glass gauge
much above
It is
not safe, however,
15 pounds per square inch.
complete installation of mixing tanks, mixers and piping made en-
tirely of
gasketed
18-8 molybdenum stainless lid is
clamped down
steel
is
shown
in
Figure 85C.
after each solution has been
The
mixed and,
air pressure (about 9 pounds), the solution is forced into the storage tanks on the floor above. Gauges on the wall indicate the
by applying
solution level in all storage tanks on the upper floor.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
206
Pumps.
â&#x20AC;&#x201D; When â&#x20AC;˘
movement
the
common
it
not feasible to use gravity or air pressure for
is
pumps
of a solution,
may
types
The most
are usually employed.
be classified into three groups, as follows:
ciprocating or piston pumps,
2.
centrifugal
pumps, and
3.
i.
re-
rotary or gear
pumps.
pump is effected by shown in Figure 86A. An intermittent flow results since the piston movement is reversed alternately. All reciprocating pumps use valves and require packing, and 1.
The
delivery of the liquid in a reciprocating
the displacement of a piston or plunger as
have an advantage over the centrifugal type require priming except the
first
in the fact that
they do not Centrif-
time used after installation.
ugal and rotary pumps, on the other hand,
may
be installed and op-
erated usually at a lower cost and are preferable, therefore, to recipro-
pumps for handling photographic solutions. The mechanical construction of a centrifugal pump is extremely simple. The only moving part is a rotor or impeller which turns in a stationary case. The rotor is surrounded by a spiral casing (the volute) The of gradually increasing cross section, as shown in Figure 86A.
cating 2.
pump is relatively free of pulsations. pump must be primed each time it is started.
flow of a centrifugal
A
centrifugal
not develop as high a suction
lift
tion of that of the reciprocating type for the less.
It
only a frac-
same duty.
Initial cost
can be connected directly to an
or belt drive as required.
The capacity
and the head varies with the square
mended
the
is
other hand, the size and weight of a centrifugal
and upkeep are
pump
It will
On
pump.
as the reciprocating
electric
motor
varies directly with the speed
of the speed.
This type
for use with photographic solutions provided
it
is
is
recom-
constructed
of a corrosion resisting material such as hard rubber or 18-8 stainless steel or
Monel metal.
Rotary pumps consist essentially of two closely fitting gears which, turning, carry the liquid around their peripheries as shown in Fig-
3.
in
ure 86A. often used
Because of the simplicity in
in
their design,
These pumps depend
They can handle
for their lubrication
on the liquid being pumped.
two types.
No
liquids containing grit or solids,
ever, should be used as the small clearance of the solid material to pass.
18-8 stainless
by how-
viscous liquids which cannot be handled effectively
either of the other
any
such pumps are
handling photographic and other chemical solutions.
steel, or
photographic solutions.
This type of
Monel metal
is
pump
if
pump made
will not
permit
of hard rubber,
very satisfactory for use with
.
STORAGE AND TRANSPORTATION A
,
novel valveless
which
is
adapted
to
pump
moves)
has been developed by Bennett
A
flexible
Three common types of pumps.
The
mounted on a
Fig. 86b
cast iron panel.
â&#x20AC;&#x201D; Bennett valveless pump.
part corresponding to the impeller of an ordinary
of a circular disc
mounted on
three ball-bearing rollers capable of radial adjustment.
A
pump.
" tractor
When
rollers
rollers are
small clearance about equal to the thickness of
the spindle
rubber tube, the
The
consists
mounted
path," an important
the compressed rubber tube exists between two of track.
pump
a driving spindle and on this are
circumscribed by a flexible band called a feature of the
(London),
rubber tube (through which the solu-
against a curved track,
lies
*
handle liquid and gases without bringing them into
contact with metal. tion
207
is
the rollers and
rotated, the tractor path sweeps along the
compress the tube, and cause a small volume of
between the two rollers to move forAt the same time, a fresh charge is drawn in be swept out by the third roller. The pump is self-priming and the
liquid in the section of the tube
ward toward the to
outlet.
may be replaced quickly Fig. 86B pumps should always be flushed out carefully with water each time they are shut down after use to remove any liquid remaining in the
rubber tube or pumping element
(
)
All
pump chamber. should be 3
"
A
made
Valveless
For further details on to the
Pump
"
pump
pump
installation,
reference
manufacturers (see page 343).
by C. M. Bennett.
lud. Chemist 11, 274 (July 1935).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
208
Siphons.
— Another well-known device
the siphon, which in
is
its
for the
movement
of liquids
simplest form consists of a bent tube used for
carrying the liquid from a higher to a lower level over some intervening obstacle as
shown
Assuming that the tube
Figure 87.
in
the liquid, as long as h^
is
soon as these distances become equal, than
Fig.
h, the flow will
— Diagram
87
of
it
The
be reversed.
a
is filled
with
greater than h, the flow will continue but as
simple
will cease or,
if
h^
becomes
less
distance h must not be greater
Fig. 88
— Two
types of siphons.
siphon.
than the height of the barometric column
This
— about
34
feet for water.
portional to the size of the siphon.
when the The rate of flow is inversely proWith long siphons, the diameter of
the short pipe should preferably be
much
is
a theoretical distance; practical siphons operate only
distance h,
is
not greater than 28
feet.
larger than the long pipe to
secure a satisfactory rate of flow.
Two
simple types of siphons are shown in Figure 88.
by compressing the rubber bulb
just previous to
Type A works
immersion in the vessel
The bend of the tube at the by adding some of the liquid to it. When the bulb is released, the suction created draws the liquid in the vessel through the column and starts the siphon. Type B starts itself by simply immersing the tube S in the liquid chamber R. The liquid fills the narrow tube T which must be im-
containing the liquid to be siphoned over. discharge end
mersed almost ing this
Y
X
is
sealed off
to the bend.
into the larger
chamber gradually
and the bubbles
The
chamber fills
of air rise
S,
liquid also flows through the open-
which surrounds the tube T, and as
the air
is
forced out through the opening
through the column of liquid
in the
tube T.
STORAGE AND TRANSPORTATION Since the weight of the liquid and air in the narrow tube
weight of the liquid height
immersed, pressure
is
in the large vessel in
siphon
If the
pushed out of the chamber
liquid emptied out,
is less
it
is
is
forced
before
all
the
must be removed,
all
the
fails to start
the siphon
S,
than the
which the siphon
exerted on the liquid in the tube and
over the bend of the siphon. air is
20Q
and the tube reimmersed.
FEED TANK
CONTINUOUS r\_ow
SYSTEM OeVELOPtNG.
MACHINE
Fig.
â&#x20AC;&#x201D; The
continuous flow method of solution circulation.
In
many
types of continuous machines,
it
is
desirable to install an
automatic means for adding replenisher and maintaining the solution level in various tanks.
Hickman
*
has described several such devices
which incorporate modifications of the siphon principle. Circulating Systems. For most types of photographic work
â&#x20AC;&#x201D;
which are carried out manually,
it is
unnecessary to circulate the solu-
done intermittently and replenisher needs to
work is when required. Automatic processing machines, however, run continuously when in use and the films are carrying a fairly definite tions because the
be added only
volume of solution out of each tank as well as exhausting the solution by virtue of the developing (fixing, hardening) process. With such 4 " Siphons and Measuring Devices for Photographic Solutions " by K. Hickman. Trans. Soc. Mot. Pict. Eng., No. 26, 37 (Nov. 1926).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
210
equipment
it is
customary practice
to arrange to feed solutions into the
processing tanks at such a rate that the volume level will remain nearly-
constant and the strength of the bath will
as little as possible
fall off
on developer exhaustion, Chapter VTI, page 132). general systems are in vogue for the addition of solutions
(see section
Two
matic processing machines, namely:
a.
to auto-
the continuous flow system and
the recirculating system.
b.
A. The continuous flow system represents the simplest instaflation problem since the scheme does not require the use of the solution more than once. As shown in the diagram (Fig. 89), the solution is fed, either by gravity or by means of a pump from the mixing tank through the feed tank and cooling coil into the machine. The point at which it enters the machine varies according to the nature of the developer and the type of film being processed. With negative film, it is advantageous to flow fresh developer into the machine at the point where the film enters, and allow the solution to flow out where the film leaves the machine. This scheme assures that development starts in a fresh developer and shadow details begin to appear before the film enters parts of the machine where the developer is partially exhausted.^
When
handling positive
film, this
as the absolute speed value
is
system
is
not quite so advantageous,
of less importance than the securing of
uniform prints by virtue of the maintenance of constant development conditions.*^
ample,
it
When
using a developer containing no bromide, for ex-
might be advantageous to feed the developer
where the solution leaves the tank so the solution
in at the point
will
be uniformly
conditioned at the point where the film enters the machine. will dictate
which system
]\Iost of the
is
photofinishing plants in this country and abroad, which
are using automatic machines, and tories,
some
of the
motion picture labora-
use an alternative procedure which consists in reviving the bath
at intervals with a replenishing solution
and composition from the
tion
Practice
best to follow.
which
original formula.
should normally be introduced at a rate which
differs
in concentra-
Replenishing solution is
proportional to the
quantity of film processed.
B.
]^Iost of the large
motion picture laboratories
abroad use a recirculation system shown 5
M.
"
L.
in this
in its simplest
country and
form
in Fig-
A Quick Test for Determining tlie Degree of Exhaustion of Developers " by Dundon, G. H. Brown, and J. G. Capstafif. /. Soc. Mot. Pict. Eng. 14, 389
(April 1930). 6 " Replenishing Solution for a Motion Picture Positive Film Developer " by
A
J. I.
Crabtree and C. E. Ives.
/.
Soc. Mot. Pict. Eng. is, (127 (Nov. 1930)-
STORAGE AXD TRANSPORTATION lire
The
90.
211
solution flows from the mixing tank into the feed or cir-
culating tank, and then
pumped
is
The
into the machines.
A pump
directed back into the circulating tank again.
is
overflow
is
necessary to
maintain the circulation and the solutions are usually piped through a cooling device located near or sometimes in the feed tank.
customary it
is
to
add replenisher
It is
usually
at intervals to the circulating tank
thoroughly mixed with the used developer before
it
where
enters the
OVCR-F-L-OW
Fig. 90
â&#x20AC;&#x201D; The
recirculation
method
of solution
circulation.
machine.
Alternately the replenisher
machine.
The
may
be added directly to the
point at which the solution enters the machine
pendent on several factors as explained above.
system
is
is
de-
The advantage
of this
fall off at
a rela-
that the developing properties of the solution
tively slow rate
depending on the capacity of the recirculating tank.
A
above, the rate of addition of replenisher must be ad-
With method
justed carefully
by
and
trial
error, so as to secure a constant rate of
development, otherwise the developer
in the relatively small
tank will
rapidly become exhausted.
The
cooling coils
culating tank as
may
shown
be arranged either around the sides of the
in
Figure 90 or the overflow
may
cir-
be cooled by
surrounding the pipe with a cooling chamber as shown at B in the Figure. The best location of an exterior chilling box obviously depends on the arrangement and size of an individual installation.
In some laboratories
it
is
not customary to circulate fixing baths or
rinse baths although a replenisher
the
life
of these solutions.
The
is
often added several times during
level of these baths
is
normally main-
by the solution carried over by the film from the previous bath. In the case of laboratories where silver recovery units have been in-
tained
— PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
212
stalled, the fixing
bath
is
recirculated
and
filtered
"
and
this insures
more
and Temperature control when using automatic machines is of utmost importance and all modern processing laboratories have means installed cleaner film.
efficient fixation
For a discussion of
for maintaining the temperature constant. ject, reference
should be
Fig. 91
Flow Meters."
made
— Types
—
It is
to
this sub-
Chapter V, page 98.
of flow meters
and controllers
frequently necessary to measure and control
the flow of solution in a pipe line, for example, during replenishment of
a developer or in a circulating system.
^Meters
may
be classified into
four types as follows: 1.
Rotameter
— Constant
Head and Calibrated
Orifice.
This type consists of a calibrated tapered glass tube containing a
float,
the position of which indicates the rate of flow through the tube.
constant head must be maintained and throttling
A
accomplished with
is
The capacity ranges from i cc (approximately 4 drams) to hundreds of gallons per minute (Fig. 91, upper right). A constant head on a calibrated 2. Float and Orifice Type. a valve.
—
~
and
"
The
W.
Electrolytic Regeneration of Fixing Baths " by K.
Weyerts.
/.
Soc. Mot. Pict. Eng. 17, 568 (Oct. 1931)
Hickman, ;
C. Sanford, also " Electrolysis of
Solutions" by K. Hickman, W. Weyerts, and O. E. Eng. Chcm. 25, 202 (Feb. 1933). * The authors wish to acknowledge the helpful assistance of R. B. Ellsworth of the Engineering and Maintenance Dept., Kodak Park, for much of the data in this Silver-Bearing Thiosulfate
Goehler.
section.
Ind.
&
STORAGE AND TRANSPORTATION maintained by a
orifice is
float
which controls a supply
213
inlet valve.
The
solution flows in at the top and the range varies from approximately
10 cc to an unlimited 3.
in a
per minute (Fig. 91, upper left).
—A
bafl float
tank controls the supply flow through an ordinary regulator valve type
(this
—
maximum
Ball Float Valve to Maintain Constant Head.
is
not shown in Fig. 91).
Mercury Manometer with Air Operated Diaphragm Valve. An orifice is inserted in the line of flow and differential pressures are
4.
measured by a mercury manometer with a float connected to a pointer. This meter is used preferably to measure large volumes of solutions although
it
is
factorily.
capable of handling fractions of gallons per minute satis-
It is
used extensively as a pneumatic controller with an air
operated valve in the line of flow, as shown at the bottom of Figure 91.
The above meters should
preferably be constructed of corrosion-re-
sistant materials such as glass or stainless steel.
Apparatus for Commercial Development of Motion Picture Film. for the
—
•
A
comprehensive discussion of apparatus
development of motion picture film
in
for
handling solutions
commercial laboratories has
been published by the Committee on Laboratory Practice of the Society of
Motion Picture Engineers.* 8
Report of the Committee on Laboratory Practice,
345 (April 1936).
7.
Soc. Mot. Pict. Etig. 26.
CHAPTER X
SUBSTITUTION OF CHEMICALS It is
poor economy to buy cheap chemicals for mixing photographic
Many
solutions.
hours of preparation for photographing a particular
scene in a motion picture studio, for example,
may
be wasted
laboratory uses a developer containing impure chemicals. loss of valuable time,
it
may
the
also be very difficult to duplicate a particu-
Such wasted time
lar exposure.
if
Besides this
may
be avoided by using only pure
chemicals supplied by a reputable manufacturer.
There
usually no
is
need, on the other hand, to purchase chemicals of the highest purity such as are used for the preparation of reagents in an analytical laboratory.
The
precision of
workmanship
possible in practical photography
sufficiently great to require the use of
Whenever
possible, solutions should be
cal
however, when the photographer
and
would be convenient
it
he had ample stock.
to
not
mixed with the particular
chemicals which are called for in the published formula. arise,
is
such chemicals.
is
Occasions
out of stock of a certain chemi-
be able to substitute another, of which
This chapter
stitution with reference to developers
will discuss the limits of
and
such sub-
The remarks
fixing baths.
will
usually apply also to solutions in general.
SUBSTITUTION IN DEVELOPING FORMULAS A.
The Developing Agent.
to replace
â&#x20AC;&#x201D; As a general
rule
it is
own
identical properties, because each developing agent has its teristics as
etc.
not possible
one developing agent by another and obtain a developer with charac-
regards rate of development, fog, color of image produced,
In some cases, however, a close approximation can be made, for
example, by substituting Elon by several times
phenol provided the developer
aminophenol
to
be dissolved.
is
its
weight of para-amino-
sufficiently dilute to allow
This applies either to an
enough paraElon or an
all
Elon-hydroquinone formula. If
para-aminophenol
is
substituted part for part for the Elon in an
Elon-hydroquinone formula and the activity of the developer creased by the addition of alkali, the effect of the alkali
is
is
in-
proportion-
ately greater on the hydroquinone than on the para-aminophenol, so
that a rapid hard working developer culty, proportionally is
used.
The
is
obtained.
more para-aminophenol
usual ratio
of Elon in the formula.
is
is
To
avoid this
required than
if
diffi-
Elon
four parts of para-aminophenol to one part
:
SUBSTITUTION OF CHEMICALS Characteristic
properties
agents are given in Table
7,
of
the most
215
commonly used developing
An
pages 216 and 217.
excellent discussion
of the properties of various developing agents will be found in the "
Photography
The
B.
â&#x20AC;&#x201D; Theory and Practice
Preservative.
â&#x20AC;&#x201D;
-
It is
"
by L.
P.
now customary
bisulphite for potassium metabisulphite weight
veloper or fixing bath formulas. the stability of commercial talline structure
and also
to substitute
by weight
a function of
is
in
is
very
little
may
actual
commercial sodium bisulphite; the
major portion of the sample consisting of sodium metabisulphite. able and
^
crys-
its
P\irthermore,
of its lack of moisture content.
these authors have proved by analysis that there
mercially dry sodium
sodium
in either de-
According to Harrison and Carrol
sodium bisulphite
sodium hydrogen sulphite present
book
Clerc*
bisulphite of satisfactory quality is
now
Comobtain-
be used in mixing formulas calling for either the meta-
bisulphite or the bisulphite.
A
very interesting discussion of the comparative properties of the
sulphites, metabisulphites,
and acid sulphites has been published by
Wall.^'
The
question
often asked as to the difference in action between
is
sodium sulphite and sodium bisulphite. Sodium bisulphite may be considered as a compound of sodium sulphite and sulphurous acid, and therefore reacts acid, while sodium sulphite
is
alkaline so that in the
case of a two-solution pyro formula where the pyro
A
solution
is
pre-
served with oxalic acid or sodium bisulphite, an equal weight of sodium sulphite
would not preserve so well since pyro oxidizes much more read-
ily in alkaline
than
in acid solution.
In the case of a one-solution developer containing, say, sodium sulphite, sodium bisulphite, and sodium carbonate, the bisulphite is converted to sulphite of
by
the sodium carbonate and an equivalent quantity
sodium bicarbonate
is
formed
Sodium
Sodium
Bisulphite
Carbonate
Sodium
~
Sodium
Sodium
Sulphite
Bicarbonate
bisulphite, therefore, neutralizes or destroys
an equivalent
quantity of sodium carbonate, thus reducing the proportion of alkali and, therefore, exerts
H. Greenwood & Co., Ltd., London, 2nd edition 1937. The Composition and Evaluation of Commercial Sodium Bisulphite " by J. B. Harrison and M. F. Carrol. J. Soc. Chcm. hid. 44, 127 T (1925). Amcr. Phot. 2 " Sulphites, Metabisulphites, and Acid Sulphite " by E. J. Wall. * 1
P.
an apparent restraining action, while the developer
"
16, 137 (19-22).
(
216
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS i-^^^.a
s
ou^gg
'g'Sbci'o
<23-:2-
^>3
•^^^•c°
"SSS-b
^U.5-H
^;< c
-2
>*-
se
o
C^O-^S
c
-^
^S
_g
c o
^S^3="
-^.S.SSiiO
iiiii f¥|ii
^i^i
o
I—
b
•ri-^^'S,
^j^o^l
J-
3
oj
X3 -5
" s
^
c c
-S
o .2^-2^
m
"5
<!
^iu>ic;'So>. .^o«cP^>. r^.SoDe^.S'-
c!>
oi
Q
*
« .^
o o
O tc t—
H » O P^ Pa
ri-
>
o<
<
SUBSTITUTION OF CHEMICALS A-
t:>
M
-^ °o
§
S
-^
£
-§
1 Oh
It-5°o
/r-'i
v
-=
^"Sa
^
5
5
^'^
>
ii -3
tS iJ
S
S
:r=
-2 I K
S
S
i_Vi
i^'l^
-S
2
.>
6I
-2
C/3
^S
217
lt/)I-.fcf)
S-E=^-
V,
S E 2 P^
^ ° ^
.-H
=.
.§
^ ^ JJ
u
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
218
keeps longer because some of the carbonate has been destroyed.
Now,
supposing we have a developer containing lo grams of sodium bisulphite, 10
grams
of
we should expect
sodium to get
sulphite,
and 20 grams of sodium carbonate,
approximately the same results by using 20
grams
of sodium sulphite and 10 grams of sodium carbonate. Experiment shows, however, that the developer containing the bisulphite keeps longer and gives slightly less fog than a corresponding developer containing only sodium sulphite which is apparently due to the fact that
the bicarbonate formed acts as an anti-fogging agent
prevent rapid oxidation of the developer. phite in a single solution developer
Sodium bisulphite
is
is
and a buffer to of sodium bisul-
The presence
therefore beneficial.
supplied abroad and to a limited extent in the
t^nited States in the form of a concentrated solution
about 300 grams (10 ounces) of bisulphite to tests
35°
Baume
(Sp. Gr. 1.32 at 6o°F.).
i
The
liter
which contains
(32 ounces) and
solution
is
fairly con-
stant in strength but deteriorates slowly on keeping, forming sulphurous
acid and a crystalline deposit of sodium sulphite
when
stock solution keeps better
The
and sulphate. The volume of water.
diluted with an equal
following table published by L. P. Clerc
^
gives the quantities of
the usual pure alkalis required to neutralize potassium metabisulphite:
TABLE For Neutralizing
100 Parts by Weight of
Sodium
Sodium
Carbonate (Anhyd.)
Carbonate {Cryst.)
Potassium Carbonate
Hydroxide
Potassium Hvdroxide
95 Parts
258 Parts
124 Parts
36 Parts
50^ Parts
Sodium
Potassium Meta-
bisulphite
The
C.
Alkali.
— The common
droxides of sodium, potassium, or
and hyBorax or sodium borate
alkalis are the carbonates
ammonium.
have also been used considerably, particularly tively
low contrast developers.
its
properties
When sodium it
is
carbonate
3
Ltd.,
—
is
rela-
less alkaline
than carbonate.
A
given on page 119. is
dissolved in water a small proportion of
reacts with the water forming
sodium, bicarbonate: this
compounding
new alkali known as Eastman Kodak Company. It is much
Kodalk was announced by the more alkaline than borax but slightly discussion of
in
In ]\Iarch 1934, a
sodium hydroxide (caustic soda), and though only a small por-
called hydrolysis
"Photography Theory and Practice" by London, 2nd edition, 193".
L. P. Clerc, H.
Greenwood &
Co.,
SUBSTITUTION OF CHEMICALS tion of the carbonate
hydroxide formed
hydrolyzed at any moment.
is
used up
is
so that
we can consider
alkali.
If in the first place
the
same
in
219
As the sodium
development, more carbonate hydrolyzes
that carbonate acts as a reservoir of caustic
a solution of sodium hydroxide was used of
alkalinity as the carbonate, this
The
would soon be used up.
use of carbonate, therefore, enables us to use a small concentration of alkali
and yet keep
it
constant during development.
It is rarely possible, therefore, to substitute caustic alkalis for
ated alkalis such as sodium or potassium carbonate. " sal soda " or
washing soda sold
for
household use
is
carbon-
The commercial usually unsatisfac-
tory as a substitute for sodium carbonate in photographic formulas bs-
cause
it
often contains a large proportion of inactive sodium sulphate and
an excess of water. Regarding the substitution of potassium pard and Anderson
^
have shown
for
sodium carbonate, Shep-
in the case of
an Elon-hydroquinone
contrast developer that no detectable difference could be found
when
the potassium salt was substituted in molecularly equivalent quantities for the
sodium
salt.
A
similar conclusion
graphic work. to
It is
was reached, according
when using process
these authors, by Trivelli
pointed out, however, that these results apply only
one developer and are not necessarily applicable
For practical purposes, the two
salts
may
to other formulas.
be substituted weight for
weight because the difference in their molecular weights
is
quite small.
The addition of about 3^^ by weight of caustic soda to the amount of sodium carbonate is sometimes recommended. Potassium carbonate the disadvantages that
very readily. carbonate
is
On
to
plates for photomicro-
is it
equivalent
more soluble than the sodium salt but it has usually more expensive and absorbs water
is
account of
its
greater solubility, however, potassium
useful in preparing concentrated developers.
For developing motion picture film on a splash on the floor, potassium carbonate
reel is
when
the developer
to be preferred to
may
sodium
carbonate, since by virtue of the deliquescent nature of potassium car-
bonate the splashes of solution remain moist, thus preventing the formation of carbonate dust in the air.
Lumiere and Seyewetz
''
have determined the relative quantities of
various alkalis which give equal photographic effects with different de-
veloping agents as given in the following table: 4 " The Developing Equivalence of Sodium and Potassium Carbonates " by S. E. Sheppard and P. A. Anderson. Brit. J. Phot. 72, 232 (1925). 5 " Contribution to the Study of the Role of Alkalis in Organic Developers " by A. & L. Lumiere and A. Seyewetz. Bull. soc. franc. Phot. 22, 32 (1906).
,
,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
220
TABLE ^
^
.
,
^
,.
9
,
Potassium
Sodium
.
Sodium ,, Hydroxide
Hydroxide
Hydroquinone
lo
14
96
75
Pyro
10
14
34.2
32.4
Metol
10
14
34-2
28.3
Glycin
10
14
10
14
Developins ,
^
*
,
Agent
Potassium ^^
.
,
.
^
Carbonate
^ l ^ Carbonate
^^^^^^^
^^^^^^^
,
,
122
74.5
Chemically equivalent quantities
26.5
34.5
In arriving at the above results, the developing agents were not com-
pounded
in a developer
formula having a fixed composition.
Since the results of Sheppard and Anderson, and Trivelli did not con-
form with the above, further
tests
were made by the authors and H. D.
Russell as follows: various developing agents were
compounded
in the
following formula: Developing agent Sodium Sulphite (anhydrous)
5.0
37.5
X
Alkali
Potassium Bromide Water to make
Sensitometric tests were ties of the alkali
taken as
made
1.5 1-0 liter
in
each case, using increasing quanti-
compared with 25 grams
standard (pH
= about 9.5).
tain characteristic curves
grams grams grams grams
It
of sodium carbonate (anhyd.) was not always possible to ob-
which were identical
ging tendency with the different alkalis varied.
in
shape because the fog-
For equal fog values, the
relative average quantities of the various alkalis required to
produce
equal densities on the straight line portion of the characteristic curves are given in the following table:
:
SUBSTITUTION OF CHEMICALS Data were developer
(pH
also obtained
with two other alkaHs
221
in
the following
= 9.0)
Elon
2.0 jirams 5.0 ftranis
Hydroquinone
Sodium
Sulphite, 'anhydrous'^
Alkali
Water
to
make
For equal fog values, the
100.0 ftrams
X
i^rams
1.0 liter
relative average quantities of alkalis re-
quired to produce equal densities are given in the following table:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
222
It
is
therefore possible to give only approximate figures for the equiva-
lence of alkalies unless a particular developer formula
Kodalk
in Developers.
â&#x20AC;&#x201D; Kodalk
is
specified.
more alkaline than borax but slightly less alkaline than carbonate. In relation to sodium carbonate, approximately 2 parts by weight of Kodalk are equivalent to i part by weight of carbonate in all ordinary formulas (except pyro) which do not is
Reference to Figure 64, page 120, will not possible to give one ratio of Kodalk to car-
contain bisulphite or other acids.
show, however, that
it is
bonate which will give developers of equal activities for
all
emulsions and
for all concentrations of these alkalis.
Figure 64 also shows that the activity of Kodalk varies almost
di-
rectly as the concentration of Kodalk, whereas with carbonate the activity increases
very rapidly at low concentrations and In other words,
higher concentrations.
it
is
falls off
rapidly at
dangerous to modify the
activity of low alkaline developers containing carbonate because very
small changes in carbonate content produce large changes in developer
with Kodalk developers to vary the by varying the Kodalk content (see also dis-
It is perfectly feasible
activity.
activity of the developer
cussion on page 119).
Borax, Tribasic Phosphate, Organic Amines and Other AlkaDevelopers. Concurrent with the wide adoption of high speed
â&#x20AC;&#x201D;
lis in
panchromatic emulsions
in recent years, extensive use
has been
made
This chemical
borax as an alkali in developers for these materials.
is
of
a
very mild alkali which gives a developer of low alkalinity and produces negatives of a relatively low degree of contrast.
Furthermore, by adding
suitable quantities of boric acid to a developer containing borax, sible to control the
development rate between rather wide
Tribasic sodium phosphate
graphic developers.
as
This
hydrolyzed
an objectionable scum and
The
hardening fixing bath
in the fixing
alkali therefore is
employed
is
(see
312), although in low concentration
it
in
with alum
salt reacts
bath to form aluminum phosphate which
swell unevenly.
pos-
used sometimes as an alkali in photo-
It is partially
reserve of caustic soda. fixing
is
it is
limits."
water and supplies a in
may
an acid hardening
deposit on the film
bath the gelatin film tends to
most useful only when a non-
Formula F-24, Appendix, page be used with some success
may
with hardening fixing baths.
The amines, which
common 7
"
constituent,
Some
Carlton and
are organic compounds containing nitrogen as a and are related to ammonia, have been suggested
Properties of Fine Grain Developers for Motion Picture Film " by H. C. Trans. Soc. Mot. Pict. Eng. No. 38, 406 (May 1929). I. Crabtree.
J.
SUBSTITUTION OF CHEMICALS for use as alkalis in developers, but these substances
223
have a tendency
to
They have
not, there-
Acetone and formaldehyde are recommended occasionally
for use in
produce dichroic fog and
to dissolve silver halides.
found any general commercial application.
fore,
These substances react with sulphite to liberate caustic soda (see discussion in Chapter VII, page 120). Acetone is a solvent for cel-
developers.
when mixed with water
lulose nitrate, but
out dissolving
it,
should not be used
Formaldehyde der the
name
it
swells the film support with-
and the gelatin emulsion tends
is
in
to
become detached.
It
high concentration in developers for films.
a gas and
" formalin."
is
normally supplied as a
It is also available in solid
37%
solution un-
form as paraform
(paraformaldehyde) prepared by slow evaporation of solutions contain-
When
ing over 30^0 of formaldehyde.
water, a solution for formaldehyde
Ammonia and ammonium
is
this
white solid
is
dissolved in
produced.
carbonate are seldom used in developers on
account of the odor and the fact that they tend to cause dichroic fog.
For a more expanded discussion of the alkalis in development refermade to the articles by Wall and by Seyewetz on this
ence should be subject.*
Desiccated and Crystal Sodas.
â&#x20AC;&#x201D; Sodium carbonate
is
usually sup-
known as the hydrate (NasCOg. loHoO) containing 37% carbonate by weight; plied in three forms: crystals with ten parts of water
tals
decacrys-
with one part of water, called monohydrated carbonate (Na.jCO,.
HoO)
containing
carbonate
85%
(NaXO.)
carbonate; and the dry powder called desiccated containing
98%
carbonate.
The
last
two named
varieties are used chiefly for photographic purposes in the United States
and the first named is used extensively in Europe. Monohydrated carbonate is sometimes stated to have
less
tendency
than desiccated carbonate to cake on mixing with water and to be affected
by atmospheric conditions on
however, that
if
desiccated carbonate
storage. is
stored with only moderate care,
in a closed bin, barrel, bottle, or can, the quantity of
water absorbed
rarely enough to have an appreciable photographic effect, while ing tendency
is
its
no greater than that of monohydrated carbonate.
cause of the water of crystallization present it is
necessary to use
17% more
less
Experiments have shown,
in the
monohydrated
than when the desiccated variety
is
cak-
Be-
variety, is
used.
8 "The Alkalis in Development" by E. J. \\'a.\\. Amcr. Phot. i6, 481 (1922). See also " Practical Equivalence of .\lkalis and Their Substitution in a Given Photographic Developer" by A. Seyewetz. Bull. soc. franc. Phot, ct Cinciuat. 24. 190-93 (Nov. 1937).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
224
Sodium sulphite is supplied for photographic work in two forms: crys(Na.SOa.yHoO) containing about 50% of sulphite, and desiccated sulphite (Na.SO,) containing about 96 to gyC^ pure sulphite. The desiccated sodium sulphite is much less liable to oxidation by the air than the tals
crystalline variety.
When
substituting the sodas, use the following ratios:
(NaXO^.ioH.O)
3 parts decahydrated carbonate
one of desiccated
to
carbonate. i^ parts monohydrated carbonate (NaoCO;..H^O) to one of desiccated
carbonate. parts of crystalline sulphite (Na.SO.,.7H.O) to one of desiccated
2
sulphite.
Desiccated sulphite
is
now
supplied in the United States in a granular
form which pours easily from a can with
less
dust formation and dissolves
equally as readily in water as the finely powdered salt previously used.
The
Restrainer.
â&#x20AC;&#x201D; Potassium bromide may be replaced by an equal The sodium
weight of sodium bromide. ever,
salt is
and therefore of variable composition.
very deliquescent, how-
Ammonium
not be used in a developer because the alkali liberates this tends to
The
produce dichroic
fog.
addition of an alkali iodide to a developer containing bromide
sometimes recommended (0.01% fog.
Low
to
0.1%)
is
to control the formation of
concentrations of iodide are effective in controlling fog but
higher concentrations (above is
bromide should
ammonia gas and
not practical to replace
all
0.1%)
retard the rate of development.
the bromide with iodide.
This
is
It
because
iodide tends to convert the silver bromide in the emulsion to silver iodide
and materially slows up the less soluble in a fixing
that
it
rate of fixation since silver iodide
bath than
silver
bromide.
Iodide
is
is
much
beneficial in
prevents the formation of abrasion marks and lessens the tendency
for dichroic fog.
Tests on the suitability of a number of organic compounds as antifogging agents in place of potassium bromide have been
made by
Trivelli
and Jensen.^ Of the substances examined, 6-nitrobenziminazole " appeared most promising and undoubtedly further research will reveal other valuable antifogging agents.
Substituting for
/.
Sodium
for Potassium Salts.
photographic purposes, a potassium
salt
â&#x20AC;&#x201D;^As a general
rule,
can be replaced by a sodium
9 " Anti-fogging Agents in Developers " by A. P. H. Trivelli and E. C. Jensen. Frank. Inst. 2io, 287 (1930) ibid. 212, 155 (1931). 10 P. Wulff, U. S. Pat. 1,696,830. ;
SUBSTITUTION OF CHEMICALS
225
weight for weight, the error caused by the difference in molecular
salt
There are many excep-
weight of the two salts being usually negligible.
however, where there
tions,
is
a difference in the physical properties of
the two salts; for example, potassium carbonate and sodium bichromate
absorb moisture rapidly on exposure to a
damp
atmosphere, while so-
dium carbonate and potassium bichromate absorb moisture only very slowly.
important, therefore, that deliquescent salts be stored in
It is
tight containers
and that they be dry when used
for substitution.
SUBSTITUTION IN THE FIXING BATH
— This chemical has been used
Sodium Thiosulphate (Hypo). most exclusively as a
fixing agent for
A
with dry plate and film emulsions, for more than half a century. clear crystalline
al-
photographic purposes, especially fine
form known as prismatic crystal hypo represents a more
rapidly soluble form than the larger pea crystal
hypo which has been
common
fixes sufficiently rapidly
many
use for
years.
It is
cheap and
in
for most types of photographic work. more rapidly and is a satisfactory substitute for sodium salt but it is more expensive. Sulphites and Bisulphites. As stated under the section on "Fixing Solutions," page 151 of Chapter VII, sodium sulphite is usu-
at concentrations of 20 to 40^c
Ammonium
thiosulphate fixes
—
added
ally
an acid hardening
to
The sodium
of sulphur.
salt is
fixing
bath to prevent the precipitation
used almost exclusively because other
alkaline sulphites are not readily available. tive are the alkali salts of organic acids, of
good example.
Other types of preserva-
which sodium acetate
These substances are known as
" buffer salts "
is
a
because
they reduce the hydrogen ion concentration of the acid employed, be-
low the limits at which sulphur
is
precipitated from
hypo by means
of
acids.
The
acid salts, sodium bisulphite and potassium metabisulphite, are
not suitable for substituting in the usual potassium alum-acetic acid
hardening fixing bath without the addition of acid because the available acidity of these salts
aluminum sulphate
may
chrome alum
Alums. double 11
"
is
insufficient to prevent the precipitation of
sulphite on adding developer to the fixing bath.
Sodium
be used, however, as a substitute for sulphuric acid
bi-
in a
fixing bath.^^
— An
salt of
Some
Soc. Mot. Pict.
alum (as used in photography) is a compound or aluminum sulphate or chromium sulphate with sodium,
Properties of Fixing Baths " by
Eng.No.
3S, 364
(May
1929)-
J. I.
Crabtree and H. A. Hartt.
Trans.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
226
potassium, or
ammonium
sulphate.
The hardening
action
only pro-
is
duced by the aluminum or chromium ion so that equivalent weights of
any sodium, potassium, or ammonium alum or aluminum, or chromium salts, such as aluminum sulphate, etc., should exert the same hardening action.
As a
result of a series of practical tests the following conclusions
have
been drawn: 1. Equal molecular quantities of potassium alum, aluminum sulphate and aluminum chloride exert the same hardening action, two parts by weight of crystalline aluminum sulphate being equivalent to three parts by weight of potassium alum. Commercially pure aluminum sulphate is
satisfactory
if
this
does not contain an excess of iron.
the usual liquid hardener formula with commercial
a slight milky suspension
and then 2.
is
When
aluminum
formed which should be allowed
mixing
sulphate, to settle
filtered off.
There
is
no appreciable difference between sodium, potassium and
ammonium alums
in their
hardening action when substituted weight for
weight in the usual formulas. action occurs, this
is
In practice,
if
any difference
in
hardening
a result of the use of impure alums, in which case,
providing the impurities are harmless, an increased quantity of the alum its content of aluminum sulphate is the same as alum called for by the particular formula. 3. Ammonium chrome alum may also be substituted weight for weight for potassium chrome alum. It has previously been stated that a fixing bath containing ammonium alum has a greater tendency to give dichroic fog than a bath containing potassium or chromium alum, because of the liberation of ammonia when the bath becomes alkaline, but recent tests have shown that this effect is not as serious as had been supposed. Commercial samples of ammonium chrome alum, however, vary considerably in their degree of purity, compared with potassium chrome alum, so that the latter salts are to be preferred. Potassium chrome alum should therefore be used whenever possible, but if ammonium alum has to be used, the fixing bath should be kept in an acid condition to prevent any
should be used so that that in the potassium
possible trouble from dichroic fog. It
is
entirely possible to prepare
chrome alum
fixing baths
which have
alum
fixing baths
properties equally as satisfactory as those of potassium
and which have superior hardening properties. It is usually not possible to substitute potassium alum by chrome alum in a potassium alum formula nor chrome alum by potassium alum in a chrome alum formula unless the
pH
values of the baths are modified.
The
pH
range for sat-
SUBSTITUTION OF CHEMICALS
227
isfactory hardening with a potassium
alum bath is usually from 4.8 to and with chrome alum baths, from 3.0 to 4.0.'Chrome alum in a fixing bath gives the most satisfactory hardening when combined with sulphuric acid whereas potassium alum works best 5.0
with organic acids such as acetic.
be
made
For further
to the discussion of fixing baths
and to the Acids.
literature
in
page 153,
\'1I,
on the subject referred to under Chapter VII.
â&#x20AC;&#x201D; The most commonly used acids are
and sometimes
should
details, reference
under Chapter
lactic acid.
acetic, citric, tartaric,
Strong acids like sulphuric are seldom used
baths containing potassium alum because of the great tendency to
liberate sulphur.
As noted above, however, sulphuric acid
most exclusively when compounding chrome alum acids like the above bear the
bonated alkali
same
any one
Acetic acid
is
strengths, glacial
acid
is
al-
Weaker
they act as a reservoir of acid,
is,
is
available for reaction in
time.
photographic purposes
usually supplied
for
(98%) and 28^ r
acid, so that
equivalent to three and a half volumes of
rule can be given
used
relation to a strong acid as a car-
to a caustic alkali, that
so that only a small proportion of the acid solution at
is
fixing baths.
when
substituting acetic acid
malic and other organic acids.
in
two
one volume of glacial
28% by
The question here
acid.
No
definite
citric acid, tartaric, is
not merely one of
relative acidities, because the degree of hardening of the gelatin pro-
duced by a given quantity of alum
in
combination with equivalent
The
quantities of different acids depends on the particular acid used.
addition of increasing quantities of an acid to an alum solution lowers its
hardening properties and the hardening
falls off at a
greater rate with
increasing additions of citric and tartaric than with acetic.
do not harden gelatin.
As a
rule, therefore,
acetic with citric or other organic acids.
The
and
it is
not advisable to replace
^^
addition of boric acid to a potassium alum fixing bath containing
acetic acid has been
shown
to be beneficial because the
the two acids tends to extend both the sludge life of
Citric
form complex ions with the aluminum ion which
tartaric acids tend to
the bath.^^
life
combination of
and the hardening
In general, 5 grams of boric acid should be added to
12 " Some Properties of Chrome Alum Stop Baths and Fixing Baths " by J. I. Crabtree and H. D. Russell. J. Soc. Mot. Pict. Rug. 14, 483 and 667 (May and June
1930). 13
"
Some
Properties of Fixing Baths " by
14 "
J. I.
Crabtree and H. A. Hartt.
(May 1929). An Improved Potassium Alum Fixing Bath Containing
Soc. Mot. Pict. Russell and
Eng.No.
J. I.
Trans.
3S, 364
Crabtree.
/.
Boric Acid " by H. D.
Soc. Mot. Pict. Eng. 21, 137 (Aug. 1933).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
228 a
a fixing bath containing hypo, potassium alum, sodium sul-
liter of
and
phite,
acetic acid to produce satisfactory results.
The minimum
concentration of acetic acid in such a fixing bath should be lo cc of glacial acetic acid (37 cc of
28%
acetic) per liter.
Nitre cake or sodium bisulphate acid in a
chrome alum
fixing bath
may
be substituted for the sulphuric
by using
5
grams (73 grains)
of the
bisulphate for each cc (| dram) of sulphuric acid.
â&#x20AC;&#x201D;
Impurities in Developing and Fixing Chemicals. It is beyond the scope of the present chapter to indicate all the possible impurities which may be present in photographic chemicals. For a more detailed account the reader is referred to a paper by H. T. Clarke.^" In this chapter
we
are only concerned with the impurities usually
present in chemicals which are not intentionally added as adulterants.
Impurities
may have
access to photographic chemicals in three ways:
A. During manufacture, B. during storage, C. during mixing and storage of the solution.
A. If chemicals of repute are purchased, the photographer need not
worry about impurities. If the
Elon, hydroquinone or pyro
is
colored, the presence of fogging
agents should be suspected, although some colored samples do not give
any more fog than colorless ones. Many metallic compounds such
as salts of copper
sulphides, etc., exert a powerful fogging action even in
minute quantities, and should be avoided.
A
and
tin,
metallic
when present only
more complete
discus-
sion of the fogging action of metallic salts has been presented in other
papers (see references under Chapter VII, page 121).
Table 8 indicates the nature and
effect of the
more common impurities
present in the chemicals used for developing and fixing baths.
B. For impurities introduced during storage see " Storage of Chemicals,"
fog is
page 192.
The developing agent
C. if
become oxidized and may cause
added after the developing agent (see Chapters VII and
ing of Developers,"
on
will
the water used for mixing contains dissolved air, and
"
Chemical Fog
15
Chcm.
"
if
IX on
and
" Storage of Solutions," respectively,
" in
Amer. Ann. Phot. 33, 20 (1919).
Examination of Organic Developing Agents " by H. T. Clarke.
10, 891 (1918).
stain
and
the sulphite
and
"
Mix-
article
/. Ind.
Eng.
SUBSTITUTIOX OF CHEMICALS
TABLE Nature and Effect of Impurities Chemical Pyro, hydroquinone,
229
12 in Photographic
Chief Impurity Oxidation products and
Chemicals
Effect of Impurities
Chemical fog
adulterants
Adulterants weaken the effect of the developer
Sodium sulphate
Keeping properties of the developer are impaired Iron gives a dirty bluish-red solution with pyro (harmless) Decreases the accelerating power
Potassium bromide
Iron and sodium sulphate Sodium carbonate Potassium chloride
Harmless
Hypo Alum
Sodium sulphite Sodium sulphate and
Diminishes the fixing power Diminishes the hardening action
etc.
Sodium *
sulphite
Sodium
bisulphite
Caustic soda
ammonium
sulphate
Chrome alum
Ammonium
Acetic acid
and sulphuric acid Water
sulphate
Excess of acid tends to cause sulphurization of the fixing bath Deficiency of acid causes milkiness of the acid fixing bath due to the precipitation of alumi-
num *
See discussion, " The Preservative," page ii6.
sulphite
CHAPTER XI STAINS ON NEGATIVES AND PRINTS* A
stain
may
be defined broadly as any deposit, foreign to the photo-
graphic image, which will absorb light and " stain "
word
therefore, capable of pro-
is,
ducing an image during printing, although,
everyday language, the
in
usually associated with something colored.
is
A
photo-
graphic stain can therefore be considered as a deposit on a photographic positive or negative
whose color
is
foreign to that of the photographic im-
This definition would therefore include colored spots, irregular
age.
The purpose of this chapter is to how such stains are produced, how to prevent them, and, whenever possible, how to remove them. Most types of stains result from carelessness, such as overworking a
colored markings, and general stain. explain
developer, using solutions at too high a temperature, lack of agitation,
Almost invariably the cause of and not the manufacturer although the
insufficient fixation or washing, etc.
stains can be traced to the user latter is often
it
blamed unjustly by the former
The diagnosis of the nature of is known at which point in the
the trouble
first
appeared.
appearance of the
stain,
A
a stain
be simplified greatly
if
processing or history of the material
second clue
namely,
for the trouble.
may
its
in the diagnosis is the visual
color, character,
and position on the
material.
Before accepting a job of restoration of a stained negative or print, the photographer should have an understanding in writing that the cus-
tomer assumes the restoration
risk.^
Also, the photographer should not
subject the original to any chemical treatment until he has
tographic copy of first
it.
In some cases, as noted
be made with the aid of suitable
later,
made
to eliminate the
filters
a pho-
an attempt should defect
photographically.
Chemical treatment of photographic materials should never be resorted to until the fundamentals underlying such treatment are thoroughly understood.
Conversely the restoration of a valuable negative or
print should never be entrusted to a novice or less
1
may
be ruined by care-
handling.
* Revised from an article originally written by Amcr. Ann. Photo. 35, 204 (1921).
Co.,
it
"
Laws Which
J.
I.
Crabtree and published
Affect the Photographer " by L. T. Parker.
Qeveland, Ohio, 1930.
in
Abel Publishing
ON NEGATIVES AND PRINTS
STAINS
The Importance
â&#x20AC;&#x201D; The object
Stains.
the gelatin
Thorough Washing
of
any soluble chemicals which might
Preventing
for
washing negatives or prints
in
231
is
remove from
to
later cause fading of the
image or interfere with a subsequent chemical treatment. Since the rate of fading size decreases,
it is
-
of
an image usually increases as the grain
obvious that negatives on fine grained emulsions
re-
more thorough washing than those on coarse grained ones. The average negative can be considered to be washed adequately if it is
quire
treated for 30 minutes, in a tray or tank into which water
a rate sufficient to replace the water in the vessel hour.
5 or 6
is
running at
times each half
Fine grained negatives should preferably be washed at least one
hour under the above conditions. Prints need to be washed longer than negatives, because the paper
Usually, a print should be wached
base tends to retain the chemicals. for at least
one hour
in a vessel in
which the water
the rate of 10 to 12 times per hour.
water
The time
which a stream of water
in the vessel into
found easily by adding to the vessel a
sufficient
is
being replaced at
required to replace the is
flowing
quantity of
may
1%
sium permanganate solution (10 grains potassium permanganate ounces water)
(i
gram
in
The
in
2^
100 cc of water) or red ink to color the water
appreciably, and noting the time required for the water to less.
be
potas-
become
color-
flow of water should then be adjusted so that the vessel
empties at least 10 to 12 times each hour.
For greatest permanence, after in
fixing, place the prints for 5
a fresh fixing bath and then wash for
2
minutes
hours under the foregoing
conditions.
Classification of Stains.
â&#x20AC;&#x201D; For purposes
of reference, stains
have
and the remarks apply
to all
photographic sensitive materials including films, plates, lantern
slides,
been
classified according to their color
paper prints and motion picture gelatin emulsion
All of these are coated with a
which after developing and
fixing consists of a layer
embedded an image of silver, or one of its comIn what follows the word " film " is used synonymously with
of gelatin in
pounds.
film.
which
is
such a gelatin silver image.
General gray stain or fog has been treated in a previous chapter (see
page 139).
In this chapter
we
will consider
a stain as a fairly large
deposit whose color differs from that of the image and which 2 "
A
Method of Testing
ture Films " by
1930).
J. I.
for the Presence of
Crabtree and
J.
F. Ross.
/.
Sodium Thiosulfate
in
may
be
Motion Pic-
Soc. Mot. Pict. Eng. 14, 419 (Apr.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
232
" local "
(when
it is
not uniform) or " general," in which case
form and of even density over the entire
it is
uni-
film.
Several specific classes of markings or stains as
may
be caused by
moisture,^ airbells,^ static/' the presence of developer fog from sulphide/
and
oils/ are discussed in detail elsewhere.
WHITE STAINS A
White Powdery Scum,
—
removed by washing, it washing of the film. hypo crystals and is due If it is insoluble in water, and therefore not removed by washing but is dissolved by sodium carbonate or acetic acid, it consists of aluminum I.
consists of
sulphite.
a
is
is
to insufficient
The
10% sodium
ing
If this
by dipping
solubility test can easily be
carbonate solution on in water.
If
made by
placing a drop of
the edge of the film
on drying the
film
is
clear,
most probably aluminum sulphite providing an alum
and then wash-
then the deposit fixing bath
was
used.
The
acid fixing bath most
commonly used
consists of a mixture of
alum, acetic acid, sodium sulphite, and hypo, or
in other
words, a mix-
hypo and aluminum sulphite dissolved in acetic acid. If sodium carbonate is added to this, the acid is neutralized forming sodium acetate, and as soon as the quantity of acid in the bath falls below a certain critical value the aluminum sulphite comes out of the solution, turning the bath milky and deposits as a white sludge which settles on the surface of the film, and is not removed in the wash water.* Since developer is carried over to the fixing bath by the film, only a ture of
definite is
number
of films or prints can be fixed before the critical point
reached and the precipitation of the sludge commences.
tures
At tempera-
around 65°F. (i8°C.) usually a further quantity of acid
added
to the fixing
bath to compensate
may
be
for this developer carried over,
3 " Moisture Markings on Motion Picture Film " by J. I. Crabtree and G. E. Matthews. Trans. Soc. Mot. Pict. Eng. No. 17, 29 (1923). Revised 192S. 4 " Rack Marks and Airbell Markings on Motion Picture Film " by J. I. Crabtree and C. E. Ives. Trans. Soc. Mot. Pict. Eng. No. 24, 95 (19-25). 5 " Static Markings on Motion Picture Film " by J. I. Crabtree and C. E. Ives.
Trans. Soc. Mot. Pict. Eng. No.. 21, 67 (1925). 6 " Sulphide Fog by Bacteria in Motion Picture Developers " by and J. I. Crabtree. Trans. Soc. Mot. Pict. Eng. No. 19, 28 (1924)7
" Oil Spots
on Motion Picture Film
Trans. Soc. Mot. Pict. Eng. No. 32, 728 * The addition of boric acid (about
"
J.
L.
I.
Dundon Crabtree.
1927)1%) greatly minimizes the sludging tendency (
of a potassium alum-acetic acid fixing bath alkalinity.
by G. E. Matthews and
M.
when used with developers
of average
STAINS though
in
ON NEGATIVES AND PRINTS
warm weather
there
233
danger of sulphurization (see page
is
185).
In order to prolong the tion of a.
as
aluminum
of the fixing bath
life
sulphite
it
and prevent the forma-
advisable to:
is
Rinse the film between the developing and fixing so as to remove developer as possible.
much b.
Avoid the use of a developer containing an excessive quantity of
alkali. c.
Use an acid
rinse bath
between the developer and
Stop
fixing bath.
baths should always be used with discretion, however, otherwise an excess of acid
is
carried over to the fixing bath which in turn causes sul-
phurization.
A
suitable rinse bath for negative materials consists of a
tion of
For
sodium bisulphite or a
3%
solution of potassium
2.5%
solu-
chrome alum.
1.25% solution of glacial acetic acid is satisfactory. aluminum sulphite sludge still appears after observing the above precautions, then either the acid hardener was not mixed correctly (probably too little acid was added) or the acid used was not up to strength, or too much sulphite was used. Precipitation or " scumming " may take place on the print or negative with a very alkaline developer even when the fixing bath is clear, prints, a
If the
if
no stop bath
is
used.
This
is
due
to the fact that precipitation occurs
before the developer has time to diffuse of the film
when
it is first
moving the excess
immersed
away from
in the fixing
the film.
bath
Agitation
will assist in re-
of developer from the surface of the film
and
will
reduce the tendency for a precipitate of aluminum sulphite to form.
The
following fixing bath formula was devised in 1934 and has the
valuable property that
normal useful
it
has a very low sludging tendency during
its
The hardening properties are also maintained durThe formula is satisfactory for use with amateur and
life.
ing this period.
professional negative materials.
Acid Hardening Fixing Bath Avoirdupois
Water (about
Hypo Sodium
125째 F.) (52째 C.)
.
.
.
ounces ounces "jounce ounce I
16 11
Sulphite, desiccated
Kodalk Acetic .\cid,
28%
Potassium Alum Cold water to make
ounces ounce ounces
214 fluid ?i
32
[F-10] Metric 500.0 cc 330.0 (>ranis 7.5 30.0 70.0 22.5
ftratns
$>rams cc
j^rams
1.0 liter
Dissolve the hypo in one-half the total volume of water and then add the remaining chemicals in the order given after dissolving in a small volume of water (about I25째F.) (52째C.). Dilute with water to the required volume.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
234
Removal of Aluminum Sulphite aluminum
bility of
dium carbonate, the scum few minutes oughly.
in a
wash the
5%
5
removed by bathing the film for a sodium carbonate and washing thor-
is
above 65°F. (i8°C.),
minutes
for 2 or 3
about
film
view of the solu-
easily
is
solution of
temperature
If the
harden the film
— In
Stain.
sulphite in sodium hydroxide (caustic soda) or so-
it
is
advisable to
and then
in the following solution,
minutes before any subsequent chemical treat-
ment:
Formalin Hardener
[SH-1]
Formalin (37% Formaldehyde solution;
Sodium Carbonate, desiccated Water 2.
to
make
Yellowish-White Opalescence.
ally visible only
made on
moved by bleaching and redeveloping sists of finely
more a. is
— This
1 .0
liter
particular stain
is
usu-
The
opal glass or celluloid.
(see
page 241).
divided or colloidal sulphur and
may
The
is
de-
not re-
stain con-
be due to one or
of the following causes:
Too much
added
tate,
10.0 cc 5.0 grams
and sodium carbonate, and
insoluble in water, acids,
is
Metric
2}2 drams 73 grains 32 ounces
on negatives or transparencies, and gives the negative
the appearance of having been posit
Avoirdupois
acid or too
to hypo, sulphur
but this
may
little is
sulphite in the fixing bath.
If,
and
therefore, the proportions of acid
phite are not correct in the fixing bath, or is
acid
be prevented by the presence of sodium sulphite
which dissolves sulphur. an excess of acid
When
thrown down as a yellowish white precipi-
if
impure sulphite
added when preparing the
sul-
used or
is
fixing bath, sulphur
is
gradually precipitated, and this precipitation takes place likewise in the
The time which elapses before sulphur is precipitated is known as the " sulphurization " life. b. The fixing bath is too warm. The sulphurization life of a correctly compounded fixing bath is relatively short at temperatures above 85 °F. The only remedy is to renew the bath as soon as sulphuriza29.5°C.) gelatin film.
.
(
tion begins. c.
The
will often
use of a plain potassium alum bath either before or after fixing
cause sulphurization, because alum behaves like an acid to-
wards hypo. free
If the
alum bath must be used, the
film should be
washed
from hypo before treatment.
Removal ing for
2
of Sulphur Stain.
—
First super-harden the film
by bath-
or 3 minutes in the alkaline solution of formalin given above
and washing thoroughly before treatment.
Then immerse
the film
ON NEGATIVES AND PRINTS
STAINS in a
warm io%
mately ioo° 3.
to
235
solution of sodium sulphite at a temperature of approxi-
i20°F. (38° to 49°C.) and wash thoroughly.
Silvery-White Opalescence.
— This
peculiar stain
is
formed
when drying negatives
or transparencies by means of denatured or wood
alcohol and especially
if
phenomenon
the drying
is
This
hastened by means of heat.
has been attributed to various causes, including the use of
impure alcohol, or alcohol containing
resins, insufficient fixing, or
wash-
ing of the film, the presence of calcium salts in the wash water, etc.
may
Although these factors
influence the
amount
duced, they are not the determining factors, since
of opalescence pro-
it is
possible to obtain
severe opalescence by immersing a film of plain gelatin in pure grain
The amount more rapid the drying and the
alcohol and drying at a temperature of 95°F. (35°C.). of opalescence produced
greater, the
is
higher the temperature of drying, but is
insufficiently
and washed
fixed
it
if
rarely occurs even
drying
if
the film
conducted at 70° F.
is
(2I°C.).
The opalescence
is
apparently due to precipitation of the gelatin by
the alcohol to a dehydrated modification which
more readily precipitated than
The
precipitation
is
warm
ing alcohol to a solution of gelatin in
also
produced by add-
water.
Hard
gelatin
is
soft gelatin.
the film is immersed in concenhypo or sodium sulphite. When a strong solution of hypo containing an excess of
is
produced
also
if
trated solutions of certain salts such as fixing a negative in
acid hardener, the fixed film often appears milky, especially in
weather, though the milkiness disappears in the wash water precipitated gelatin returns to the hydrated modification.
escence will often appear solution of
when removing sulphur
sodium sulphite
Removal of Opalescence.
— Immersion
in
fixed,
washed, immersed
in
volumes of water, wiped
if
warm
on washing.
water and drying at
normal temperatures removes the opalescence completely. ing with alcohol, opalescence rarely occurs
the
This opal-
stains with a
(see above) but disappears
warm
when
the film
is
When
dry-
thoroughly
a mixture of 90 volumes of alcohol and 10
off carefully,
and then dried by a fan
at a
temperature not exceeding 7o°F. (21'^C.).
To Summarize.
—
It
is,
of course, possible for
of white stains to be present on the stain, therefore, the film
should
first
same
film.
two or more
varieties
To remove an unknown
of all be fixed in plain hypo, washed,
and bathed in a 10% solution of sodium carbonate and washed to remove any aluminum sulphite. If a stain still persists this is due to sulphur, and is removed by first hardening the film for two or three minutes,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
236
formalin hardener (page 234), immersing in a 10% solution of at 100° to i20°F. (38° to 49°C.) and washing.
in the
sodium sulphite 4.
Yellowish-White Stain.
— This
particular stain occurs princi-
pally on old D. O. P. prints, the effect being a faded appearance chiefly
where there
in the highlights is
is
least silver,
and the
to the conversion of the silver
image
image
color of the
This stain which develops with age
usually yellowish white.
is
due
to a yellowish-white modification
That such a modification does exist can be shown by immersing a piece of well washed and unexposed printing-out paper, the
of silver sulphide.
emulsion of which consists essentially of silver chloride, in a
sodium sulphide.
tion of
2%
solu-
Prolonged action of the bath produces a yel-
lowish-white image whose color resembles that of the stain in question.
The formation
of the silver sulphide
may
be due either to internal or
Internal agents are usually thiosulphates left in the
external causes.
and washing as explained above. Owing atmosphere and moisture these thiosulphates are
print from insufficient fixing to the action of the
oxidized,
and
at the
same time the
silver
image of the print
is
converted
to silver sulphide. If the print is fixed in a
sulphur, caused by too
sulphurized bath which
much
is
slowly depositing
acid in the fixing bath, or
by the use
of a
too strongly acid rinse bath (see sulphur stains, page 234), the sulphur is left
in the print
image
to
form
even after washing, and
silver sulphide.
image of a print
is
The
this
combines with the
relative ease with
which the
sulphurized as compared with a negative image
silver
silver is
due
to the fineness of grain of the print image.
Some of the factors which determine the degree of fading are: 1. The quantity of hypo or of silver thiosulphate left in the image. The coarser the grain, the less readily 2. The grain size of the image. is it
attacked and, therefore, the image has
less
tendency to fade.
At room temperature 3. The temperature and humidity of storage. iio°F. while at 6 months, (43 °C.) the same an image may fade within image
may
fade overnight.
External agents are sulphurous gases in the air such as hydrogen sulphide, while the hypo, which
may
be decomposed and
may
act in a
be present in the mount of a print
manner
similar to that of the thiosul-
phates left in the print as outlined above.
Fading
may
be minimized by the following procedures:
images are fixed thoroughly with agitation in a fresh acid fixing bath which is perfectly clear and not depositing sulphur, and are then washed thoroughly, fading and therefore yellowish white stains may I.
If
STAINS
ON NEGATIVES AND PRINTS
largely be prevented. i-i
minimum 2.
Developing-out papers require washing from
an adequate stream of pure water
to 2 hours in
propensity to
in
order to insure a
fade.**
Bleach the fixed and washed image
in the
chloride-sulphuric acid bath and redevelop and
page 241.
237
This treatment destroys any traces of
permanganate-sodium wash as explained on harmful sulphur com-
pounds, probably converting them to inert sulphates. 3.
Convert the
silver
image
to silver sulphide
by sulphide toning
in
the usual manner. 4.
Treat the washed print
in a s'y(
solution of sodium carbonate at
This converts any
a temperature of iio°F. (43°C.) and then wash.
compound
residual sulphur
sodium sulphide which washes out more
to
readily.
Most pastes are hygroscopic 5. Avoid the use of paste adhesives. and the presence of moisture tends to accelerate fading. Ordinary starch paste or photo paste have a
minimum tendency
extreme permanency, use only dry mounting
to cause fading but, for
tissue.
Also,
when
storing
negatives in paper envelopes, the pasted seam should be along the edge
and not
in contact
of Yellowish-White Stain.
or rather the restoration of the image to
simple matter but
The image
apt to occur shellac adhe-
â&#x20AC;&#x201D; The removal
of the stains,
with the image.
sive should preferably be used.
Removal
is
A
middle of the envelopes because fading
in the
where the pasted part comes
may
its
original color,
is
often a very
also prove to be a complicated procedure.
of the stained print
may
consist of several substances in-
cluding unchanged silver, silver sulphide, possibly oxidation and silver
and possibly
stain (see page 238), undissolved thiosulphate, tohalides.
moval print,
Usually bleaching and redeveloping as
of oxidation stain
though
silver
pho-
in the case of the re-
(see page 241) will thoroughly restore the
in a severe case
proceed as follows:
from the print by rubbing with artgum or by dabbing with a piece of stiff dough made from wheat flour. Grease marks can be removed with benzol, or gasoline, and the print finally rubbed over
Remove
all dirt
with alcohol.
If the print
is
mounted, detach
it
from the mount by
first
thoroughly soaking in water, then place face downward on a sheet of smooth paper and tear the mount away from the print. This is important, otherwise
8
"
A
Method
if
is
made
to pull the print
of Testing for the Presence of Ross. J. I. Crabtree and J. F.
Picture Films" by
(Apr. 1930).
an attempt
away from
Sodium Thiosulphate /.
in
the
Motion
Soc. Mot. Pict. Eng. 14, 419
238
PHOTOGRAPHIC CHE:MICALS AND SOLUTIONS
mount
it
be torn.
will inevitably
dry mounted, heat
If the print is
in a
press and strip.
Now
the print thoroughly in plain
fix
hypo
to
remove any undis-
solved silver halide, wash thoroughly, and then harden
two or three minutes wash.
If
by bathing
should be removed in a
2%
solution of potassium cyanide, removing the
print as soon as the image begins to be attacked (cyanide
poison and should be used with great care).
The
for
an alkaline formalin solution (page 234) and the highlights are stained this is due to silver stain which in
print should
now be bleached
in the
is
a deadly
Then wash thoroughly.
permanganate bath and
re-
developed as recommended for the removal of developer stain (see page
The permanganate bath converts
241).
the image consisting of silver
sulphide to silver chloride and this develops to a black silver image in the redevelopment.
The above treatment out papers.
is
satisfactory only for images on developing-
Gold toned images on printing-out papers are ruined by
the treatment since the gold image
is
converted to soluble gold chloride
by the bleaching bath. Faded images on printing-out paper can usually be improved by bleaching in a saturated solution of mercuric chloride, washing very thoroughly, and then redeveloping
in the
developer given on page 242.
YELLOW STAINS Yellow stains II. silver stain, I.
may
and
be of three kinds:
I.
developer or oxidation stain,
III. silver sulphide stain.
Developer or Oxidation Stain.
â&#x20AC;&#x201D; This
stain
is
caused by oxi-
dation products of the developer which are transparent like a yellow dye.
The
stain
may
be either
" local
"'
or " general."
Owing
to the fact
that printing papers are usually sensitive chiefly to blue light which
is
strongly absorbed by a yellow color, the stain acts as though a yellow filter
were placed over the negative.
Local yellow stain, therefore,
causes the image on the print to be weaker in those spots where the stain
is
present.
General yellow stain which covers the entire film just as though the film
had been uniformly dyed yellow has no harmful
effect other
than
to increase the printing exposure.
A. Local Developer Stain. pyro, hydroquinone,
oxygen especially
etc.,
â&#x20AC;&#x201D;
All developing agents, such as Elon,
have the property of readily combining with
in alkaline solution to
form oxidation products which
are often colored yellow or dark brown, and which have the property
ON NEGATIVES AND PRINTS
STAINS
of staining gelatin just like
a developer
is
exposed
and the developer turns yellow more or
to the air oxidation takes place less
When
an acid dye.
239
rapidly according to the temperature, the nature of the developer
and the amount of surface of developer exposed.
The
oxidation products, however, can in turn be reduced back again
by substances
to a colorless condition
so that
if
sodium sulphite or bisulphite
like
the developer contains an excess of sulphite, the rate of for-
mation of the oxidation stain
slow and usually proportional to the
is
quantity of sulphite or preservative present.
Apart from is
development the developing agent
aerial oxidation, during
being used up by virtue of
silver salt to metallic silver
reducing action in changing the exposed
its
and
in
so doing
is
it
oxidized
itself,
the
product formed probably being identical with that produced by aerial oxidation.
The amount
of oxidation product
formed
in this
way
is,
of
course, proportional to the quantity of silver developed, so that the pho-
tographic image
on a
silver
is
of a duplex nature consisting of a stain superimposed
That such an image
image.
immersing a pyro developed negative
moves the black
exists
in
image, leaving a yellow image which
silver
of the oxidation product of development.
image
is
The
is
utility of this stained
a stain image, though with developers like
glycin whose oxidation product the developer, the stain image
is
is
readily decolorized
by the sulphite
tanning gelatin, so
very feeble.*
much
that
so,
if
a negative developed with, say,
placed in hot water, the gelatin in the clear and
is
unhardened portions dissolves away leaving a relief image. Local irregular shaped stains are caused by local oxidation developer which
may
of the
be due to:
Careless handling of the film by incomplete immersion in the de-
veloper or fixing bath. films or prints in
responding
A
slight curl of the film or print, or too
many
some part of the surface exposed take place and a yellow patch will appear cor-
one tray,
to the air, oxidation will
air.
in
oxidation product, apart from being colored, has the property of
caustic hydroquinone
I.
re-
composed
explained below.
Most developers form such
The
can readily be seen by
Farmer's reducer which
will leave
in size to that of the
In motion picture work,
if
submerged a yellow oxidation film at regular intervals.
To
portion of the emulsion exposed to the
the top of the film rack stain
is
is
not thoroughly
produced which appears on the
prevent such stains
it is
obviously neces-
* In the presence of sodium sulphite, the oxidation products of hydro<|uinone probably consist of colorless hydroquinone mono- and di-sulphonates (see discussion
under Chapter VII, page 133).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
240
sary to immerse the films or prints completely in the developer or fixing bath. 2.
An
Since a developer oxidizes more rapidly
alkaline fixing bath.
in alkaline
than in neutral or acid solution, as the acid
in the fixing
bath
becomes neutralized by the developer carried over by the film, this developer oxidizes more and more rapidly and stains the fixing or rinse bath. When the fixing bath froths readily, it is probably alkaline and should be thrown away, though in some cases, acidity
by adding further quantities always important
It is
to
move
it is
prints or films around in the fixing
bath so that the alkaline developer in the print the acid in the fixing bath.
possible to renew the
of acid at intervals.
is
neutralized at once
by
simply thrown into
If the prints or films are
the bath and allowed to remain at rest, the developer clings to the film and the acid in the bath is not strong enough to neutralize it completely, so that the developer oxidizes and stains the film locally wherever there is an excess of developer, and especially if the film is locally exposed to the
air.
An
acid rinse bath between developing and fixing
in the developer in the film before
it
an almost certain
is
This neutralizes the alkali
cure for local developer stain (see page 233).
reaches the fixing bath, thus re-
ducing the tendency for further oxidation.
B. General Developer Stain. entire surface of the film 1.
and
is
â&#x20AC;&#x201D; This
exists
uniformly over the
caused by:
Old or discolored developer or a developer containing an insuffiimpure sulphite. General pyro stain is the
cient quantity of sulphite or
most common on negatives. In the case of prints, general yellow stain is
forced in a
warm
rinsed too long after developing
not agitated 2.
The
when
a.
in
produced
first
immersed
and before
fixing, or
of Developer or Oxidation Stain.
two ways:
a.
photographically, and
Local yellow stains
imposing a deep yellow
may filter
if
development
if
the prints are
if
the prints are
in the fixing bath.
use of a plain alkaline fixing bath.
Removal moved
is
developer, or in a dirty tray, or
b.
â&#x20AC;&#x201D; This
can be
re-
chemically.
be removed photographically by superover the negative and making a master
positive from this in a printing frame on a panchromatic film or plate just as w'hen
making
a paper print
from a negative.
Wratten G, and a suitable emulsion chromatic film or the Wratten Panchromatic plate. filter is
the
Panchromatic
film
is
is
sensitive to light transmitted
A
suitable yellow
Commercial Pan-
by the
G
filter
and
ON NEGATIVES AND PRINTS
STAINS in
turn the
G
filter is
a deeper yellow than most yellow stains, which are,
therefore, eliminated provided the stain
the stain contains any gray deposit the
nate
241
completely transparent.
is
filter
If
will obviously not elimi-
it.
An
method is to illuminate the negative by transmitted when copying or making an enlarged, reduced, or full sized and use a sheet of the filter film or a filter mounted between
alternative
light as
positive,
In this case a piece of
glass over the lens.
the diameter of the lens
Caution:
mount
filter
only slightly larger than
required.
Filter film consists of sheets of
mounted between
dyed gelatin and when not
be kept dry and free from finger marks. made it is a simple matter to make a dupli-
glass should
After the master positive cate negative on, say, in the usual
is
is
Eastman Commercial
film or
an Eastman 33 plate
way.
When making
master positives or duplicate negatives, care should be
taken to give sufficient exposure so as to produce clearest parts of the image.
A
full detail in
even the
good duplicate negative has no clear
shadows.
remove almost any colored
It is possible to
manner by a
print in a similar stain in question It is
muddy
as
if it
simply necessary to choose a
through the
be used
which blue
not
is
filter,
is
filter will
filter
provided the
such that on viewing the stain
and so on, taking care
sensitive to all colors.
from a negative or
filters,
were mixed with a black medium.
the stain becomes invisible.
for a red stain
stain
suitable choice of
Thus, a red to use
filter
should
panchromatic
film,
In the case of a blue black ink stain a
cut out only the blue.
It
better to
is
remove such
stains
by chemical means. b.
the oxidation product of the developer
If
(oxidation stain)
treated with an acid solution of potassium permanganate, further to a colorless substance which
is
it
is
is
oxidized
soluble in water. Such an acid
solution would dissolve the silver image also, but
if
sodium chloride
is
added, the bath converts the silver image to one of silver chloride while the stain is being oxidized. If the silver chloride image is now exposed to light
image
is
and developed in a non-staining developer, the restored free from stain.
To remove First
developer stain, therefore, proceed as follows:
harden the film by bathing
wise the gelatin
Then
is
apt to
for
2
or 3 minutes in an alka-
page 234) and wash for 5 minutes, othersoften and frill during the subsequent treat-
line solution of formalin (see
ment.
original silver
bleach in the following:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
242
Stain Remover
[S-6]
Metric
Avoirdupois
Stock Solution A Potassium Permanganate
Water
to
make
Stock Solution B Sodium Chloride (table salt) Sulphuric Acid, C. P. (concentrated)
A 5% but as
>^
32
A
parts of
75.0 grams 16.0 cc
ounce ounces
1.0 liter
and B.
solution of hydrochloric acid can be used instead of Solution B;
it is
often of uncertain strength,
A
use
its
is
not recommended.
if
kept separately, but not when mixed,
for this reason the bleaching
bath should be prepared as required.
Solutions
and
ounces
Hi ounces
Water to make
Use equal
5.3 grams 1.0 liter
grains
75 32
When
and B keep well
preparing Solution A,
make
sure that no particles of undiswill cause spots
solved potassium permanganate remain because they
and blemishes
in the negative.
The bleaching should be complete there
usually
is
manganese
oxide,
the image.
It is
then placing in a
left
a general brown
and especially best to remove
1%
about
in
or 4 minutes
3
in those parts previously this stain
solution of
when
stain all over the film due to
sodium
by
first
occupied by
rinsing in water
Wash
bisulphite.
and
for 3 or 4
minutes, and expose to a strong light {sunlight or arc light) until the
white image turns purple.
such as Nepera solution
Then develop
(dil.
in a non-staining developer,
1:2) or the following developer:
Diaminophenol Developer
[D-51]
Metric
Avoirdupois
Water (about
Sodium
ounces
24 350
125° F.) (52° C.)
Sulphite, desiccated
grains
H
Diaminophenol Hydrochloride (Amidol) Cold
When
vv'ater
to
make
removing stains by
32
this
750.0 cc 24.0 grams 7.5 grams 1.0 liter
ounce ounces
method, markings caused by drying a
negative without removing the drops of water (water markings), are usually removed also unless the markings are of long standing.^
— Although
most photographic stains are objectionable, a developer stain image, which is formed in position along with the silver image during development as explained
Usefulness o£ Developer Stain.
on page 239
is
often of great value because
it is
capable of producing a
same way that a print is produced by a silver image. Photographic papers are usually sensitive to blue light only, which is strongly absorbed by a yellow stain. The stain, therefore, behaves photoprint just in the
graphically like a black image.
Figures 93 A and 93 B illustrate this
9 " Moisture Markings on Motion Picture Film " by J. Matthews. Trans. Soc. Mot. Pict. Eng. No. 17, 29 (1923)-
Crabtree and G. E. Revised 1928.
I.
STAINS Figure
point.
93A
ON NEGATIVES AND PRINTS
a reproduction of a print
is
This negative was then phiced
tive.
silver
was removed, leaving
in
a yellow stain
243
from a pyro-stained nega-
Farmer's reducer until
all
the
image (see Figure 93B).
A. Print from negative having both
silver
and
stain images.
B. Print Fig. 93
from
ne^'ative
â&#x20AC;&#x201D; Effect
having only a stain image.
of pyro stain image on effective
printing contrast.
Of course, pyro
is
not the only developer which will give a stain image.
Developers such as hydroquinone give tion products,
and these can be
warm brown and reddish oxidawarm tones by
utilized in obtaining
direct development.
The
printing value of a stain image explains
why an
apparently weak
looking pyro negative will give good prints on a soft printing paper.
This is
is
because the stain which appears transparent and weak to the eye
really
opaque photographically.
So far as
it
has been possible to determine, a pyro stain image merely
intensifies the black silver
image and does not otherwise
alter the photo-
graphic quality, so that usually the same result in printing can be obtained
by prolonging development
be attained by intensification.
of the negative.
This result can also
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
244
The question
is
often asked, therefore,
if it is
better to develop for a
longer time in a non-staining developer like Elon-hydroquinone or for
a shorter time in a staining pyro developer.
If it
necessary always to
is
duplicate results as in the case of developing motion picture film in a
deep tank, a non-staining developer conditions
it is
is
desirable because under these
impossible to duplicate results with a staining developer
as explained below.
—
Control of Developer Stain. It is practically impossible to obimage which is free from general stain and vice versa. The proportion of general stain to image stain depends on the following tain a stain
factors a.
The quantity
of sulphite or preservative in the developer.
greater the quantity of sulphite present, the less
and vice
is
The
the stain produced
versa.
If the
developer
is
old, it rapidly
produces general stain with
little
becomes highly colored and then
or no silver or stain image, because the
developer has been converted largely to oxidation products which will not develop an image. b.
The time
of rinsing between developing
and
fixing.
A
long rinse
permits further oxidation of the developer by the oxygen dissolved in the
wash water and
c.
The nature
this
produces general stain. Since sulphite or bisulphite bleaches
of the fixing bath.
out stain and prevents oxidation of the developer, an acid fixing bath, therefore, destroys both general stain
order to produce the
maximum
and the stain image.
Hence,
in
quantity of stain image, use a fresh
developer containing low sulphite, rinse quickly between developing and fixing,
and
The
fix in
a large volume of fresh hypo.
following pyro formula
when used
image with a minimum of general
good stain
Pyro-Stain Developer
[SD-1] Water (about
Sodium
Avoirdupois 16 ounces
125° F.) (52° C.)
Sulphite, desiccated
20 40 75 32
Pyro
Sodium Carbonate,
desiccated
Water to make
Develop fix in
fresh will give a
stain.
for 6
minutes at 65 °F. (i8°C.)
Metric 500.0 cc
grams grams grams
grains grains grains
1.4 2.8 5.3
ounces
1.0 liter
in a shallow tray, rinse
and
a plain hypo bath.
The above
reasons explain
on a practical scale such as
why
it is
in small
impossible to produce pyro stain
amateur tanks or
in
deep tanks.
As
the developer becomes older the proportion of oxidation stain to stain
image changes, which
in turn
changes the quality of the negative.
STAINS
ON NEGATIVES AND PRINTS
If a negative is stained too strongly, the stain
removing
it
entirely
by bleaching
in a
may
245
be reduced by
first
permanganate-chloride bath (page
242) and then redeveloping in a mildly staining pyro developer (Formula D-i, page 281). This procedure usually gives more general stain,
however,
in
proportion to the stain image than
had been developed with the staining developer
Yellow Silver Stain.
II.
compounds
â&#x20AC;&#x201D; Another form
observation, though
it is
one or more of the following causes:
is
it
is
more
of a dirty
use of an old and exhausted fixing bath containing an excess
of silver in solution so that
if
the film
not sufficiently washed, some
is
This compound
colorless,
but
gradually changed to yellow silver sulphide on exposure to the
air.
of the silver salt remains after drying. is
to
It
can be either local or general and
may be due
to
due
usually less transparent and
Like oxidation stain
The
is
and washing.
from oxidation stain by ordinary
yellow color.
a.
the original emulsion
of yellow stain
of silver left in the film after fixing
to distinguish silver stain
difficult
if
in the first place.
To prevent such
stains, therefore,
acid fixing solution b.
and
to
Insufficient agitation
it
is
is
important to use only a fresh
wash thoroughly. on
first
immersing the films
In the absence of agitation, the developer
in the fixing bath.
in contact
with the film
re-
duces the silver halide dissolved out by the hypo back again to yellow metallic silver. The propensity for this stain to form is greatest with
very alkaline developers and with old fixing baths which have become neutral or alkaline. c.
A common
cause of silver stain when handling
development and fixation
of
two lengths of
roll
film placed
film
back
is
the
to back.
this may save space, it is false economy, because it is impossiwash the backs of the films which stick together. The result is that hypo containing silver is left in the gelatin backing which turns to silver sulphide on exposure to the air, so that while the emulsion side
Although ble to
of the film
is
clear the gelatin backing
is
stained.
In the case of films with anti-halation backings this procedure will obviously cause irregular stains.
When
the emulsion side of one film adheres to either the emulsion side
or back of another, the trapped developer reduces the dissolved silver
compounds
as explained in paragraph b, above,
silver stain.
Removal moved
of Yellow Silver Stain.
â&#x20AC;&#x201D;
and produces a
local
Silver stain cannot be re-
by bleaching and redeveloping as in the case of oxidation stain,
5
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
246
because this has simply the effect of converting the yellow silver sulphide
and then
to silver chloride
to silver so that the yellow stain is
changed
to a black stain of metallic silver.
There
no
is
way
of
always completely removing
silver stain,
though
the following methods are frequently successful:
After thoroughly washing to remove any hypo, bathe the film in a
a.
1%
solution of potassium cyanide {cyanide
and a
a deadly poison
is
solution in water emits fumes of poisonous hydrocyanic acid so that
The cyanide
should be used only in a well ventilated room).
it
will dis-
and some silver sulphide, though in image so that the film should be removed from the bath and thoroughly washed as soon as any signs of reduction
solve
any
time
it
silver thiosulphate present
dissolves the silver
of the image appear.
weak
In the case of an old negative, treatment with a
solution of
acid permanganate, washing, and then immersing in the cyanide will
often remove obstinate stains. b.
G
Copying the negative or print through a
paragraph
a.
page 240
will reduce,
filter
as described under
but not always completely remove,
silver stain. c.
The
stained gelatin backing
may
be removed from a non-curling
down onto
negative film as follows: squeegee the negative emulsion side
a sheet of Kodaloid previously coated with rubber cement diluted with
benzene, containing
5%
amyl
acetate,
and allow
it
Then
to dry.
place
the film and backing in a tray containing 5% sulphuric acid maintained o ° F. 8° The backing will dissolve in about 1 00 ° to 1 1 to 43 ° C ) ( 3 minutes and, after washing and drying, the Kodaloid
at
1
.
.
may
be stripped
may
also be re-
off.
d. The silver stain on moved by swabbing with
[SS-1]
the gelatin backing of films the following solution:
Iodine-Cyanide Stain Remover Avoirdupois 18 grains 36 grains 4 ounces
Iodine crystals
Potassium Cyanide (Poison!) Water to make
This solution rapidly dissolves the advisable to protect the emulsion side
under
c.
III. tains
silver first
Metric 1.3 2.5
grams grams
125.0 cc
image so that
it
is
usually
with Kodaloid as described
before treatment.
Yellow Silver Sulphide Stain.
an excess of
silver, this is
—
If
a hypo alum bath con-
converted to colloidal silver sulphide by
the free sulphur in the bath and this deposits in the highlights of a
STAINS
under certain conditions, as a yellow
print,
tions
ON NEGATIVES AND PRINTS
where a nucleus
247
In the shadow por-
stain.
for a deposition exists, the sulphide apparently
deposited in a coarser condition, and the resulting tone
is
is
not materially
affected.
stain may be prevented by maintaining the temperature hypo alum bath not higher than 125° F. (52° C.) and by adding further quantities of hypo solution free from silver, as the toning bath
The yellow
of the
ages.
When
negatives or prints are treated with Farmer's reducer (ferri-
cyanide-hypo) a yellow stain invariably remains
if
reduce a dense portion of the image completely. of silver sulphide;
it
may
iodide in excess of this is
apt to result.
in
a second
Removal
35%
hypo.
0.5%
— Since the
particles
finer than the image proper, a
such as a
1%
If the permanganate treatment
followed by immersion in a
weak
weak
is
may
used,
be used for it
should be
bisulphite solution to clear
up the
stain formed.
To Summarize.
— A yellow
following substances:
silver,
stain
may
consist of one or
more
cided to attempt
its
in case the stained
treatment.
This
Then is
removal,
first
photograph
find out
of the
silver sulphide, silver halide or photo-
halide together with oxidation products of the developer.
stain.
compos-
solvent of
solution of potassium cyanide (a deadly
solution of potassium permanganate,
treating the print.
brown
slowed up greatly, immerse the negative
bath containing
much
If a quantity of
usually being sufficient.
of Silver Sulphide Stain.
ing the stain are
attempted to
added, trouble from slow or incomplete fixation
If fixation is
fixing
silver sulphide,
poison) or a
is
is
be prevented by the addition of potassium
1%
iodide to the fixing bath,
it
This stain consists
is
make
If
it
is
a copy through a suitable
de-
filter
ruined completely in the subsequent
by a preliminary
done by cutting a narrow
test the exact
strip
nature of the
from the edge of the
washing and bleaching and redeveloping as above.
film,
If the stain is en-
removed and is not replaced by a black deposit, the stain is pure oxidation stain and the entire negative may be treated in this way. If the stain is only partially removed, treat the narrow strip with cyanide as for the removal of silver stain, wash well, and if a transparent yellow tirely
stain remains, treat this as for oxidation stain. in
removing the stains from the narrow
The degree
procedure necessary for the rest of the negative. The stained gelatin backing of films may be removed by ing the emulsion surface
by squeegeeing
of success
strip will serve as a guide to the
it
first
protect-
onto a sheet of Kodaloid, and
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
248
subsequently soaking the film (so protected) in warm, dilute sulphuric acid solution (page 246).
MISCELLANEOUS STAINS Yellowish-Brown with iron or iron rust.
If these reels are rusty, the rust
reels.
winding and
The
settle
may
stain
ammonium
A
roll film or
re-
stain.
50%
solution of
5%
solution of
removed by bleaching and redeveloping
stain.
â&#x20AC;&#x201D; This occurs
Brown Scum.
during
off
deep red coloration indicates the presence
stains are usually
when removing developer
oping
be scraped
be identified by placing a drop of a
thiocyanate.
The
of iron.
may
between the convolutions of the film causing the
on the stain and then adding a drop of a
nitric acid
as
â&#x20AC;&#x201D;
Stains. These are usually caused by contact Motion picture film is usually wound on iron film
motion picture
in
deep tank development when devel-
film.
If the developer does not contain
enough preservative, a layer of insoluble oxidation product of the developer forms as a scum on the surface and this is picked up by the film.
The scum forms most is
readily on the surface of the fixing bath
if
it
allowed to stand for any length of time, for instance, over the week
end.
When
the bath
is
any hydrogen sulphide
exhausted and contains an excess of silver in the air reacts
salts,
with the silver thiosulphate at
the surface of the liquid, forming silver sulphide which floats as a scum.
This
picked up when the film
is
is
immersed
in or
withdrawn from the
solution.
A
brown scum has
a peculiar appearance under the microscope
and
characterized by a series of cracks or fissures which are formed the
scum
broken up on immersion of the film
is
in the tank.
page 41 shows an enlargement of such a scum fissures are
is
to
morning
made by Fig. 20,
Figure 21,
which the cracks or
very pronounced.
The most film
in
is
when
effective
means
of preventing
brown scum markings on the
skim the surface of both the developer and
fixing
bath each
either with the edge of a sheet of blotting paper, or a
skimmer
stretching several layers of cheesecloth over a wire frame (see
page 40).
The width
of the
skimmer should be adjusted
to
fit
the width of the tank for most efficient results.
Scum markings can
occasionally be removed
by the bleach and
re-
development method given on page 241, or by bathing the film in a 1% solution of potassium cyanide {this chemical is very poisonous and
ON NEGATIVES AND PRINTS
STAINS
Weak
should be always handled with eare).
249
cyanide also attacks the
image and the film should therefore be removed and washed thoroughly as soon as any reduction occurs. silver
Green Stain or Dichroic Fog,
— Dichroic fog appears
lowish or reddish green metallic sheen flected light, or a pinkish tint
ing
by transmitted
it
light.
when a
film
when looking through
is
as a yel-
examined by
re-
the film or examin-
In view of this dual character
called
is
it
dichroic or two-colored fog.
When examined
under the ultra-microscope the fog
of extremely fine particles
to consist of metallic silver.
The
size of the particles
by transmitted light, those that are red those which are green or blue. color
Dichroic fog
is
is
seen to consist
which by chemical analysis have been shown
always formed either
fixing bath.
determines their
in color being smaller
than
in i. the developer or 2. the
—
Dichroic Fog in the Developer. In order that the deposition may take place in the developer some solvent of silver bromide, such as hypo, ammonia, or an excess of sulphite or carbonate, must be present, when under certain conditions the dissolved silver salt is reduced I.
of fog
to metallic silver in a
very
fine
state of division, particularly in the
shadows or unexposed portions of the emulsion where no bromide is liberated during development. A pyro-ammonia developer is apt to give dichroic fog especially with fine grained emulsions for this reason.
Some in a
of the factors
which contribute
to the formation of dichroic fog
developer are as follows:
a.
Presence of Sulphide and
a Silver Solvent.
—A
trace of so-
dium sulphide in a developer in the presence of a silver solvent such as hypo favors the formation of dichroic fog, due probably to the fact that the sodium sulphide first precipitates miriute particles of silver sulphide on the surface of the emulsion and these in turn act as nuclei for physical development."
Hypo
is
apt to be transferred to the developer
by wooden motion picture film developing racks which have been incompletely washed, or by film hangers which tend to retain hypo. Sodium sulphide can form in a developer as a result of the presence of bacteria,
which reduce the sodium sulphite
quent sterilization of the tanks
and
sodium sulphide.^ ^
L.
The Staining
Dundon.
J. I.
Crabtree.
Fre-
a satisfactory preventive.
Properties of Motion Picture Developers " by J. 25, 108 (1926). Traxs. Soc. Mot. Fict. lliiy. 11 " Sulphide Fog by Bacteria in Motion Picture Developers " by
10 "
M.
is
to
N
I.
Crabtree and
.
Trans. Soc. Mot. Pict. Eug. No. 19, 28 (1924).
M.
L.
Dundon
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
250
Fine grained emulsions
which the grains of
in
silver halide are
very
small and. therefore, more readily soluble are most susceptible to this
form of
fog. especially
if
the development
Prolonged Immersion
b.
is left
forced.
is
Used Developer.
in a
— In case
accidentally in a well-used developer over night, a
form of dichroic fog largely
is
Ordinary dichroic fog
produced.
on the surface of the emulsion, but
The
ates the entire gelatin layer.
more
is
filled
usually
by
trans-
light.
The
usually brown
mitted light and possesses a coppery luster by reflected
shadows are often
is
type thoroughly perme-
this
deposit
a film
insidious
with a deposit so dense that
it
is
impossible to
In some portions the negative image
obtain satisfactory prints.
may
also be reversed completely. c.
Presence of Sulphide
in a
Preliminary Desensitizer Bath.
— A desensitizer bath may become contaminated
with sodium sulphide
•
as a result of bacterial growth acting on the sulphite carried into the
bath from the developer or the fixing bath by film sulphide
carried into the developer
is
produced as described under 2.
erally
or
a.
by
above.
— Dichroic fog
Dichroic Fog in the Fixing Bath. formed
if it is
old
in the fixing
bath, especially
and exhausted, when
and partially spent developer.
it
if
the fixing bath
is is
most gennot acid,
contains an excess of dissolved silver
In such a case, as the silver halide
slowly dissolved out of the emulsion, metallic silver
When this may be
clips.
the film, dichroic fog
it
by the developer present.
is
is
reduced to finely divided
It is
possible also to get di-
chroic fog with a fresh fixing bath of plain hypo, because the silver salt is
redeveloped back to dichroic silver by the developer carried over by
the film to the fixing bath. of the film
are
is
This
is
abnormally thick, and
especially true if
if
the gelatin coating
the developing and fixing solutions
warm. The developer does not have time to diffuse out of the gelatin hypo begins to dissolve away the silver halide. which is
film before the
reduced in situ to dichroic
silver.
A
slow fixing emulsion
is
apt to give
dichroic fog for the above reasons.
Dichroic fog can also occur
in
a fresh fixing bath
if
two films or
prints stick together face to face, thus forming local pockets containing
developer.
Such a condition
is
namely, an insufficiency of h\-po Stencil effects are
negative or print film in the fixing
ideal for the formation of dichroic fog, in the
presence of an excess of developer.
sometimes produced
in the
when another film with dense bath. The result is that the
chroic fog except in those places where
it
was
in
shadow portions
of a
lettering adheres to the film
is
covered with di-
contact with the lettering.
ON NEGATIVES AND PRINTS
STAINS This
251
because the developer in contact with the clear portions of the
is
negative
lettered
comparatively fresh, but wherever the lettering
is
occurs, the developer
formed
comparatively exhausted, so that no fog
is
in the region of the lettering,
The potassium bromide which
is
thus producing the stencil
formed locally
is
effect.
in excess in the region
of the lettering (as a product of development), also tends to retard the
formation of the fog, thus accentuating the stencil
Prevention of Dichroic Fog.
effect.
â&#x20AC;&#x201D; Dichroic fog can be prevented as
follows:
By
a.
and
keeping the fixing bath acid by renewing at frequent intervals,
possible rinsing the film well before fixing, or using an acid
if
bath
rinse
between
developing
and
fixing.
In
this
quantity of developer transferred to the fixing bath
manner the reduced to a
is
minimum.
By
b.
agitating the film at regular
development and
By
c.
liter
silver halide dissolved is
intervals during both
adding potassium iodide to the developer, about
or 22 grains per 32 ounces.
which
and frequent
fixation.
This has the
by solvents
reduced to silver only with
dichroic fog to be formed d. If there is a
sodium sulphide
is
in
1.5
grams per
effect of converting
the developer to
silver
difficulty, so that the
any
iodide,
tendency for
restrained.
slimy deposit on the walls of the developing tanks,
may
be formed as a result of the action of bacteria or
fungi on the sulphite present in the developer. The sodium sulphide is removed from the developer by contact with a silver halide emulsion,
which
is
converted to silver sulphide so that the fogging effect usually
disappears after developing a certain quantity of film. for a
After standing
few days, the bacteria form a further quantity of sodium sulphide
which again produces
stain.
The immediate remedy is to add lead acetate to the developer in the proportion of i gram per liter (60 grains per gallon) of solution. The acetate should be dissolved in a small quantity of water and added slowly with stirring.
harm
if
Usually a milky precipitate forms but this does no
allowed to settle out.
In order to prevent the growth of bacteria,
the tank should be cleaned out at frequent intervals by scrubbing the walls with hot water
A pound
and chloride
of lime obtainable at
any drug or paint
two of the chloride of lime should be added to a bucket of water, and the walls of the tank scrubbed thoroughly with the
store.
milky solution. water.
or
Then
flush the walls thoroughly several times with plain
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
252
Removal of Dichroic Fog. ticles of silver in
— Since
dichroic fog consists of par-
a finer state of division than the particles composing
the image, they are more readily attacked and therefore dissolved by solvents of silver such as potassium cyanide, acid permanganate, etc.
may be
Advantage
Bathe the
a.
taken of this fact in removing the fog as follows
film in a
%
i
solution of potassium cyanide
As soon
film gently with a tuft of cotton.
image occur, wash well
tion of the
in
as
any
and rub the
visible signs of reduc-
running water (note remarks about
poisonous nature of potassium cyanide on page 271). b. In place of cyanide the less toxic thiocarbamide, or thiourea,
Harden the film first Then bathe the film page 234) be used.
.
in
may
an alkaline solution of formalin (see
in the following solution:
Acid Thiourea Stain Remover
[SS-2]
Metric
Avoirdupois
Thiourea
20 grains 20 grains 4 ounces
Citric Acid Water to make
1 .4
1.4
grams grams
125.0 cc
Treat the film with a weak solution of Farmer's reducer made by little potassium ferricyanide to a 5% solution of hypo, or with
c.
adding a
a weak acid permanganate solution (about 0.5%). d.
The
insidious form of dichroic fog resulting from leaving film over
night in a developer first,
may
harden the negative for
page 234), wash, and
(see
be removed fairly satisfactorily as follows: 5
minutes
treat for 5
neutral potassium permanganate.
h3^o for and dry.
An
e.
5
a
an alkaline formalin solution
Then wash, and
minutes, and finally clear in a
10%
in plain
30%
bisulphite solution,
wash
warm
warm solution.^- This can readily be
solution of acid
removing dichroic if
fog.
seen
hypo when the image A hypo bath is,
preciably in a very few minutes.
hours
fix
ordinary fresh acid fixing bath will slowly dissolve silver
especially in in
in
minutes with a 0.5% solution of
by placing a print
will
be reduced ap-
therefore, useful for
in the hypo bath for 24 removed, though the action
Allow the film to stand
necessary or longer, until the fog
is
can be hastened by gently warming, not above 90°F. (32 °C.).
Blue-Green Stain and Scum.
—A
general bluish-green stain
often caused, especially with certain grades of matte paper,
is
by using an
exhausted chrome alum stop bath or a fixing bath at high temperatures. 12
and
"
The Reducing Action
J. I.
Crabtree.
/.
of Fixing Baths on the Silver Image," by H. D. Russell
Soc. Mot. Pict. Eng. 18, 371-97
(March 1932).
STAINS
ON NEGATIVES AND PRINTS
253
The remedy is to use a fresh bath at normal temperatures, because there It is preferable is no known way of subsequently removing this stain. to use a
alum
potassium alum fixing bath for papers, rather than a chrome tendency of the latter.
fixing bath, because of the slight staining
Fig. 94
When
a
â&#x20AC;&#x201D; Print
chrome alum
from film stained with chrome alum scum.
fixing
bath
is
used in conjunction with a de-
veloper having a high carbonate concentration, the gelatin of a film or plate
is
often stained green, particularly
temperatures.
with
5%
The
potassium
if
the fixing bath
is
used at high
removed by treating the film should be hardened first in the
stain can usually be citrate.
The
film
alkaline formalin solution (page 234) because the citrate softens the gelatin greatly. it is
A
Provided the green stain
is
uniform over the entire
film,
usually not objectionable from a photographic standpoint. bluish-green
scum
is
likewise apt to form on films or plates
using a chrome alum hardening rinse bath or fixing bath consists of
chromium hydroxide and may be a
(
Fig. 94)
.
when This
result of a. insufficient
agitation on placing the film in the rinse bath or fixing bath, b. the use of
an exhausted or insufficiently acid rinse or fixing bath, or c. the use of a much alkali. If such a scum forms on the film
developer containing too this it is
should be removed by swabbing with cotton before drying, otherwise almost impossible to remove it after the film has dried.
Yellow Stains on Glossy Prints. often caused by
â&#x20AC;&#x201D; Deep lemon yellow
insufficient fixation of glossy prints
stains are
which have been
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
254
developed with a developer containing potassium iodide (sometimes
added
The potassium
to prevent abrasion).
iodide converts the surface
layer of the silver bromide emulsion to silver iodide, which
much more
yellow and which fixes
is
deep lemon
slowly than silver bromide and does
not darken on exposure to light.
The
removed completely by bathing
stain can usually be
in a fresh
fixing bath.
Brown tives
Stains.
â&#x20AC;&#x201D; Local brown stains are sometimes formed on nega-
which have been stored
in those parts
The
velope.
which were
stain
is
in
paper envelopes, the stains being present
in contact with the pasted
seam
of the en-
a result of decomposition of acid products which
attack the silver image.
Such stains can often be partially removed by bleaching and redeveloping as described on page 241, but usually the negative cannot be restored completely
The
stains
at the edge
may
by
and not
or shellac adhesive,
placing the seam of the envelope
a.
in the center, b. using
and
that the emulsion side tive in
this treatment.
be prevented by
only a pure starch, dextrine,
by inserting the negative in away from the seam. Dipping
c.
is
a nitrocellulose varnish
will also
the envelope so the entire nega-
minimize the danger of formation
of such stains.
Dye
Stains,
â&#x20AC;&#x201D;-During
recent years, dyes have
come
into
more and
tensive use for sensitizing emulsions, for anti-halation backings, " internal " filters such as in duplicate negative emulsions. stains are encountered as a result of
some
The dyes used
in the film after processing.
exfor
Occasionally
dye remaining locally such purposes are mostly
of the for
water soluble or are discharged from the film in an alkaline solution such as a developer.
If traces of the
A
color sometimes returns.
dye are retained by the
served in a processed panchromatic film or plate
is
the sensitizing dye remaining in the gelatin layer. tionable and harmless,
it
caused by traces of
Although unobjec-
can be removed by bleaching and redeveloping
as outlined on page 241 or
gram (15
film, the
residual pink or blue color sometimes ob-
by treatment with a solution containing i and 12 cc (3 drams) of concentrated
grains) of sodium nitrite
hydrochloric acid per
liter
(32 ounces).
Traces of the pink or blue anti-halation dye sometimes remain in amateur roll films after processing and give rise to a peculiar mottled appearance.
Such stains are entirely harmless photographically as
STAIXS
ON NEGATIVES AND PRINTS
they do not absorb the printing
by bathing
in
255
They may be removed,
light.
if
desired,
an 0.5% sokition of sodium sulphite and then washing
thoroughly. Desensitizing dyes occasionally cause stains on films or plates treated
with a solution of the dye.
For the most part, such stains
nored as they do not absorb light when printing.
According
may
to
be
ig-
Wright
'â&#x20AC;˘'
by safranine dyes may be removed from a fixed and if desired, by treating with an acid solusodium nitrite as given above. Faint green stains produced
stains caused
thoroughly washed negative, tion of
when using Pinakryptol green
are harmless.
Stains due to dyes, indelible pencils, or red and black writing inks
are removed
photographically or by bleaching and redeveloping as In the case of some samples of red ink a slight
described on page 241.
trace of stain remains after the chemical treatment, but this can be re-
moved photographically.
may
Figures
95A and 95B
illustrate
how
ink stains
be removed completely, by chemical treatment.
Figure 95A is a copy on an ordinary film of a photograph stained with " waterproof "' red ink. Figure 95 B is a copy of the same photograph after the red stain was removed by bleaching in the permanganate-chloride bath and redevelop-
No
ing.
sign of the stain
is
visible.
Stains from Vegetable Matter.
â&#x20AC;&#x201D; Yellowish brown
highlights of prints are sometimes caused
stains in the
by the presence
in the
wash
water of dissolved extracts from decayed vegetable matter and the bark of trees.
It is a difficult
matter to remove economically the coloring
matter from such waters, but filtration through activated charcoal
The
usually effective.
print stains
may
is
be removed by bleaching and
redeveloping as described on page 241.
The
use of a bisulphite fixing bath (Formula F-24) in
gives less stain since the
alum present
in the regular acid
many
cases
fixing
bath
tends to mordant the coloring matter onto the print.
Blue Stains.
â&#x20AC;&#x201D; These occur usually on paper
prints after treatment
with solutions containing ferro- or ferricyanides and consist of Prussian blue formed by reaction of the ferro- or ferricyanide with an iron salt
which
may
be present
iron or iron oxide I'i
5,
may
in
some
of the reacting chemicals.
also be present in the
"Treating Stained Negatives" by
1931).
F. V.
Wright.
Particles of
wash water or processing Bril. J. Phot. 78, 334
(June
256
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
trays.
The
removed by treatment and then washing thoroughly.
stains can usually be
tion of potassium oxalate
A.
B.
Copy
Copy
of print
showing
in a
io%
solu-
stain.
of print after treatment of print in bleach
and redeveloper
solutions.
â&#x20AC;&#x201D;
Illustrating the use of permanganate 95 bleach for removal of a dye stain on a print.
Fig.
Stains During After Treatment. ing of negative or positive materials
â&#x20AC;&#x201D; Thorough is
fi.xation
and wash-
absolutely necessary in order
to avoid stains during subsequent reduction, intensification, or toning
processes.
With mercury
cient fixing or
intensification, stains will result
from
insuffi-
washing or too short washing after bleaching and before
STAINS ON NEGATIVES According to Wright
darkening.
^*
such stains
of the following treatments: a. lengthy
bath;
b.
AND PRINTS may
immersion
be removed by one
in a fresh acid fixing
bleaching and redevelopment, according to the method de-
scribed on page 241 but this will not remove silver stains. ,
ing and before clearing, to
desirable to
wash
Brown
in several
stains left
2%
Summary
changes of acidified water (30 cc of 28% ( i ounce of 28% acetic acid per 32 ounces)
by potassium permanganate may be eliminated by
metabisulphite or bisulphite solution.
of All
Types of
Stains.
â&#x20AC;&#x201D; Table 13 on page 258 gives a
of the majority of the classes of stains, their cause,
prevention, and removal as discussed in this chapter.
erence should be 14
'â&#x20AC;˘
Wright
it is
rinse briefly in plain water before clearing with bisulphite.
bathing in a
summary
After bleach-
remove the soluble mercury compounds,
acetic acid per liter of water)
and then
257
Stains on
made
to
of
ref-
to the text as noted.
by F. P. Wright. Brit. J. Phot. 78, 321 (May 29, 1931). removing other miscellaneous stains but the authors confirm these results which probably apply to specific cases.
Prints "
also gives instructions for
have been unable
method
For details
258
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
^p.•s
^ .S
"
-^
*J
o
STAINS
ON NEGATIVES AND PRINTS
-i"
ca
5
o.
B
o c
13
5 ^
O)
-r:
'
6
U H
•£
g Ph
—B O
o
s
m
•£
si pa
^
a's.
U
o
be
S S
ix:
i/2
H
259
PHOTOGRAPHIC CHEMIC\LS AND SOLUTIONS
260
:^ C •^
B'l C >>
5
"
h
i
M p :^
E
.!:;
13
S
^
ii
jj
v:
s
E
< H CO
o
ij
a
o
-^ --. J= "^
^
H
^
5. -Si
H I =
«;
<^
I
"i
S ^
ID
^>
—
""
£ o s
-^
^
i
o
.2
s
"
T3
< ^
<:
^55
ui
^
J - i
>,
- ^ ^ ^ 3
2
_i
^ -jn
tn
i_
-c .S
S
E _3
^
- -r
6 S "-
- t c "
rt
5
c
£-
o
i 2 t)
-3
if
.'
^ -^
c
-So
o <U
5 ?
«
< CO
CO
-o
2
3
=
§
C—
i
5
.=
E O
~u
5 E 5 b
o"
_
>
-^
§ i
^ 5
si
•S
>>
~
I 2
STAINS ON NEGATIVES
rt
M
E
AND PRINTS
261
CHAPTER
XII
CLEANING PHOTOGRAPHIC PROCESSING APPARATUS AND REMOVAL OF STAINS FROM THE HANDS AND CLOTHING Apparatus used for mixing and containing photographic chemicals and solutions becomes discolored and sometimes coated with decomposiIn certain cases this does no harm
tion products of the solutions.
especially
but
if
the container
much
it is
emptied.
is
always used for the same kind of solution
better technique to clean all containers each time they are
Small bottles and old trays are sometimes very
clean satisfactorily and
new ones. The simplest method is
difficult to
and use
better to discard such receptacles
of cleaning a tray or small tank
several times with water
This procedure
is
it
wash
to
is
and then wipe the surfaces with a clean
it
out
cloth.
preferable in the case of trays, at least, to the constant
use of a strong oxidizing solution such as the usual acid bichromate tray cleaner which tends to etch the enamel slightly each time
Such cleaning agents should be resorted
to only
when
is
used.
stains
cling
it
tenaciously to the surface.
Most cleaning
solutions are either strong alkalis or acids
and should be
used with the same discretion given these chemicals when mixing photographic solutions.
The
principle of a cleaning solution
the stain or deposit and changes in the cleaning
agent or
may
it
is
that
it
acts on
over to a soluble form which dissolves
Sometimes the
be washed out with water.
cleaning agent merely softens up the deposit sufficiently so that
it
may
be removed by the use of an abrading substance like sand or glass beads.
CLASSIFICATION OF STAINS Oxidized Developer Stains. brown or yellowish-brown
color.
â&#x20AC;&#x201D; Developer
Fresh stains
stains are usually of a
may
often be removed
washing the vessel with soap and water and wiping with a stains require the use of
cloth.
an oxidizing solution such as acid bichromate of
the following composition:
[TC-1] Water Potassium Bichromate Sulpliuric Acid, C. P. (concentrated).
Add
by
Severe
Avoirdupois
Metric
32 ounces
1.0 liter
^ .
.
ounces
3 ounces
90.0 grams 96.0 cc
the acid slowly with stirring to the bichromate solution.
CLEANING PROCESSING APPARATUS
263
For use: Pour a small volume of the solution into the vessel Rinse around so that it has access to all parts, then pour
to
cleaned.
and wash the container
until all traces of the solution
it
be out
have disappeared.
Warning: This solution should not be used with chromium plated metal trays because it tends to destroy the copper undercoating. Such surfaces and stainless steel are best cleaned
and a
be permitted to stand
in
metal containers for any length of time because
A
of danger of their corrosive action.
known to corrode stainless tanks made of this material.
been or
Other solutions which (followed
by treatment
manganese
stain)
40%
;
by scrubbing with a brush
Strongly oxidizing solutions should never
powder.
fine scouring
will
5%
in
steel
ferricyanide-bromide bleach has
and
it
should not be used in trays
be found useful are bisulphite to
i%
permanganate
remove the residual brown
sodium hydroxide (caustic soda)
;
and any of
the strong mineral acids, sulphuric, hydrochloric, and nitric.
removal of the
stain, the vessel should
After
be washed thoroughly to insure
complete removal of the cleaning agent.
Sulphur and Silver Sulphide Deposits.
â&#x20AC;&#x201D; When
a fixing bath
sulphurizes, the colloidal sulphur formed adheres tenaciously to the
walls of the vessel. silver sulphide is
If the fixing
formed and
the walls of the vessel.
bath has been
this deposits as a
in use for
some time,
brownish-black layer on
Bottles used for storing
hypo alum toning baths
often exhibit this type of deposit.
A
hot concentrated solution of sodium sulphite (about
usually dissolve sulphur.
A warm 10%
(sometimes called Oakite) If the deposit
will also dissolve a
adheres to the surface,
it
20%)
will
solution of tri-sodium phosphate
may
sulphur deposit easily.
be loosened by adding glass
beads or sand to the vessel and shaking vigorously.
A 1%
solution of permanganate
sulphide deposit. to
is
often effective in removing a silver
This treatment should be followed with
5%
bisulphite
remove the manganese dioxide formed. Another useful cleaning agent
(about 2%).
This substance
is
is
a dilute solution of potassium cyanide
a deadly poison
and a solution
emits fumes of poisonous hydrocyanic acid so that in a well ventilated room.
such a solution.
It
it
water
Care should also be taken when discarding
should never be added to a sink where any acid
standing or poisonous hydrogen cyanide gas will be formed.
stream of water should be run into the sink when the solution
down
in
should be used only
the drain.
Silver Deposits.
â&#x20AC;&#x201D; Most
A is
is
strong
poured
so-called fine grain developers are essen-
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
264
tially physical
solution
The
developers and deposit a sludge of silver in the developing
and on the
sides of the developer container.
(Formula In-5) deposits a very heavy layer of Such stains may be removed by a silver solvent
silver intensifier
on the container.
silver
such as
acid-bichromate,
I.
cyanide-hypo), or IVIost
Farmer's reducer (Formula R-4)
2.
(ferri-
iodine-cyanide (see page 246).
3.
metals or alloys tend to accumulate a plating of silver when
immersed
in a
With metal
used fixing bath which contains dissolved silver
and
film hangers
spongy nature and
their
clips,
salts.
such deposits occasionally are of a
rough surface scratches the gelatin emulsion of
films or plates, particularly
if
the solution temperature rises above 70°F.
(2I°C.).
There are four methods of removing such deposits, as follows: Acetic Acid Treatment. Soak the hangers or clips
—
a.
hour
in a tray or
tank
filled
The
luted with 9 parts of water).
wash with
10%
with
acetic acid
(
i
for
an
part glacial acid di-
acid tends to loosen the deposit.
Then
and scrub the deposit with a stiff brush. Most deposits can be loosened and removed by this treatment. b. Acid Bichromate Treatment. If a silver deposit clings tenaclear water
—
ciously to the metal hanger,
it is
necessary to treat
such as acid bichromate, which will dissolve the
on page 262 part of
The
is
TC-i
satisfactory for use provided
it is
with a solution
Formula TC-i
diluted as follows:
i
to 2 parts of water.
length of time the hangers or clips should remain in this solution
depends on the quantity of minutes
is
may
silver to
usually sufficient.
solution, rinse
which
it
silver.
When
be removed.
them thoroughly and brush
adhere to the hanger or
An immersion
of 10
the articles are removed from the
clip.
off
any reddish colored
scale
It is advisable to use a glass or
hard-rubber tray as a container for the cleaning solution rather than an
Note chromium plated
enamelled tray which becomes etched slowly by the solution.
warning
against the use of acid bichromate for cleaning
apparatus, given on page c.
2
63
Tri-Sodium Phosphate Treatment.
cially useful for cleaning silver
— This
method
is
espe-
deposits which have formed as a spongy
layer in gelatin on film hangers or clips.
The equipment should be
allowed to soak for several minutes in a boiling solution of trisodium
phosphate
(about
thoroughly with a d.
10 to stiff
Sandblasting.
15%).
The
surface
should
be scrubbed
brush after the phosphate treatment.
— Heavy
deposits on partially corroded clips or
hangers are best removed by sandblasting.
CLEANING PROCESSING APPARATUS Dye
Stains.
265
â&#x20AC;&#x201D; Enameled trays or tanks which have been used with
strongly alkaline developers or caustic solutions gradually lose their glossy surface and
become roughened, when they
discolor easily.
such containers are used with dye solutions, the dye pores of the enamel, and
it
is
is
If
taken up in the
a very difficult matter to remove
it
com-
^lany dye stains may be oxidized by treatment with a 0.5% solution of potassium permanganate acidified with about 0.5% sulphuric If a manganese dioxide stain remains afterwards, this may be acid. pletely,
removed by treating with a 5% bisulphite solution. Basic dye stains often be removed by adding a little glacial acetic acid to the tray and rinsing it around several times. If the stain is not removed, a more
may
25%)
dilute solution of the acid (about
should be allowed to stand in
the vessel overnight.
Trays stained with acid dyes can often be cleaned up merely by wash-
and scrubbing with a brush. Badly discolored trays which are not cleaned up by treatment with acid permanganate should be discarded as it is not worth the time to ing with water
attempt to clean them.
If
a badly colored tray
intended to be used
is
again for the same dye solution, the stain obviously
is
harmless and the
tray need not be discarded.
Slime, Fungus, Mold, Etc.
â&#x20AC;&#x201D; Large
tanks of wood, Alberene, or
stoneware, after several weeks of use as containers for developers, be-
come coated with a
layer of slime.
The
slime
gelatin, organic matter, fungus growths, molds,
is
composed
and
chiefly of
dust.
Certain fungi or molds have the property of reacting with the sulphite in the developer
and converting
fogging agent. ^
Trouble from
it
to
sodium sulphide which
this source
may
is
a strong
be avoided entirely by
tank at regular intervals, especially during warm weather. Stone tanks can be sterilized by scrubbing the sides and bottom thor-
sterilizing the
oughly with solid calcium hypochlorite or chloride of lime, also called bleaching powder, to which enough water has been added to form a paste.
The tank should then be
rinsed thoroughly (five or six times)
with clear water.
For wooden tanks, the walls should be scrubbed thoroughly with a wire brush, and then the tank filled with sodium hypochlorite solution (i part hypochlorite solution to 6 parts of water)
overnight. 1
" Sulphide
Dundon and
and allowed
to stand
The tank should be emptied the next morning, given anFog Produced by Bacteria
J. I.
Crabtree.
in
Motion Picture Developers
" by
Trans. Soc. Mot. Pict. Eng. No. 19, 28 (1924)-
M.
L.
A
FHOTOGRAPHIC CHEMICALS AXD SOLUTIONS
266
other thorough scrubbing and five or six washings, before being used again.
Method
of Preparing
Sodium Hypochlorite
stock solution of fajpochlorite
is
Solution.
prepared by making up a
4'
V
—
solution
and adding 10^ sodium carbonate solution The solution is then allowed to stand The all the precipitate settles to the bottom of the container. liquid then should be drawn oflf for use as a stock solution.
of calcium hypochlorite until
until
clear
no more precipitate forms.
REMOVAL OF STAINS FROM THE HANDS 1.
Developer and Ink Stains.
hands
— The removal of stains from ^
The
a comparatively simple matter.
is
the
following stain remo\er
works equall}- well with most ink stains as with developer stains. For such stams. immerse the hands in a small volume of the following solution:
i;
Potassium Permanganate Sulphuric
Add
Metric
Avoirdupois ounces 32
Water .\civl.
C. P.
concentrated
1.0 liter
ounce
minims
75
15.0 arams 5.0 cc
the sulphuric acid slowly to the permanganate solution while
Xotc: See suggestions on dissolving
stirring the latter solution rapidly.
permanganate
in
water on page 171.
After bathing in the permanganate bath, rinse in water and apply a
5fc solution of sodium bisulphite or immerse the hands in a fresh acid fixing bath. If the one application is not sufficient, rinse the hands thor-
oughly and repeat the operation.
Warming
the permanganate solution
will assbt in remo\-ing obstinate stains.
This treatment
will
remove the stains caused by any of the ordinary
writing or stamping inks, as well as practically stains. 2.
Silver Stains.
— Treatment of
all
silver stains
forms of develop)er
with the permanga-
nate solution given above wiU remove slight stains but severe stains,
such as are produced by
silver nitrate, should
following methods. a.
Bleach Bath Treatment.
be treated by any of the
— This method
consists in
immersing
or washing the silver stain with an ordinar>- bleach bath used for sepia toning, or with the following solution:
Water Potassiam Ferricyanide Potassium Bromide
.\voirdupois
Metric
32 ounces
1.0 liter ?0.0 arams
1 1
ounce ounce
,?O.0
grams
CLEAXIXG PROCESSING APPAR.ATUS
267
Rinse and then immerse the hands in an acid hyjx) bath; then wash thoroughly.
Iodine-Cyanide Treatment.
b.
ferred, since this
— The
one uses cyanide which
is
method
first
a. is to
a deadly poison.
be pre-
If care is
used to avoid the presence of acid on the hands before the treatment and to
wash thoroughly
The
method.
after«-ards, there
solution to be used
is
is
no great danger from using
Metric
Avoirdupois
Water
Sodium
32 ouncres 145 grains 100 grains
or Potassium Cyanide
Iodine
quickly
down
the drain.
If CN'anide is
1 .0
10.0 6.7
Do
After use. wash the hands very thoroughly. tion in a sink unless a strong stream of water it
this
as follows:
is
liter
grams grams
not discard the solu-
running so as
to
wash
brought in contact with an acid,
the deadly poisonous hydrogen cyanide gas
formed.
is
REMOVAL OF STAINS FROM CLOTHING Developer and Ink Stains. White Fabrics. The acid permanganate
I.
—
a.
solution
recommended
previously for the hands (page 266) will likewise remove stains from
cotton fabrics, although the fabric
A
less
harmful method
is
is
apt to be weakened in the process.
the following: soak the stained portion of the
wash powder
fabric in a 5^c solution of oxalic acid or acetic acid for 2 minutes, for
I
or
2 minutes, then apply a saturated solution of bleaching
(calcium hj-pochlorite
) .
If after 10
minutes the stain does not disap-
wash and reapply the acid solution and. if necessary, the hj^pochlorite solution, and finally wash thoroughly. Both the acid permanganate and the oxalic acid and bleaching powder
pear,
A
treatment should be restricted to cotton fabrics.
ment and one which sists of
is fairly
Care must be used with
of treatment, however, to avoid the possibility of
of the fabric. b.
safe for use with all types of fabrics con-
bathing in hydrogen peroxide solution.
any tvpe
less severe treat-
Colored Fabrics.
break-down
— The permanganate bath given on page 266
should never be used with colored fabrics unless a
trial
on a small area
shows that the solution does not bleach out the color. A should next be made with the oxalic acid and bleaching powder
of the fabric trial
treatment which will usually remove color in the fabric.
If the
all stains
without
afi'ecting the
preliminary test shows any sign of affecting
the color in the fabric, a trial should be
made
of the p)eroxide treatment.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
268
2.
Silver Stains. a.
rics
—
White Fabrics.
Silver stains
by the same methods
A
from the hands.
plain
i%
for
removal of such stains
also satisfactory for use with cotton fabrics but
the addition of iodide
is
silk or wool.
is
be removed from white fab-
solution of potassium cyanide without
should not be used on
cyanide
may
recommended
as
Warning: As mentioned previously,
Adequate
a deadly poison and should be handled with care.
ventilation in the
workroom, freedom from contact with any
when discarding
a strong flow of water
acid,
in a sink are the usual
it
and
precau-
tions to be observed.
A
removal
less severe solution for silver stain
is
the regular ferri-
cyanide-bromide bleach bath followed by hypo, given below under b.
Colored Fabrics.
10 minutes, wash for
io%
or plain
2
— Treat
minutes, and then apply an acid fixing solution
Then wash
hypo.
thoroughly.
Water Potassium Ferricyanide Potassium Bromide If the stain is not
b.
with the following bleach bath for
Avoirdupois
Metric
ounces ounce ounce
1.0 liter
32 1
}4
30.0 7.5
grams grams
removed with one application, the treatment should
be repeated.
Iodine Stains.
— Iodine
moved by applying
stains
on the hands or clothing
may
be
re-
weak solution of hypo (io%) or a few drops of The hypo or fixing bath should, of course, be a fresh fixing bath. removed from the fabric by washing. The dye in some fabrics may be affected by the acid fixing bath. A preliminary test should be made and if any action on the color is observed, the bath should be diluted a
before application.
Dye
Stains.
classified into
— Dyes used
for
photographic work
two groups, acid dyes and basic dyes.
may
be roughly
Other classes of
dyes are used in connection with color processes but these are not em-
ployed very extensively.
Most
acid dyes will dye gelatin or fabrics di-
rectly or in the presence of a trace of acetic acid.
Basic dyes are usu-
employed following treatment with a mordanting solution. The mordant attaches itself to the gelatin or fabric and the dye becomes
ally
attached to the mordant.
When wash the
attempting to remove a dye stain from the hands or clothing, stain thoroughly with water, as
If the stain
is
many
dyes are water soluble.
not removed, wash next with denatured or
wood
alcohol.
CLEANING PROCESSING APPARATUS If it is still
unaffected and
//
the fabric
is
269
white, treat with a
0.5%
solu-
permanganate containing about 0.25% sulphuric acid. Then rinse and moisten with 5% sodium bisulphite to remove any manganese dioxide stain and finally wash thoroughly with water. This tion of potassium
treatment will usually remove most dyes. If the fabric is colored, the acid
permanganate treatment should not
be used or the color will be bleached out of the fabric. stain should be moistened with dilute
the stain
is
Instead, the
ammonia (3%) and washed.
unaffected, the dye probably cannot be
removed without
If
also
destroying the color in the fabric.
Use of an Ink Eradicator.
â&#x20AC;&#x201D; The ordinary ink
eradicator which
usually consists of solutions of oxalic acid and hypochlorite, respectively, is
often effective in removing stains.
preliminary test should
first
As with
all
other treatments, a
be made on a small area of the fabric be-
fore applying the chemicals to the entire stained area. If
a stain
is
ods outlined,
especially difficult to it
is
remove from a fabric by the meth-
better to send the garment to a reliable dyer and
cleaner than to attempt further treatment. ]\Iany valuable hints on stain removal from fabrics will be found in
Farmer's Bulletin No. 14 issued by the U.
S.
Dept. of Agriculture (ob-
tainable from the Superintendent of Documents, Office,
Washington, D.
C,
at 5 cents per copy).
Government Printing
CHAPTER
XIII
GENERAL SUGGESTIONS AND PRECAUTIONS ON HANDLING PHOTOGRAPHIC CHEMICALS Only
a comparatively small
number
of photographic chemicals are
capable of producing harmful effects and no trouble need be anticipated
when handling them provided ordinary
care
is
exercised.
Skin irritation or dermatitis occasionally encountered by photographic
workers
often due to the careless use of a strong alkali or oxidizing
is
agent when attempting the elimination of a stain on the hands or arms rather than the direct action of
According
to
Dr.
S.
some common photographic chemical.
Overton, alkalis hold
of causative agents for dermatitis.^
the
body
is
covered with a
stated to be " far
more
cell
The
known
formation
tolerant to acids
first
place
among
the groups
surface layer or epidermis of
and
which are
as horn-cells
in stronger solutions
than
Alkalis have a macerating action on the keratin of the skin;
to alkalis.
and the horn
is to protect the more delicate become disorganized, separate, and thus allow
the function of which
cells,
structures beneath them,
the irritant to penetrate the
first line
of defense."
In the handling and mixing of photographic chemicals, unpleasant reactions
may become
manifest in one or more of the following ways: A. as
surface or skin effects from continued contact with specific chemicals,
B. as internal effects caused
by inhalation
of vapors or dust,
and absorp-
tion through the pores of the skin, C. a combination of effects
In the
first
place
it
A
and B.
should be clearly understood that the susceptibil-
chemical irritation depends to a large extent on the individual,
ity to
and that practically every chemical substance varying severity on the skin of
effects of
many
will
produce
irritating
persons, providing the
tion.
is handled repeatedly and under conditions favoring its reacWith some chemicals, only the smallest trace is required for cer-
tain
susceptible " individuals to produce a severe reaction as
substance
by ivy poisoning, which is caused by by the ivy in minute quantities.
for example,
given
off
The
following
list
is
shown,
compound
of substances represents a compilation of those
chemicals
commonly used
caution.
It
substance.
a chemical
in
photography which should be handled with
does not imply that everyone
Xo attempt has been made
1 "Discussion on Industrial Dermatoses." (June 1929).
is
likely to be affected
by each and
to give details of diagnosis Proc. Roy. Soc. Med. 22,
1
151-66
-
GENERAL SUGGESTIONS AND PRECAUTIONS
271
treatment for each material as such information can be obtained from a
known
physician and from the
texts
on industrial poisons and toxicol-
ogy, several of which are listed at the end of the chapter.
Gases and Liquids. rapher
is
â&#x20AC;&#x201D; The
most toxic gases
likely to be subjected are
to
which a photog-
hydrogen cyanide, sulphur dioxide,
hydrogen sulphide, ammonia, and fumes from formaldehyde, strong
and organic solvents. The importance oj adequate
acids,
ventilation
and good
circulation of air in
rooms where chemicals arc handled cannot be overestimated. For example, bad cases of headache have been known to occur in rooms where motion picture film was being cleaned with carbon tetrachloride
all
because of insufficient air circulation and change.
In such rooms, fresh
and withdrawn, but precautions near and around the cleaning machine
cool air should not only be admitted
should be taken to see that the air
The
does not remain stagnant during the ventilation process. tice,
obviously,
is
to provide
space or part of a machine where toxic gases are being given
scheme insures quick removal room. to the
known
best prac-
a hood and air exhaust fan adjacent to the
of the gas before
it
off.
This
can dissipate into the
In addition to causing headache, prolonged or frequent exposure
fumes of carbon tetrachloride
in a
poorly ventilated room has been
to bring on severe disorders of the liver and kidneys especially in
the case of an individual
who
has used alcohol freely.
Potassium cyanide is used only to a limited extent by modern photographers for special work such as reduction of negatives, rapid fixation, or for stain
removal (see Chapters
XI and XII).
poisonous when taken internally; 0.2 to 0.3 gram cause death and,
measure
to
when handling
wear rubber gloves
if
this chemical,
it
It is
deadly
(3 to 5 grains) will is
a good preventive
Cyanide
there are cuts on the hands.
should be stored in a locked cabinet when not in use and the user should
always wash his hands thoroughly after using
it.
potassium cyanide or a solution of the salt is brought in contact with any common acid, the very poisonous hydrogen cyanide gas is formed. It is important, therefore, to avoid using cyanide in a
When
solid
sink where any acid tion in the
is
room where
standing, and to see that there it is
to be used.
When
is
ample
the solution
is
ventila-
discarded,
a vigorous stream of water should be used to insure rapid and complete
removal of the solution from the sink. .Solvents " published by Medical Re2 " The Toxicity of Industrial Organic " Carbon search Council, Industrial Health Research Board, London, 1937. See also Tetrachloride as an Industrial Hazard " by P. A. Davis. /. Amer. Med. Asso. 103,
961 (1934)-
PHOTOGRAPHIC CHE^VHCALS AND SOLUTIONS
272
Vapors of sulphur dioxide are sometimes given hardener solution for a fixing bath.
The
off
when mixing a
gas on contact with moist
or the respiratory tract, forms sulphurous acid which
is
an
irritant.
air,
The
concentration rarely becomes great enough to be harmful and the use of a fan to
blow the gas away from the top of the tank toward an air open window will usually avoid any trouble, although
outlet duct or an its
vapors are always unpleasant even in small concentrations.
Hydrogen sulphide tion of
when
sodium sulphide
gas
given
is
when making up
off
for sepia toning.
It
There
inhaled in excess produces nausea.
a stock solu-
has an offensive odor, and is
very
little
danger,
however, of getting an excessive dose when working with sulphide, par-
This gas
will fog sensi-
and a toning bath should therefore not be used where unexposed films are handled.
in the vicinity
ticularly
if it is
used
in a well ventilated
room.
tive films,
Ammonia
is
used only occasionally
in
photography and,
centrations, the vapors are quite harmless but,
centrated solution
{
28%
)
low conthe con-
of the gas, care should be exercised, preferably
working near an open window or tion, the gas
in
when handling
air outlet because, in
high concentra-
produces severe smarting of the eyes, nose, and throat.
Formalin consists of a 37 to 37.5% solution of the gas formaldehyde The odor of formalin is very unpleasant to most persons and,
in water.
in contact with the tissues,
which
is
apt to irritate the
Compressed cylinders
formaldehyde
membrane
changed into formic acid
and
throat.^
of gases, such as oxygen, nitrogen, sulphur di-
oxide, etc., are occasionally used
moved
ders should always be
is
of the nose
by photographic concerns.
Such cylin-
or handled in the cradles provided for
them by the companies manufacturing the gas, because if a cylinder is dropped and a valve broken off there is great danger of an explosion or asphyxiation.
In addition to the above mentioned liquids, the following should be
handled with care:
The vapors nitric,
and
of the
common
concentrated acids, such as hydrochloric,
and very
acetic acids are distinctly unpleasant
corrosive.
]Men handling large carboys of acid should wear high rubber boots, rubber aprons, and gloves as a protection against burns in case of accidental breakage.
Suitable goggles should always be
worn
to protect the
eyes against acid burns.
Large carboys of acid should always be 3
H.
Bull.
Phot. 28, 357
W. Haggard,
page 129.
left in
the
wooden
crates in
(1926); also "Noxious Gases" by Y. Henderson and Chemical Catalog Co., N. Y. 1927.
GENERAL SUGGESTIONS AND PRECAUTIONS
273
which they are shipped and the acid emptied out with the aid of a cartilter. These are supplied to fit around the crate and their use
boy
greatly minimizes the possibility of an accident.
The
glass carboys for
such acids should be examined at regular intervals and rejected
show any
Many and
of these acids exert a very corrosive action
clothing.
spilled
Concentrated
on them.
they
all
on wood, metals,
nitric acid, for instance, will ignite rags if
The vapors
boys are commonly handled able at
if
signs of cracking.
of nitric acid are very harmful.
in a particular
times to flush the acid
down
If car-
room, a hose should be avail-
a drain in the event of breakage.
Also, a shower fitted with a quick opening valve should be available for
an employee acid.
Water
to is
run under the best
in the
first
event of accidental splashing of the
aid treatment for acid or alkali burns,
which should be followed by immediate medical treatment.
When
di-
luting sulphuric acid the acid should always be poured slowly into the
water and never the water into the concentrated acid. Bottles of acid should always be stored near the floor.
high shelves, there always
is
If stored
on
the great danger that the acid will be spilled
on the face or body when attempting to remove the bottle from the shelf. Several organic solvents are used by photographers including methyl alcohol, turpentine, acetone, carbon tetrachloride, benzene, ether, chloro-
form, amyl and ethyl acetate, and a few others.
Most
of these solvents
more or less irritating vapors and the vapors from methyl alcohol and benzene are very objectionable and may have harmful effects when breathed for long periods in low concentration. Liquids such as benzene and ether are quite inflammable, and therefore should never be used near open flames or where smoking is allowed. Some organic solvents are particularly unpleasant to work with in confined spaces, and
give off
even though not violently poisonous tend to produce severe headaches
and sometimes nausea.
Carbon tetrachloride has an
effect that
should be mentioned in addi-
tion to the toxicity of its vapors noted previously.
Liquid tetrachloride
hydrolyzes in contact with moisture and liberates hydrochloric acid
which tends to
to attack tender skin tissue.
Constant exposure of the skin
carbon tetrachloride causes drying and cracking of the tissues
which condition the skin Standard practices
in
is
in
very susceptible to irritation.
the handling of acids and alkalis have been
outlined and discussed by the National Safety Council.* 4
Acids and Caustics.
Safety Council, Chicago,
III.
Safe Practices Pamphlet No. 25, published by National
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
274
— The average photographer does not usually have occasion
Solids.
to handle sufficient bulk of
that
is
and dust from them
dry chemicals to introduce a dust problem
Where
at all serious.
large quantities of chemicals are handled
be drawn into the respiratory passages
likely to
is
of the worker, the simple precaution of wearing a dust respirator should
The dust from
be taken.
come dium
offensive
if
may
be-
sodium bisulphite,
so-
the following powdered chemicals
liberated in large quantities:
bisulphate, sodium carbonate, sodium
and potassium hydroxides.
Strong alkalis such as sodium or potassium hydroxide will produce
burns
any
of
if
allowed to enter cracks or open sores on the body.
alkali should not
Solutions
be allowed to dry on the hands repeatedly or
the surface layer of skin will be attacked (see discussion on page
Flash
2
70)
of Photo-
has largely replaced flash powders for flashlight purposes.
flash bulbs
The former
An
— The extensive use
Lamps and Flash Powders. are
much
and smokeless.
safer to use as they are noiseless
occasional bulb shatters, however, so they should not be placed too
close to the face of the subject, a safe distance being 5 or 6 feet.
Flash powders may be divided into two groups: a. pure magnesium powder which is usually blown through a flame, and b. magnesium mixed with some substance rich in oxygen which can be fired either with a cap, electrically, or with a pyrophoric spark.
The second group should
never be used in a blow lamp because of the danger of explosion.
The mixing
or
compounding
of flash
should never be undertaken by a novice. cussion and should be handled or of
powders
moved with
powders are those which are kept
in
is
a skilled art and
IMany powders
two parts
until
ignite
The
great care.
on per-
best types
ready for
firing.
Flash powders should be stored in a dry place, preferably away from the
workroom.
A
small metal cabinet out of doors or on the roof,
equipped with sprinkler heads, represents the best storage condition.
The door
of the cabinet should be kept closed
by means
of a spring so
that in the event of accidental ignition, the products of combustion can
escape freely.
Only enough
for
immediate use should be stored.
Skin Irritations Caused by Developers. pecially during 19 16-18,
the United States
occasionally
and
many impure
— Several years ago,
es-
developing agents were sold
at that time skin irritations
in
were encountered
by photographers which could be traced directly to the use and substitutes. has investigated a number of the derivatives of the phenyl-
of the so-called metol equivalents
Hanzlik
'"
5 The Pharmacology of Some Phcnylcncdiamincs by Hygiene 4, 386 and 448 (1923).
P.
J.
Hanzlik.
/.
Ind.
GENER.\L SUGGESTIONS
AND PRECAUTIONS
enediamines and reported on their toxicity.
one of the
toxic
series
He
275
considered the most
examined was symmetrical dimethyl paraphenyl-
enediamine. The compound paraphenylenediamine as used in many " fine grain " developer formulas is very toxic to many individuals.
Ermen
In 1923
"
isolated symmetrical dimethyl
paraphenylenediamine
samples of metol and proved that the majority of cases of
in certain
dermatitis were a result of the presence of this substance as an impurity.
Since that date, practically
all
aminophenol have improved
the manufacturers of mono-methyl para-
methods
their
of
manufacture
in order to
eliminate the possibility of the formation of any of this constituent.
Cases of skin irritation by metol, therefore, are comparatively un-
known
at the present time but are occasionally encountered.
â&#x20AC;&#x201D;
Diagnosis and Treatment for Skin Irritation from Metol. Usually the trouble commences with a tingling sensation followed by itching and local reddening of the skin. Swelling and the formation of water
occur next, especially in the region of the nails and be-
blisters
tween the
fingers,
and
in severe cases these blisters
large one, encircling the entire hand. tion, the blisters subside,
the patient
with
is
well,
difficulty,
In
all
cases
and there
-it
is
and
though is
if
in
At
combine
to
form one
with careful atten-
this stage,
two weeks the skin begins to
peel,
danger of bacterial infection.
advisable to consult a physician as the condition of
No
the health has an important bearing on disorders of this nature. specific eliminant
in
and
the blisters burst sores are left which heal
appears to have
" been discovered, the usual " cures
the form of ointments serving merely to allay the inflammation.
After the skin has peeled, the parts affected are usually more sensitive to the poison so that special precautions
must be taken
in the future
when
handling this chemical.
Precautions Against Skin Trouble with Metol and Amidol.
â&#x20AC;&#x201D; The simplest precaution
is
to rinse the
hands
in a dilute
acid solution
after using a developer containing these reducing agents or their equivalents.
The
usual acid short stop containing about i\^/c acetic acid rep-
resents a satisfactory acid bath.
Weak
centrated acid to 80 parts of water)
is
hydrochloric acid (i part conalso satisfactory.
several times with plain water, following which soap
Then
rinse
and water may be
used.
Immediate application or dilute acid f
is
of soap
The Preparation of Metol by W.
(1923).
and water before rinsing
in
hot water
not advisable because this tends to precipitate the F. A.
Ermen.
Phot.
J.
63.
in-
(X. S. 47) 223
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
276
soluble base of the developing agent which
and remains
is
sparingly soluble in water
in the skin pores.
Also, developing solutions should never be allowed to dry on the hands
because crystallization of the chemical constituents of the developer (so-
dium
suphite, carbonate, etc.) causes cracking of the skin, thereby per-
mitting easy access of the developing agent to the under layers, therefore facilitating irritation.
A
bath of weak acetic acid (2 to
3%)
should always be within access
darkroom sink (the usual acid short stop is satisfactory) and, before drying the hands which have been wetted with developer, they of the
should be treated as follows:
and then
and water
bathe in the acid bath for 3 to
a.
5
seconds,
wash with warm water. They may then be washed with soap
b.
if
necessary but never before giving treatment
Stains on the hands
may
or b. or both.
a.
be removed by the use of a weak solution of
potassium permanganate (0.5%) acidified with sulphuric acid (about 0.25%). After treatment with this solution, rinse in water and remove
any manganese
stain with
an immersion
5%
in
Then wash
bisulphite.
thoroughly in plain water, dry carefully, and apply a
little
lanoline
cream.
Amidol
may
stains are
be produced
if
more severe than metol, however, and skin troubles strong alkalis, acids, oxidizing agents,
indiscriminately to remove the stains.
with weak acid permanganate
The preceding remarks on summarized as 1.
Most
is
usually effective.
may
be
follows:
cases of skin trouble from metol occur only as a result of the
Many
made
previous to 1925.
cases of skin irritation are the result of using strong alkalis,
acids, or oxidizing agents to clean developer stains off the
not caused by the developer 3.
are used
skin reactions from developers
use of old samples of this developing agent 2.
etc.,
Treatment as described above
Skin irritation from metol
trouble appear
hands and are
itself.
may
be prevented largely
by taking the precaution
to bathe the
if
signs of the
hands
in dilute
acetic acid or hydrochloric acid after handling the developer solution.
This converts any free base of the developing agent into a water soluble salt.
4.
Then wash in warm water and finally in soap and water. Never use soap on the hands directly after handling a developing
solution, without first rinsing thoroughly with hot water. 5.
If irritation persists in spite of the
developer formula
DK-93
p-aminophenol (Kodelon)
above precautions, a
trial of
(Appendix, page 304) containing a is
recommended.
the
salt of
GENERAL SUGGESTIONS AND PRECAUTIONS General Suggestions on
Ways
of
Avoiding Accidents
277
When
Handling Chemicals Keep the chemical storage and mixing rooms Never lift heavy boxes of chemicals. Use a
clean.
truck, traveling skid, or
hoist.
Never take large acid carboys from their crates. Use a carboy tiller when emptying a carboy. Store acids on low shelves near the floor. If acids or alkalis are spilled on the floor, wash them down the drain rapidly with a strong stream of water.
wash them
or body,
off
with water and
If acids are spilled if
on the hands
signs of a burn appear, go at
once to a doctor for treatment.
Sweep
wash up any
or
may
or the dust
solid chemical accidentally
dumped on
the floor
be carried into the air circulation system and spoil sen-
which it comes into contact. Never work with solvents such as carbon tetrachloride, benzene, turpentine, etc., in a closed room. Work near an open window or arrange sitized films with
to
is
have the vapors carried out by means of an exhaust fan. Inflammable liquids should never be opened in rooms where smoking permitted. If any liquids of this type are spilled on the floor while
they are being transported from one room to another, they should be
wiped up at once.
If ignited, the fire will travel
and may cause a
ter-
rible explosion.
Tanks of liquid should always be covered to prevent any contaminaby foreign matter and, in the case of large tanks, to prevent any-
tion
one falling into the tank. Sensitized photographic materials should preferably be stored in a
room
some distance from the chemical
at
storage, mixing, developing, or
toning rooms to avoid possible contamination by gases or chemical dust
suspended
in the air.
All poisonous chemicals should be kept under lock
and key when not
in use.
IMost
all
cases of poisoning, acid burns, asphyxiations,
and explosions and
result from carelessness or the worker's failure to heed warnings
instructions
regarding the approved ways of handling photographic
chemicals. useful hints regarding approved industrial practice are contained in the booklet " Fire Prevention and Safe Practices " distributed
Many
by Eastman Kodak
Stores, Inc.
following bibliography.
Additional references are given in the
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
278
Bibliography on Industrial Poisoning and Hazards "
Health Hazards of the Chemical Industry
" Special Bull.
No. 96,
Dept. of Labor, Albany, N. Y., Nov. 1919. " Industrial Poisons in the
millan Co.,
New
United States
"
by
Alice Hamilton.
Mac-
York, 1925.
" Noxious Gases and the Principles of Respiration Influencing Their Action " by Y. Henderson and H. W. Haggard. The Chemical Catalog
Co., Inc., "
New
York, 1927.
Memoranda
iston's
"
Son
&
of Toxicology "
by M. Trumper.
2nd Edit.
of Labor Statistics " U. S. Dept. of Labor, Government Printing Office, Washington, 1929.
Handbook
491, U.
S.
P. Blak-
Co., Philadelphia, Pa., 1929.
" Industrial Toxicology "
by Alice Hamilton,
New
Bull.
No.
York, Harper
&
Bros., 1934. " Toxicity of Industrial
Organic Solvents
"
Summaries
of published
work, compiled under the direction of the British Medical Research Council
and Industrial Health Research Board.
Office,
London, 1937.
His Majesty's Stationery
CHAPTER XIV APPENDIX
PART The
A.
FORMULARY
following formulas, although those of one manufacturer, repre-
sent typical formulas as used in each branch of the photographic industry in the United States. The numbers given are those used by the Eastman Kodak Company to designate their formulas in their publications. The formulas are arranged in order of their number and are also indexed according to their use. Developer numbers are prefixed by the letter " D "; fixing baths by the letter " F," etc.
From
this
group of formulas,
will give a satisfactory result
Why many
it
is
possible to select a formula which
with any given photographic material.
the Multiplicity of Developing Formulas?
â&#x20AC;&#x201D; Although
developing formulas will give equally good results with different
sensitive materials, certain emulsions require specific formulas in order
optimum
to insure
results, while
different results are
often required
with the same emulsion and these cannot always be obtained by changing the dilution of a particular formula.
There because
is it
duced with
a tendency for pyro to
fall
into disuse as a developing agent
tends to give pyro-stained images which cannot be repro-
Pyro as a de-
sufficiently precise printing characteristics.
veloping agent
is
rapidly being replaced by Elon and hydroquinone.
Pyro, however,
is
very satisfactory for tray development when condi-
tions are favorable for the production of aerial oxidation fog because
pyro It
is
an anti-aerial fogging agent.
has been considered desirable to include both Elon-hydroquinone
and pyro formulas even though, Selection of a Developer,
in
many
cases, they are supplementary.
â&#x20AC;&#x201D; When choosing a developer, the user
should follow the manufacturer's directions whenever possible. realized,
however, that such instructions do not cover
the user must sometimes be confused by the
should not be
difficult
number
formula
is
cases
It is
and that
of formulas.
It
to choose formulas for specific types of work, but
for general applications, the following suggestions
No
all
known
may
prove helpful.
which can be applied with equally satisfactory
and papers. The standard paper developer formula D-72 probably approaches most nearly such an ideal developer, and has been recommended in a limited number of cases for use with negative materials, where rapid development with a fairly high conresults to films, plates,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
280
trast is desired
On
raphy.
and
such as for some types of copying and for press photog-
the other hand, the contrast negative developers for films
D-19 and D-igb,
plates, formulas
will
papers by diluting the developer 1:1 or 1:2.
with
these formulas
all
when they
work with some grades
of
Best results are secured
are used with the materials for which
See Formula Index, pages 348-357.
they were worked out.
For general tank or tray use, the following formulas
will give satis-
factory results with negative materials:
—
For low contrast and maximum shadow detail. D-76 DK-50, D-7, and D-6ia For average contrast. D-19 and D-ii For high contrast. For very high contrast. D-8 and D-9 minimum graininess. DK-20 For
—
Time
—
— —
of Development.
— The time
gamma
degree of contrast or
of
development determines the
of the negative or positive.
The
actual
density contrast or difference in density between highlight and shadow is
determined both by the brightness contrast of the subject and the
To
degree of development.
obtain a negative having a standard density
contrast, in the case of a subject with a high brightness contrast, a rela-
development
tively short time of
is
necessary, whereas with a flatly
lighted subject, the time of development should be increased.
It is
therefore not possible to give a definite time of development for a given
negative but the range of times indicated represents the average times of
development necessary with average subjects.
Replenishing Solutions for Developers. oper gradually becomes ing agents
less active
due
— During use a
devel-
to the exhaustion of the develop-
and the accumulation of developer reaction products, but the more or less restored by the addition of replenishing so-
activity can be
lutions
which usually contain a high concentration of developing agents
but no bromide.
For tank development, the replenishing formula
is
usually so designed
that the time of development to secure a given degree of contrast
constant when ishing solution.
withdrawn
is
the level of the developer
This
is
is
is
maintained with the replen-
on the assumption that the volume of developer
proportional to the quantity of films developed, and this
condition maintains
if
the films are drained for a constant time.
With a replenished developer, when developing trast, there is some loss of shadow detail but, for loss of detail is negligible.
to a fixed density con-
practical purposes the
FORMULARY
281
DEVELOPERS Three-Solution Pyro Developer Tank
(For General
Stock Solution A
9.8 grams 60.0 ftrams
140
Pyro Potassium Bromide
make Stock Solution B to
Water
Sodium
Metric
Avoirdupois grains
Sodium Bisulphite Water
[D-l]
or Tray Use)
Sulphite, desiccated
2 16
ounces grains
l.I
32
ounces
1.0 liter
32 ounces 3J2 ounces
105.0
ounces ounces
75.0
grams
1.0 liter
grams
C
Stock Solution
Water
32
Sodium Carbonate, desiccated
...
2' 2
.
1.0 liter
grams
Dissolve chemicals in the order given.
For tank, take
part of A,
i
Develop about
water.
For tray, take of water.
12
part of A,
i
Develop about
part of B,
i
C and
part of
i
ii parts
minutes at 65 °F. (i8°C.). part of B,
i
6 minutes at
part of
i
C and
Prepare fresh developer for each batch of
film.
Elon-Pyro Developer Tank
(For General
Stock Solution A Water (about 125° Elon
parts
7
65°F. (i8°C.).
[D-7]
or Tray Use)
Avoirdupois ounces 16
F.) (52° C.)
% M
Sodium Bisulphite Pyro
I
Potassium Bromide Cold water to make
Metric 500.0 cc
ounce ounce ounce
7.5 7.5 30.0 4.2
60 32
grains
32
ounces ounces
150.0
ounces 32 2)^ ounces
75.0
ounces
grams grams grams grams
1.0 liter
Stock Solution B
Water
Sodium
Sulphite, desiccated
Stock Solution
5
1.0 liter
grams
C
Water
Sodium Carbonate, desiccated
....
1.0 liter
grams
Dissolve chemicals in the order given.
For tank, take
i
part of A,
water.
Develop about
be used
2
in the
A
by addition
or 3 weeks
proportion of
i
i
part of B,
part of
i
C and
11 minutes at 65°F. (i8°C.). of fresh developer
part each of A, B, and
C
13 parts of
Developer
may
whenever necessary,
to 4 parts of water.
form of a shallow boat made of Kodaloid or 18-8 or a paraffin paper floated on the solution should be used
floating lid in the
stainless steel
to prevent aerial oxidation.
For water.
tray, take
i
part of A,
i
part of B,
i
part of
Develop about 8 minutes at 65°F. (i8°C.).
C and
8 parts of
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
282
PROCESS FILM AND PLATE DEVELOPERS The
D-g
following Hydroquinone-Caustic Process Developers
will give
very high density and
D-8 and
be found best for line work.
will
Formula D-8 has somewhat better keeping properties in an open tray than D-9 and gives a slightly higher density in a shorter time of development. Both formulas should be used at a temperature of 65°F. (i8°C.), not warmer, and not colder than 55°F. (i3°C.). It is important to wash all negatives very thoroughly before fixing, or stains and dichroic fog will result.
Fix in an acid-hardening fixing bath.
Single Solution Hydroquinone-Caustic Developer
[D-8]
(For High Contrast
on Process Films and
*Water
Sodium Hydroxide
12
(caustic soda) ....
Potassium Bromide Water to make
1
Dissolve chemicals
2
gallon
the order given.
in
parts of stock solution and
2
3.0 liters
360.0 grams 180.0 grams 150.0 grams 120.0 grams 4.0 liters
ounces 6 ounces 5 ounces 4 ounces
Sulphite, desiccated
Hydroquinone
For use, take
Metric
96 ounces
Sodium
about
Plates)
Avoirdupois
Stock Solution
i
part of water.
Develop
minutes at 65 °F. (i8°C.).
This formula
especially
is
recommended
for
making
line
and halftone
screen negatives intended for printing directly on metal.
A
formula which
is
slightly less alkaline
and gives almost as much
density can be obtained by using 3! ounces of sodium hydroxide per gallon of stock solution (112 grams per 4 liters) instead of the quantity
given in the formula.
[D-9]
Two
Solution Hydroquinone-Caustic Process Developer (For Tray Use)
Stock Solution A Water (about 125°
Avoirdupois ounces 16
F.) (52° C.)
% % %
Sodium Bisulphite Hydroquinone Potassium Bromide Water
to
make
32
Metric 500.0 cc 22.5 grams 22.5 grams 22.5 grams
ounce ounce ounce ounces
1.0 liter
Stock Solution B *Cold water 32 ounces Sodium Hydroxide (caustic soda) 1% ounces Dissolve chemicals in the order given. .
*
1.0 liter
52.5
grams
Cold water should always be used when dissolving sodivmi hydro.xide (caustic
soda) because considerable heat boil
.
with violence and
or face.
may
is
evolved.
If hot
cause serious burns
if
water
is
used, the solution will
the alkali spatters on the hands
:
FORMULARY Use equal parts velop about
when mixed and
A
of
A
and B.
Shake bottles well before using.
minutes at 65°F. (i8°C.).
2
therefore
is
283
This developer
will not
not suitable for tank development.
much
developer which gives almost as
be used for tank or tray developing,
is
density, keeps well,
(For
Tank
125° F.) (52° C.)
Sulphite, desiccated
to
make
1.0
ounces
75.0 9.0 25.0 5.0
grains grains grains
130 365 73 32
Sodium Carbonate, desiccated Potassium Bromide
500.0 cc
grains
2} o
Hydroqulnone
Metric
ounces
16 15
Elon
Water
[D-ll]
or Tray Use)
Avoirdupois
Sodium
and can
given below:
Elon-Hydroquinone Developer Water (about
Dekeep
ounces
1 .0
gram grams grams grams grams liter
Dissolve chemicals in the order given.
Use
Develop about
full strength.
minutes
5
in a
tank or 4 minutes
in
a tray at 65°F. (i8°C.).
This formula is useful for general commercial photography and for making halftone screen negatives from which positive transparencies are to be made for dot etching. When great contrast is not desired, dilute the mixed developer with an equal volume of water. Formula D-ii is also recommended for development of lantern slides of line drawings. Use without dilution and develop about 6 minutes in a tank or 5 minutes in a tray at 65°F. (i8°C.).
DEVELOPMENT AT HIGH TEMPERATURES (75° to 90° F.} (24° to 32° C.)
develop films or plates in most developers (except
It is possible to
those which oxidize very rapidly) at temperatures to 75° F.
(24°C.)
by shortening the development time proportionately from that used 65 °F. (i8°C.). solutions
and
if
If
the
it is
at
not possible to control the temperature of the
wash water temperature
is
higher than 75°F. (24°C.)
special developers are required as follows
Tropical Process Developer
[E)-13]
(Para-.\mlnophenol-Hydroqulnone)
Water rabout 125''F.) (52° C.) Para-aminophenol Hydrochloride
Sodium
Sulphite, desiccated
Hydroqulnone
Sodium Carbonate, desiccated
Avoirdupois ounces 24 ..
.
75
grains grains
5.2 52.5 10.5
ounces
52.5
1% ounces 150 IJ^
Metric 750.0 cc
grams grams grams grams grams grams
grains 2.1 30 45.0 1,4 ounces Sulphate, desiccated ounces 1.0 liter 32 Cold water to make Dissolve chemicals in the order given. * If crystalline sodium sulphate is preferred, use i'A ounces per quart (105 grams
Potassium Iodide
Sodium
per liter) of developer.
PHOTOGRAPHIC CHEAHCALS AND SOLUTIONS
284
Use without
Develop 6
dilution.
minutes at 85°F. (29°C.) or
to 7
for proportionately longer times at lower temperatures.
oughly lution
for
30 seconds and immerse
(37% formaldehyde, Then wash
water).
for
diluted
minute,
i
minutes
for 3 i
fix
5%
in
Rinse thorformalin so-
part formaldehyde to 19 parts for 5 to 10
minutes
in
an acid
hardening fixing bath (Formula F-5) and wash for 15 to 20 minutes. It is important to rinse for the time stated after development, otherwise the formalin will soon become discolored with oxidized developer. It is
necessary to remove most of the formalin before fixing, otherwise
the formalin would turn the fixing bath milky and produce dichroic fog.
Kodalk Tropical Developer
[DK-15]
(For General Use with Films
and
Plates)
Avoirdupois
Water (about
125° F.) (52° C.)
Elon
82
Sodium
Cold water to
grains
5.7 90.0 22.5
27 grains 1}^ ounces
45.0
3
make
750.0 cc
ounces ounce
Sulphite, desiccated
Kodalk Potassium Bromide *Sodium Sulphate, desiccated
Metric
ounces
24
%
32
1.9
ounces
grams grams grams grams grams
1.0 liter
Dissolve chemicals in the order given. * If crystalline sodium sulphate is preferred, use 3^ ounces per quart (105 grams per liter) of developer.
Average times of tray development
for roll film, sheet film,
and plates
are as follows:
Time
Temperature 65° 70° 75° 80° 85° 90°
F. F. F. F. F. F.
(18° C.) (21° C.) (24° C.) (26.5° C.) (29.5° C.) (32° C.)
Increase the time given about trast
may
10
8 bVi 5
i% 21^
25%
for
minutes minutes minutes minutes minutes minutes
tank use.
Greater or less con-
be obtained by developing longer or shorter times than those
specified.
A
formula giving
much
may
less contrast
be obtained by
using only 73 grains of Kodalk per 32 ounces of developer (5 grams per liter) instead of the quantities given above. This formula is known as
DK-i5a. Prolonging the development time sive swelling
and softening
at high temperatures, the
is
very undesirable because exces-
of the gelatin will result.
For best results
development time should be as short as pos-
sible.
Formula
DK-15
(18° to 24°C.)
if
will
develop more rapidly when used at 65° to 75 °F.
the sulphate
is
omitted, but
it
should always be used
when working above 75°F. (24°C.). The times should be decreased about 2>:i% when the sulphate is omitted.
FORMULARY An
285
and which gives is Formula
alternative formula which does not contain Elon
results very free
from fog and with a minimum of swelling
D-91, page 304. Warning: It is important to agitate the films or plates when first immersing them in the developer and at intervals during development to avoid streakiness. After development, rinse for i or 2 seconds in water and then immerse for 3 minutes in the tropical hardening bath Formula SB-4, page 308). Omit the water rinse if the film tends to soften but include {
it if
of a
the
possible because
it
helps minimize the tendency for the formation
chromium scum when the alkaline developer on the film reacts with acid chrome alum bath. After hardening, fix for at least 10 minutes
in the
hardening bath (Formula F-5) before transferring to the w^ash
water.
The temperature
of the
wash water should not be over 95 °F.
(35°C.).
Reference should be
made
to
Chapter VIII, page 178,
for a
more com-
plete discussion of handling solutions at high temperatures.
Development of Fine Grain Panchromatic Films at Temperatures Above 75°F. (24°C.) Negatives with low graininess and a maximum of shadow detail on fine grain panchromatic films may be obtained by using D-76 (page 293) which gives lower contrast than either DK-15 or D-91. When working above 75°F. (24°C.) add i^ ounces per quart (45 grams per desiccated sodium sulphate to Formula D-76 and increase the
liter) of
normal development time about 33 7^- An improved ultra-fine grain developer giving a minimum emulsion speed loss and much finer
D-76
grained image than
is
known
as
DK-20.
This formula
is
given
on page 337.
Tank Developer
for
Motion Picture
Positive
Avoirdupois
Water (about
—
125° F.) (52° C.)
Elon
5
Sodium
ounces
39H pounds pounds 6 18?i pounds
Sulphite, desiccated
Hydroquinone .Sodium Carbonate, desiccated
ounces HH ounces
Potassium Bromide Citric Acid
11
IH pounds
Potassium Metabisulphite Water to make
120
gallons
Film
[D-16]
Metric 500.0 cc 0.31 ftram 39.6 grams 6.0 18.7 0.86
grams grams
0.68
gram gram
1.5 1.0
liter
grams
Dissolve chemicals in the order given.
For large
scale mixing, see suggestions on
Average time of development:
s to
page 126, Chapter VII.
lo minutes at 65°F. (i8°C.).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
286
This formula
medium
recommended
also
is
or high contrast
is
for negative
development when
required, for development of variable width
sound negatives, and for both variable density and variable width sound prints.
Replenisher for Formula D-16
[D-16R] Water (about
125° F.) (52° C.)
.
.
Sodium
750.0 cc
ounces 350 grains
4 40
Sulphite, desiccated. ...
Hydroquinone
38
.
Citric Acid
11
0.3 ftram
pounds pounds pounds
9
Sodium Carbonate, desiccated ..
Metric
*Avoirdupois
—
.
Elon
40.0 9.0
38.0
H ounces
0.7
I'a pounds gallons 120
Potassium Metabisulphite Water to make
grams grams grams gram grams
1.5 1.0 liter
Dissolve chemicals in the order given. *
See suggestions on large scale mixing, page 126, Chapter VII.
Add by
tank as needed to
to the
the film.
When added
in this
make up
for the developer carried out
manner, the developer activity
maintained approximately constant with respect to positive
will
be
film.
Contrast Developer
[D-19]
(For Press, Infrared, Metallographic, and Spectrographic Photography)
Stock Solution Water (about 125° Elon
Sodium
Sulphite, desiccated ...
12
.
Hydroquinone
1
Sodium Carbonate, desiccated ... Potassium Bromide
6
2.0 liters 8.8 grams
ounces 360 grains ounce 75 grains ounces 180 grains
300 grains 1 gallon
make
Cold water to
Metric
Avoirdupois 64 ounces 128 grains
F.) (52° C.)
384.0 35.2 192.0 20.0
grams grams grams grams
4.0 liters
Dissolve chemicals in the order given.
Use without
dilution.
Develop
3 to 6 minutes in a tray at
(i8°C.) according to the contrast desired.
65°F.
Increase the time about
25%
for tank development.
I
For infrared landscape photography, dilute as follows: stock solution Develop about 5 minutes in a tray at 65 °F.
part, water 4 parts.
(i8°C.).
This developer
may
where high contrast
[D-19b]
is
also be used for x-ray films
and
in
most cases
desired.
Aero and X-Ray Film Developer (For Tray or
Water (about
125° F.) (52° C.)
Elon
Sodium Sulphite, desiccated Hydroquinone
Sodium Carbonate, desiccated Potassium Bromide Cold water to make
Tank
Use)
Avoirdupois 64 ounces 128 grains 9 ounces 265 grains 1 ounce 75 grains 6 ounces 180 grains 240 grains 1
gallon
Dissolve chemicals in the order given.
Metric 2.0 liters 8.8 grams
288.0 35.2 192.0 16.0
grams grams grams grams
4.0 liters
FORMULARY Develop aero
film about 15 minutes at
287
65°F. (i8^C.)
in a
tank of
fresh developer.
Decrease the development time about (Fahrenheit)
rise in
Develop x-ray This
is
-\
minute
each degree
for
temperature.
film about 5 minutes at 65 °F. (i8°C.) in a tank.
one of the most satisfactory developers available.
Motion Picture Sound Film Negative Developer (For Variable
Avoirdupois
Water (about
750.0 cc
pounds pounds pounds pounds pound
6
Sulphite, desiccated
30
Hydroquinone Kodalk Potassium Bromide Cold water to
Metric
—
125° F.) (52° C.)
Elon
Sodium
[DK-30]
Width Sound Records)
3
40 1
make
6.0 30.0 3.0
40.0
drams grams grams grams
1.0 gram 1.0 liter
120 gallons
Dissolve chemicals in the order given. *
See suggestions on large scale mixing, page 126, Chapter VII.
Use without
Develop about
dilution.
minutes at 65 °F. (i8°C.)
5
in
a tank of fresh developer.
By
increasing or decreasing the
Kodalk
in the formula,
possible
it is
to a. increase or decrease the contrast obtained in a given time of devel-
opment, or
b.
decrease or increase the time of development required to
obtain a given degree of contrast.
Lantern Slide Developer (For
Stock Solution A Water (about 125°
Sodium
Warm
Avoirdupois F.) (52° C.)
16
Hydroquinone Potassium Bromide Citric Acid
make
Stock Solution B Cold water Sodium Carbonate, desiccated Sodium Hydroxide (caustic soda) Dissolve chemicals
For I
use, take equal parts of
part of
about
5
A and
2
parts of B.
ounces
90 grains 100 grains 50 grains 10 grains 32 ounces
Sulphite, desiccated
Cold water to
32 ounces 1
...
in
A and Stir
minutes at 70'F. (2i''C.).
[D-32]
Black Tones)
ounce
60 grains
Metric 500.0 cc 6.3 7.0 3.5 0.7
grams grams grams gram
1.0 liter
1.0 liter
30.0 4.2
grams grams
the order given.
B.
For
still
warmer
tones, take
thoroughly before use.
Develop
PHOTOGRAPHIC CHEMICALS AXD SOLUTIONS
288
*
Lantern Slide Developer
[D-34]
(For Cold Black Tones)
Stock Solution A Water (about 125° Elon
Sodium
16
ounces
60
grains
H
Sulphite, desiccated
Hydroquinone Cold water to
Metric
Avoirdupois F.) (52° C.)
Ji
make
32
500.0 cc 4.2 15.0 15.0
ounce ounce ounces
grams grams grams
1.0 liter
Stock Solution B \\
ater
32
Sodium Carbonate, desiccated
....
}-i
Potassium Bromide
ounces ounce
1.0 liter
15.0
grains
30
2.1
grams grams
Dissolve chemicals in the order given. *
Formula D--2
For
also
recommended
A
use, take equal parts of
This formula
7o°F. (2i°C.). contrast,
A
is
Formula D-ii
is
for lantern slides, see page 292.
Develop i^
and B.
may
to 3
minutes at
be used for line work; for
maximum
recommended. (Formula R-4, page
brief treatment with dilute Farmer's reducer
319) after fixing and washing will give added brilliance to the For softer tones, take equal parts of A, B, and water.
slide.
Elon-Hydrcquinone-Kodalk Developer
[DK-40]
Motion Picture
(For
Positive Film)
Metric
*Avoirdupois
Water (about
—
125° F.) (52° C.)
Elon
1
Sodium
Sulphite, desiccated
30 4 20
Hydroquinone Kodalk Potassium Bromide Cold water to
750.0 cc
pound pounds pounds pounds
grams
4.0 grams 20.0 grams 0.5 gram 1.0 liter
8 ounces 120 gallons
make
gram
1.0
30.0
Dissolve chemicals in the order given. *
See suggestions on large scale mixing, page 126, Chapter VII.
Use without
Develop
dilution.
5 to 7
minutes at 65 'F. (i8°C.)
a tank of fresh developer according to the contrast desired.
mula
By a. to
is
This
in
for-
also satisfactory for use with Duplicating Positive film.
increasing or decreasing the
Kodalk
in the
formula,
it is
possible
increase or decrease the contrast obtained in a given time of de-
velopment, or
b. to
decrease or increase the time of development with-
out affecting the contrast.
[DK-50]
Elon-Hydroquinone- Kodalk Developer (For
Roll Films, Film Packs Professional Films and Plates)
Normal Contrast on
Stock Solution Water (about 125° Elon
Sodium
Avoirdupois F.) (52°C.) ...
Sulphite, desiccated
Hydroquinone Kodalk Potassium Bromide Cold water to
make
...
64 ounces 145 grains 4 ounces 145 grains 1 ounce 145 grains 29 grains 1
gallon
Dissolve chemicals in the order given.
and Metric 2.0 liters 10.0 grams
120.0 10.0 40.0
grams grams grams grams
2.0 4.0 liters
.
FORMULARY For tank use I
65"F. (i8°C.)
with professional films and plates, take
for portraiture
part stock solution and
289
i
part water and develop 8 to 12 minutes at
in the fresh
developer according to the contrast desired.
For commercial photography use without dilution and develop in a tank 6 to 10 minutes at 65T. ( i8°C.) according to the contrast desired. For tray, use without dilution
and develop 4
minutes at 65
to 6
These development times are satisfactory
for
"^F.
(18 '€.).
copy negatives and trans-
parencies.
Develop 65°F.
roll films
(i8°C.)
and panchromatic
packs about 10 minutes at This developer
machine development
satisfactory for deep tank or
Develop orthochromatic
plants.
film
the undiluted fresh developer.
in
packs about lo^c
film
is
in photofinishing
longer than
roll films.
Greater or
less contrast
may
be obtained by developing longer or
shorter times than those indicated.
By it is
increasing or decreasing the quantity of
Kodalk
in the formula,
possible a. to increase or decrease the contrast obtained in a given
time of development, or
ment without
b. to
decrease or increase the time of develop-
affecting the contrast.
[DK-50R]
Replenisher Solution (For Use with Formulas
DK-50 and DK-60) Avoirdupois
Water
(125° F.; (52° C.)
Sodium
Sulphite, desiccated
.
Hydroquinone Kodalk Cold water to
grains
ounces ounce 145 grains ounces
1
5K
make
Metric
ounces
96 290 4
Elon
gallon
1
3.0 20.0 120.0 40.0 160.0 4.0
liters
ftrams ftrams
grams grams liters
Dissolve chemicals in the order given.
For sheet films and plates, dilute with an equal part of water and add to the
For
tank as needed to maintain the level of the solution. roll films
and
film packs, use without dilution
and add
to the
tank
as needed to maintain the level of the solution.
When discard to
used with Formula
some
DK-60, page
of the used developer
290,
when adding
it
may
be necessary to
the replenisher in order
maintain an approximately constant developing time.*
Amidol Developer Stock Solution Water fabout 125°
Sodium
for
Bromide Papers Avoirdupois
F.) (52° C.)
Sulphite, desiccated
24 4
ounces ounces
750.0 cc 120.0 grams
Di-aminophenol Ilydrochlorlde (Amidol)
Cold water to
IJi
make
32
ounces ounces
[D-51]
Metric
37.5
grams
1.0 liter
Di.ssolve chemicals in the order given.
See comment on the use of the Special Kodalk Replenisher for use with DK-60, as given on page 290. *
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
290
For use take 6 ounces (i8o cc) stock solution, | dram (3 cc)
10%
potassium bromide solution, and 24 ounces (750 cc) of water. Develop i^ to 3 minutes at 7o°F. (2i°C.). Use at once after dilution with water as the solution oxidizes rapidly on exposure to air.
Portrait Paper Developer
[D-52]
Stock Solution Water (about 125° Elon
Sodium
Avoirdupois F.) (52° C.)
22
Sulphite, desiccated
1.5
ounce ounce
22
grains
1.5
32
ounces
1
Yi
make
grains
grains
90
Sodium Carbonate, desiccated Potassium Bromide
Metric 500.0 cc 22.5 6.3 15.0
J^
Hydroquinone Cold water to
ounces
16
grams grams grams grams grams
.0 liter
Dissolve chemicals in the order given.
For professional contact papers, use stock solution I
i
part, water,
part.
For professional enlarging papers and bromide papers, use
full
strength
solution.
Develop Note
may
:
papers not
all
than \\ minutes at 7o°F. (2i°C.).
less
This developer contains the
be added
warmer tones are
if
minimum
More bromide
quantity of bromide.
desired.
Rapid Machine Developer
[DK-60] (For Rapid
Machine Development
of Roll Films
and Film Packs)
Avoirdupois
Water (about
125° F.) (52°
C).
Elon
Sodium
Sulphite, desiccated
.
.
5
290
make
10
2.5
30.0
3M ounces 1
pound
Metric 500.0 cc
3J^ ounces 2J^ pounds
Hydroquinone Kodalk Potassium Bromide Cold water to
gallons
IOI/2
ounces
grains gallons
grams grams
2.5 grams 20.0 grams 0.5 gram 1.0 liter
Dissolve chemicals in the order given.
Develop
roll films
65°F. (i8°C.)
and panchromatic
in the fresh developer.
film
packs about
7
minutes at
Develop orthochromatic
film
20% longer than roll film. Formula DK-50R, page 289, is recommended as a replenisher for DK-60 developer. Eastman Special Kodalk Replenisher * may also packs for
be used and
will
maintain the developing time approximately constant
provided about 6 gallons of developer are removed per 1000
rolls of
film developed.
Greater or less contrast
may
shorter time than indicated. *
Supplied
in
packages.
be obtained by developing a longer or
FORMULARY By it
increasing or decreasing the quantity of
possible
is
291
time of development, or
ment without
The
Kodalk
in the
formula,
increase or decrease the contrast obtained in a given
a. to
b. to
decrease or increase the time of develop-
affecting the contrast.
following table gives the times of tank development for amateur
roll films at
65°F. (i8-C.)
same quantity Formulas DK-50 and ing the
for equal contrast
with a developer contain-
of developing agents, sulphite,
DK-60
Time
Kodalk Concentration Per GaUon grains
290 1
2
(DK-60)
2
4
(Saturation Limit)
.
5M
.
Tank Develop-
of
ment*
in the Developer
(DK-50)
and bromide as
with varying quantities of Kodalk.
65°F.(18°C.)
Per Liter
ounce 145 grains ounces ounces 290 grains ounces ounces
5.0 10.0 15.0 20.0 30.0 40.0
grams grams grams grams grams grams
15 10
%% 7 b]4,
5
minutes minutes minutes minutes minutes minutes
These times give approximately equal contrast.
*
These concentrations of Kodalk cover the range of development time In the most concentrated formula
considered to be of practical interest.
(5^ ounces of Kodalk per gallon) (40 grams per
liter)
the concentra-
same as that used for the replenisher solution, DK-50R. With the more concentrated solutions, it will be necessary usually to discard some of the used developer in the tank when adding the replention
is
isher
the
(DK-50R)
in order to
maintain an approximately constant de-
veloping time.
When
temperature control
must be varied
to
is
not possible, the time of development
maintain equal contrasts in accordance with the
fol-
lowing table:
Time-Temperature Table
for Fresh Developers
for Roll Films To Maintain Equal Contrasts 55°F. (12°C.) 60° F. (15° C.) 65° F. (18° C.) Standard. 70° F. (21° C.) 75° F. (24° C.)
Note:
DK-60
DK-50
Temperature
.
.
14 12 10 8 7
minutes minutes minutes minutes minutes
If a different standard time
10 9 7 6 5 is
used
minutes minutes minutes minutes minutes tlian
20%
for tray development.
26 20 15 12
D-76 D minutes minutes minutes minutes minutes
76 (Kodalk)* 29 24 20 16 13
minutes minutes minutes minutes minutes
given in the above table, the times
at the other temperatures should be varied proportionately.
about
33
Decrease the times given
Increase the times given about
20%
for ortho-
chromatic film packs. * A developer having the same time of development at 6s°F. (i8°C.) may be obtained by substituting an equal quantity of Kodalk for the borax in D-76. The temperature coefficient of the resulting developer differs slightly from that of regular
D-76
as
shown by the
table under
D-76 (Kodalk).
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
292
Elon-Hydroquinone Developer
[D-61a]
Tank
or Tray Use with Professional Films
Stock Solution
Avoirdupois
(For
Water
and
Metric
64 ounces 45 grains
Elon
Sodium Sulphite, desiccated Sodium Bisulphite Hydroquinone
Sodium Carbonate,
desiccated
Potassium Bromide Cold water to make
3
30 85 165 24 32
Plates)
500.0 cc 3.1
ounces
90.0
grains grains grains grains
2.1
5.9 11.5
grams grams grams grams grams grams
1.7 1.0 liter
ounces
Dissolve chemicals in the order given.
For tank, take
i
part stock solution and 3 parts water. Develop about Add stock solution (diluted 1:3) at in-
14 minutes at 65° F. (i8°C.).
below to main-
tervals to maintain the volume, or the replenisher given tain the strength of the solution.
For tray take 7
i
part stock solution and
i
Develop about
part water.
minutes at 65°F. (i8°C.).
Replenisher for Tank Dilution D-61a
[D-61R]
Stock Solution A Water (about 125° Elon
F.) (52° C.)
Sodium Sulphite, desiccated Sodium Bisulphite Hydroquinone Potassium Bromide Cold water to
make B
to
make
3.0 liters 5.9 grams
grains
6 55 170 45 1}4
ounces
180.0
grains grains grains gallons
3.8 11.9
8
ounces ounces
240.0
Stock Solution Sodium Carbonate, desiccated ....
Water
Metric
Avoirdupois ounces
96 85
64
grams grams grams grams
3.1 6.0 liters
grams
2.0 liters
Dissolve chemicals in the order given.
For use take as needed.
Do
A and A and B
3 parts of
not mix
i
part of
B and add
to the tank developer
until ready to use.
Universal Paper Developer
[D-72] (For
Amateur Contact Prints and Enlargements)
Stock Solution Water (about 125° F.) Elon
Sodium
Avoirdupois (52° C.)
Sulphite, desiccated
Hydroquinone Sodium Carbonate, desiccated Potassium Bromide Water to make
16
ounces
45
grains
1}4 ounces grains 175 2}4 ounces 27 grains
32
ounces
Metric 500.0 cc 3.1
45.0 12.0 67.5
grams grams grams grams grams
1.9 1.0 liter
Dissolve chemicals in the order given.
For chloride papers take stock solution
i
part, water 2 parts.
Develop
i
part, water 4 parts.
Develop
45 seconds at 7o°F. (2i°C.).
For bromide papers take stock solution
not less than i^ minutes at 70°F. (2i°C.).
.
.
FORMULARY For lantern I
slides take stock solution
minutes at 7o°F. (2i°C.).
to 2
For
for less contrast, 1:4.
i
293
part, water 2 parts.
Develop
For greater contrast dilute 1:1 and
line drawings.
Formula D-i
i
is
recommended
(page 283).
This formula velop about
For
is
less
recommended
also
For average
tives.
development of press nega-
for the
use, take stock solution
minutes
part, water
i
i
part.
De-
tank or 4 minutes in a tray at 65°F. (i8°C.). 5 contrast, dilute 1:2. For greater contrast, use full strength.
Greater or
in a
less contrast
may
also be obtained
by developing longer or
shorter times than those indicated.
Paper Developer for Blue-Black Tones
[D-73]
(For use with Chloride Papers)
Stock Solution Water about Elon
Sodium
Metric
Avoirdupois (125° F.) {52°C.)..
16
40
Sulphite, desiccated
.
Hydroquinone
ounces
500.0 cc
grains
1
ounce
155
grains
140 grains
2^ ounces
Sodium Carbonate, desiccated Potassium Bromide Water to make
12
grains
32
ounces
2.8 40.0 10.8 75.0 0.8
grams grams grams grams
gram
1.0 liter
Dissolve chemicals in the order given.
For use take stock solution
Develop
for
i
part, water 2 parts.
45 seconds at 7o°F. (2i°C.).
Elon-Hydroquinone-Borax Developer (For
[D-76]
Amateur, Professional, Aero and Motion Picture Negatives on Panchromatic Materials and for Variable Density Sound Records)
Water (about
125° F.) (52°
C
)..
Elon
— 2
Sodium Sulphite, Hydroquinone
desiccated.
5
Borax, granular
Water to make For small
100 2
Metric
Avoirdupois
pounds pounds pounds pounds
96 116 1314 290 116
120 gallons
1
ounces
750.0 cc
grains
ounces
2.0
100.0
grains grains gallon
grams grams
5.0 grams 2.0 grams 1.0 liter
scale use, dissolve the chemicals in the order given.
Develop amateur
roll films
and aero
films about 20 minutes in a tank
or 16 minutes in a tray of fresh developer at 65°F. (i8°C.).
Develop professional 65°F.
(
the time about fine grain
A
films
and plates 10
to 25
minutes
in a
tank at
For tray use, decrease This developer gives greatest shadow detail on
i8°C.) according to the contrast desired.
20%.
panchromatic
films.
working developer can be obtained by increasing the quantity of borax as shown in the following table. A still more active developer can be obtained by replacing the borax by Kodalk. When the faster
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
294
D-76
regular quantity of borax in
Kodalk [D-76 (Kodalk)J, the
replaced by an equal quantity of
is
resulting formula has similar properties
but the activity increases proportionately more as the quantity of Kodalk is
as
increased compared with an equal increase in the borax concentration
shown below. of Tank Development of Films or Plates for Equal Contrast with Varying Quantities of Granular Borax in D-76 and Kodalk in D-76 (Without Borax) [D-76]
Times
Borax Concentration Per Gallon Avoirdupois 116 grains
(Regular)
(5X)
1
2 2
X)
(10
Development
Per Liter Metric
ounce 145 grains. ounces ounces 290 grains
.
.
.
.
2.0 10.0 15.0 20.0
Time
grams grams grams grams
20 15 12}^ 10
minutes minutes minutes minutes
[D-76 (Kodalk)] (Borax replaced by Kodalk)
Kodalk Concentration Per Gallon Avoirdupois 116 grains 290 grains 1 ounce 145 grains 2 ounces 290 grains
(Regular)
X)
(21^
(5X) (lOX)
10.0 20.0
.
The formula containing tration represents the
The
Per Liter Metric ^Ticm^ 2.0 5.0
lo times
maximum
grams grams grams grams
(loX)
Development
Time 20 10
7H 5
the original alkali concen-
practical concentration for use.
contrast obtained at 65°F. in 20 minutes (tank) in
(Kodalk)
DK-50
will
minutes minutes minutes minutes
D-76
or
D-76
be slightly lower than that obtained in 10 minutes in
or 7 minutes in
DK-60, but
development of miniature negatives
this is considered desirable for the
for
which D-76 and D-76 (Kodalk)
are especially suitable.
When
temperature control
must be varied
is
not possible, the time of development
to maintain equal contrasts in accordance with the table
on page 291. Directions for Large Scale Mixing: First dissolve the Elon in a small
volume
of water (about i25°F.)
Then
tank.
(52°C.) and add the solution to the
dissolve approximately one-quarter of the sulphite sepa-
rately in hot water (about i6o°F.)
(7i°C.) and add the hydroquinone
with stirring until completely dissolved.
Now
Add
this solution to the tank.
dissolve the remainder of the sulphite in hot water, add the borax,
and when dissolved, pour the entire solution into the tank and dilute to the required volume with cold water. Average development time for panchromatic motion picture negative film
is
8 to 12 minutes at 65°F. (i8°C.) in the fresh developer according
to the contrast desired.
FORMULARY
295
The developer tank
usually becomes coated with
The developer
a thin white deposit of silver but this will do no harm.
may become
muddy due
slightly
loidal silver but
it is
to the
formation of a suspension of col-
harmless and can be ignored.
For duplicate negative
average time of development
film,
is
6 to 9
minutes at 65°F. (iS'^C).
Normal
D-76
contrast of negatives developed in
is
low
(gamma
=
0.5 to i.o).
Replenisher Solution (For
Tank Use with Formula
[D-76R]
D-76)
Avoirdupois
Water (about
125° F.) (52°
C).
.
Elon
Sodium
Sulphite, desiccated
Metric
96 ounces 175 grains 13J4 ounces
.
....
3.0 liters 12.0 grams
400.0
Hydroquinone
1
*Borax, granular
2
ounce ounces 290 grains
1
gallon
Water
to
make
.^0.0
80.0
grams grams grams
4.0 liters
Dissolve chemicals in the order given.
Discard some developer before adding replenisher.
*
Use the replenisher without the level of the solution.
times as great
is
required,
mula D-76R
is
of
substituted for borax in Formula
it is
to
maintain
at least five
D-76 and a
replen-
necessary to substitute Kodalk for borax in For-
as follows:
D-76 (Kodalk) ^
'
Borax Replaced by Kodalk) Per Liter Per Gallon 2.0 grams 116 grains 5.0 grams 290 grains 10.0 grams 1 ounce 145 grains 20.0 grams 2 ounces 290 grains *
and add to the tank Formula D-76 will be
dilution life
this replenisher is used.
if
When Kodalk isher
The
^^ ^ ^ ^^J"® Development
D-76R (Kodalk)
(Tank)
(Borax Replaced by Kodalk) Per Liter Per Gallon
20 10 7}/^
5
minutes minutes minutes minutes
^
7.5
20.0 40.0 *40.0
grams grams grams grams
1
2
5 5
'
ounce ounces 290 grains ounces 145 grains ounces 145 grains
Discard some developer before adding replenisher.
FINE GRAIN DEVELOPMENT The
introduction of small cameras taking small negatives has stimu-
lated interest in developers
The
which give images with a minimum graininess.
relative value of developers with regard to their ability to give
fine grain
images can only be measured provided a comparison
is
made
of images which have a. equal densities, and h. which received equal de-
grees of development.*
Most * "
fine grain
developers produce
The Maintenance
warm
of Negative Quality " by J.
800-804, 874-880, (1937).
toned images the effective I.
Crabtree.
Amer. Phot.
31,
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
296
photographic printing density of which so that,
if
compared with black
is
greater than the visual density
or neutral images obtained in regular
developers, fine grained negatives should be slightly underdeveloped in
order to obtain matched prints.
When comparing
developers for
graininess, therefore, the negatives should be developed for times such
that
matched prints are obtained when the prints (on a given paper)
are developed for equal times.
Diminished graininess tive slightly
is
usually obtained by underdeveloping a nega-
because the graininess of a negative having a given density
increases as the development factor or
gamma
increases.
Development
should not be too short, however, because any scratches or abrasions on the negative will then
At the present
show up
to a greater extent in the finished print.
state of our knowledge,
any
duces graininess at the expense of some loss
in
fine grain
developer re-
emulsion speed.
Even
with the most satisfactory fine grain developers, this speed loss varies
from 25
to
50%
but
it
should be remembered that a
25%
speed
loss
is
only just perceptible in the negative.
In most cases,
if
the alkalinity of a given line grain developer
creased so as to speed up development, graininess
no ultra rapid
fine grain
is
is in-
increased so that
developers are available at present.
Of the common developing
agents,
paraphenylenediamine and
its
analogues have the property of giving fine grained images but with
some speed
loss.
phenylenediamine
A
formula containing 10 grams (145 grains) of paratogether with 100 grams (3 ounces, 145
(base)
grains) of sodium sulphite (desiccated) per liter (32 ounces)
factory as any of the properties as
(page 337).
many
is
as satis-
published formulas and has the following
compared with D-76 and the
fine grain
developer
DK-20
.
FORMULARY
297
There is very little difference in the graininess produced by developers other than the recognized " fine grain '" developers when images are compared at
equal densities,
a.
sion speeds.
It is
b.
equal gammas, and
c.
equal effective emul-
generally possible to diminish the graininess attained
with any developer by adding a speed reducing addition agent such as
potassium bromide or other anti-fogging compound, but the graininess reduction
DK-20
usually not so great as that obtained with
is
DK-20. Formula
a fme grain developer having good keeping properties,
is
reasonable short development time.
minimum
The emulsion speed
and a
loss is also a
(see page 337).
Low and Normal Contrast (For Photomicrojiraphy, Metallography,
Developer
Avoirdupois
Water (about
125° F.) (52° C.)
Sodium
Sulphite, desiccated
Potassium
Iodide,
grains
13'4'
Hydroquinone
1%
tPotassium Bromide, Cold water to make
solution solution
2. 5^7
ounces
10
dram drams
1
gallon
1
3.0 liters 8.0 ftrams
400.0
grams
20.0 grams 8.0 grams 4.0 cc 40.0 cc 4.0 liters
grains grains
290 116
Borax, granular
Metric
ounces
96 116
Elon
[D-76c]
and Spectroscopy)
Dissolve chemicals in the order given. *
A 1%
grams)
solution of potassium iodide is prepared by dissolving 44 grains (3 few ounces (cc) of water and adding water to make 10 ounces (300 cc.)
in a
of solution. t
A 2j^%
grams)
in a
solution of potassium bromide is prepared by dissolving ^ ounce (7.5 few ounces (cc) of water and adding water to make 10 ounces (300 cc)
of solution.
Use without dilution. Develop in a tray about 5 minutes for low conand 6^ minutes for normal contrast at 65°F. (i8°C.). For tank development, increase the times given by about 25%. For high and extreme contrast photomicrography, use Formula D-19 trast
given on page 286.
Buffered Borax Negative Developer (For Motion Picture Negatives
Avoirdupois
Water (about
125° F.) (52° C.)
—
Sulphite, desiccated
2
2.0
100
100.0
Hydroquinone Borax, granular Boric Acid
Water *
to
make
Crystalline boric acid
slowly, and
its
5.0 8.0 8.0
120 gallons
should
be used.
Metric 7.50.0
pounds pounds 5 pounds 8 pounds 8 pounds
Elon
Sodium
[D-76d]
and Variable Density Sound Records)
Powdered
cc
grams grams grams grams grams
1.0 liter
boric
acid
dissolves
very
use should be avoided.
Directions for Use: see mixing directions given for Formula D-76, page 294. Use without dilution. Develop 10 to 25 minutes at 65 °F.
(i8°C.) according to the contrast desired.
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
298
This developer trast.
particularly useful for obtaining images of low con-
is
contrast can be obtained
With non-buffered developers low
dilution but the exhaustion life of the buffered developer above
is
by
greater
D-76 diluted to give the same contrast in the same time. With a ratio of 8 grams borax to 8 grams boric acid, the rate of development is unchanged from that of D-76. By increasing the quanthan that of
tity of
borax with a corresponding decrease
development rate
increased.
is
By
in the boric acid content, the
decreasing the borax and increasing
the boric acid proportionately, the development rate
is
decreased.
mixed sample of the Buffered Borax
Note: The (Formula D-76d) may be controlled by adding 15 grains bromide per gallon (0.25 gram per liter) of the mixed developer. slight initial fog of a freshly
veloper
of
de-
potassium
Glycin Negative Developer
[D-78]
Metric
*Avoirdupois
Water
Sodium
Sulphite, desiccated
Glycin (Athenon) Sodium Carbonate, desiccated
Water
make
to
80 gallons
750.0 cc
3 pounds 3 pounds 6 pounds 120 gallons
3.0 3.0 6.0
grams grams grams
1.0 liter
Dissolve chemicals in the order given.
Average time of development: 15
minutes at65°F. (i8°C.).
to 25
Pyro Tank Developer
[D-79]
(For Negative
Motion Picture Film) Metric
Avoirdupois
—
Water
Sodium
25
Sulphite, desiccated
Sodium Carbonate, desiccated Potassium Bromide to
2.5 grams 5.0 grams 0.5 gram 1.0 liter
2H pounds
Pyro
Water
pounds
750.0 cc 25.0 grams
make
5
pounds
8 120
ounces gallons
Dissolve chemicals in the order given.
Average time of development: 9 to 12 minutes at 65°F. (i8°C.). This solution oxidizes rapidly and should therefore be used within one hour after mixing.
[D-8O]
Motion Picture Negative Film Developer (For Use with Reel Developing Outfits)
Avoirdupois 125° F.) (52° C.)
—
Sulphite, desiccated
100
Water (about
5
pounds pounds pounds pounds pounds
120
gallons
Elon
Sodium
2}'2
Hydroquinone
10
tPotassium Carbonate, desiccated .. Potassium Bromide Water to make
50
Metric 750.0 cc 2.5
100.0 10.0 50.0
grams grams grams grams grams
5.0 1.0 liter
Dissolve chemicals in the order given.
Average time of development: 6 * t
to 20
minutes at 65°F. (i8°C.).
See suggestions on large scale mixing, page 126, Chapter VII. See next formula.
FORMULARY
299
Motion Picture Positive Developer
[D-81]
(For Use with Reel Developinft Outfits)
Water (about Elon
Sodium
Sulphite, desiccated
Avoirdupois
—
125° F.) (52" C.) ..
.
Hydroquinone tPotassium Carbonate Potassium Bromide Water to malce
Metric 750.0 cc
8 ounces 100 pounds 10
100 3
pounds pounds pounds
li
ounces
120 gallons
0.5 t^ram 100.0 grams 10.0 lirams 100.0 grams 3.8 grams 1.0 liter
Dissolve chemicals in the order Kiveii.
Average time of development: 4
minutes at 65' F. (i8°C.).
to 10
*
See suggestions on large scale mixing, page 126, Chapter VII. t An equal weight of sodium carbonate may be used but since potassium carbonate is deliquescent any developer which is splashed on the floor does not dry out and becomes a source of harmful chemical du.st.
Maximum (For Use with
Energy Developer Metric
Avoirdupois
Water (about
Wood
125° F.) (52° C.)
24
Alcohol
l)-2
Elon
ounces ounces
750.0 cc 48.0 cc
grains
200
Sodium
1% ounces
Sulphite, desiccated
Hydroquinone
grains grains grains
200 125 125 32
Sodium Hydroxide (Caustic Soda) .. Potassium Bromide Cold water to make ounces Dissolve chemicals in the order given. .
Use without If
wood
dilution.
Develop 4
alcohol
is
minutes
to 5
The prepared developer does
(i8°C.).
[D-82]
Extreme Underexposures)
14.0 52.5 14.0 8.8 8.8
grams grams grams grams grams
1.0 liter
in a tray at
65°F.
not keep more than a few days.
not added and the developer
is
diluted, the solution
is
not as active as in the concentrated form.
Kodalith Negative Film, Plate, or Paper Developer
[D-85]
(For Line or Halftone Negatives of Extreme Contrast)
Water about
Sodium
2.0 liters
120.0 grams 30.0 grams 10.5 grams 30.0 grams 90.0 grams 6.3 grams 4.0 liters
4 ounces
Sulphite, desiccated
Paraformaldehyde Potassium Metabisulphite
1
ounce
150 grains
Boric Acid, crystals
1
Hydroquinone Potassium Bromide Cold water to
Metric
Avoirdupois 64 ounces
90° F.) (32° C.)
3
ounce ounces
90 grains 1 gallon
make
Dissolve chemicals in the order given.
The mixed pered until
solution should be added to a bottle and kept tightly stop-
it is
used.
Before pouring into a tray, the solution should be
brought to a temperature of 65°F. (i8°C.).
removed from the
is
pouring
into a bottle of smaller size,
tightly.
it
If
only a portion of the
bottle, the balance should
developer
be saved by
which should then be stoppered
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
300
Allow the developer
to
stand about two hours after mixing.
Average time of development: i^
to 2
minutes for
and With a
line negatives
not over 2\ minutes at 65°F. (i8°C.) for halftone negatives.
correctly timed exposure, the image should appear in about 45 seconds.
A
longer time of appearance indicates underexposure
;
a shorter time in-
dicates overexposure.
This formula when used with Kodalith emulsions has the property of giving extreme contrast in the low densities which insures clean dot for-
mation
in
erties for
A
This developer retains
halftone negatives.
about one month
if
much
developer having similar characteristics and
properties as a stock solution
[D-85b]
Two
its
original prop-
stored in a tightly stoppered bottle. better keeping
the following:
is
Solution Kodalith Negative Film, Plate, or Paper Developer
(For Line or Halftone Negatives of
Stock Solution A Water (about 1 25° F.
)
(52° C.
64 ounces 4 ounces
)
Sodium Sulphite, desiccated Boric Acid, crystals
1
Hydroquinone Potassium Bromide Cold water to
Extreme Contrast)
Avoirdupois
3
120.0 30.0 90.0 6.3
ounce ounces
90 grains 96 ounces
make B (Keep
Metric 2.0 liters
grams grams grams grams
3.0 liters
Stock Solution in a well-stoppered brown bottle) Water (about 90° F.) (32° C.) 24 ounces 750.0 cc Potassium Metabisulphite 10.5 grams 150 grains
Sodium
Sulphite, desiccated
15 grains
Paraformaldehyde *Phenosafranine (1 1000 solution) Cold water to make :
Dissolve chemicals * I
in
.
.
1
ounce
5
drams
gram
1.0
30.0 grams 20.0 cc
32 ounces
1.0 liter
each solution in the order given.
To prepare a
liter
i :iooo solution, dissolve i gram (15 grains) of phenosafranine in (32 ounces) of distilled water at i25°F. (52°C.). Allow to cool before use.
For use add inspection for
i
part of Solution
i-}
to 2
B
minutes for
for halftone negatives at
Develop by
to 3 parts of Solution A. line negatives or not over
65°F. (i8°C.).
With
2^ minutes
correct exposures the
flash up in about 45 seconds. A yellow or orange safelight be used after development has progressed for jo seconds. The
image should
may
stock solutions keep satisfactorily for several months.
[D-87]
Pyro Contrast Developer for Aero Films (For General Use at Normal Temperatures) 65° F. to 70° F. (18° C. to 21° C.)
Avoirdupois
Sodium Sulphite, desiccated Sodium Carbonate, desiccated Potassium Bromide Potassium Metabisulphite Pyro Water to make
1 1
ounce 60 grains ounce 125 grains
73 grains 57 grains 165 grains 1
gallon
Metric 34.4 38.4 5.0
grams grams grams grams grams
4.0 11.6 4.0 liters
FORMULARY
301
Directions: This developer oxidizes rapidly, so that the pyro should
be added just before use.
and add
to the tank.
Dissolve the sulphite, carbonate, and bromide
Dissolve the nietabisulphite separately in a small
When
volume of water; then add the pyro.
ready to develop, add the
make up
metabisulphite-pyro solution to the tank and
is
to
volume with
Develop about 30 minutes at 65째F. (i8째C.).
water.
Xotc: Because of the comparatively short keeping properties of this developer, when developing each roll of film.
it
desirable to use a fresh solution
When mended
the use of pyro
staining, 2. keeps well
not preferred, Formula
is
page 286).
(see
D-igb
is
has the following advantages:
It
and may be used several times,
3.
recomnon-
i.
works
satis-
factorily at high temperatures.
DIRECT REVERSAL PROCESS ON PAPER The times
required for each chemical treatment of the exposed paper
in the reversal printing process are as follows: 1.
Development
3.
Clearing
4.
Redevelopment
(45 seconds- 1 minute) 2.
(30 seconds)
Bleach (30 seconds) 5.
(30 seconds)
Fixation
(if
desired, but not necessary)
(30 seconds) necessary to wash the prints well in running water for at least
It is
redeveloper
is
used,
it is
Where
the
recommended
necessary to expose the paper to
artificial light
15 seconds between the different solutions.
If convenient, the white light
or daylight before redevelopment.
can
be turned on as soon as the prints are placed in the clearing bath.
brown tones are will
desired, the sulphide redeveloper
be unnecessary to use white
may
be used when
Avoirdupois
ounces ounces 3J4 ounces H ounce
Water
96
Sulphite, desiccated
6J
Hydroquinone *Boric .\cid, crystals
Potassium Bromide Sodium Hydroxide (caustic soda). Water to make Dissolve chemicals *
Use
crystalline boric
great difficulty and
its
acid
as
it
light.
First Developer for Direct Positive Prints
Sodium
If
2
150 .
.
.
in
grains
iH
ounces
1
gallon
[D-88]
Metric 750.0 cc 48.8 grams 24.4 ftrams 5.b (irams 2.6 grams
24.4 1 .0
grams liter
the order given.
specified
use should be avoided.
;
powdered boric acid dissolves with
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
302
It
volume
desirable to dissolve the caustic soda in a small
is
a separate container and then add
Then
stituents.
tainer
dilute the
employed
is
whole to the required volume.
should
dissolved, to prevent cracking the
is
by the heat evolved.
glass container full
a glass con-
If
in dissolving the caustic soda, the solution
be stirred constantly until the soda
Use
of water in
to the solution of the other con-
it
strength at 7o°F. (2i°C.).
Special Direct Positive Paper Developer
[SD-2]
Avoirdupois
Water (about
ounces ounce 7' 2 ounces 2)4 ounces
125° F.) (52° C.)
96
Elon
1
Sodium
Sulphite, desiccated ....;...
Hydroquinone Potassium Bromide
grains
150
Sodium Hydroxide (caustic soda). Cold water to make
.
.
.
31^2
ounces
1
gallon
Metric 750.0 cc 7.5 56.3 18.8 2.6 26.3
grams grams grams grams grams
1.0 liter
Dissolve chemicals in the order given.
Use
full
65^to 7o°F. (i8° to 2i°C.). recommended particularly as a first developer when desired on redevelopment. It is not suitable for making
strength at
This formula sepia tones are
is
enlargements.
Bleaching Solution
[R-9]
Avoirdupois
Bleaching Bath
Use
Water Potassium Bichromate
1
gallon
1)4
Sulphuric Acid (pure cone.)
1)^ fluid
ounces ounces
full
strength at 65° to 7o°F. (18° to 2i°C.).
Metric 1.0 liter 9.6 grams
12.0 cc
For more rapid
bleaching, however, the quantities of acid and bichromate
may
be
in-
creased. Clearing Bath Sodium Sulphite, desiccated.
Water
to
make
...
12 1
ounces
90.0
gallon
grams
1.0 liter
Redeveloper A. Black and white prints.
Use
first
developer (Formula D-88)
(i8° to 2i°C.).
full
strength at 65°to 70°F.
This operation must be conducted
in the light,
either strong artificial light or sunlight.
B. Sepia Tones. If sepia tones are desired,
white light
is
unnecessary and the
lowing redeveloper should be used after clearing:
fol-
FORMULARY
303
Sulphide Redeveloper
[T-19] Metric 20.0 f^rams
Avoirdupois
Sodium Sulphide Water
Use
to
inot sulphite)
300 i^rains 32 ounces
make
1.0 liter
strength at 65° to 7o°F. (18° to 2i°C.).
full
Fixing Bath Prints of slightly greater brilliancy
(Formula F-5)
regular fixing bath
D-88.
It
is
may
be secured by fixing in the
Formula
after redevelopment in
important to wash for at least 10 niinutcs to insure removal
of the fixing bath from the print.
It is
not necessary to use the fixing
bath after the sulphide redeveloper.
Rack and Tank Developer for Panchromatic Motion Picture Film
[D-89]
(Elon-Borax-Pinakryptol Green) It is
necessary sometimes to develop panchromatic motion picture
For such work
negatives without sampling.
it is
very convenient to be
able to inspect the negatives at intervals and observe the progress of de-
This
velopment. tion light
may
3.8 volt bulb
is
An
possible with the following developer.
inspec-
be prepared by fitting a two-cell hand ilashlight with a
and a
Series 3
filter.
Two
thicknesses of
white paper should be placed between the
filter
medium weight
glasses to reduce the
light intensity further.*
Metric
Avoirdupois
Elon
Sodium Sulphite, desiccated Borax, granular tPinakryptol Green (1 500 solution) :
Water
to
make
3 100 5
pounds pounds pounds
77 fluid ounces 120 gallons
3.0 )irams 100.0 ftrams 5.0 grams 5.0 cc 1 .0 liter
Dissolve chemicals in the order given. t
A
may
stock solution of the dye
be
made up by
dissolving
i
part of dye in
500 parts of water at i6o°F. (7i°C.).
Film should be developed
at least
i
minute
in
complete darkness be-
The properties of the developer are Formula D-76. The desensitizing action decreases
fore inspection with a safelight.
similar to those of
with age whether the solution
is
used or not.
If the
bath has stood for
some time, the desensitizing action should be determined and more dye added if necessary. Average time of development for panchromatic negative motion picture film
is
8 to 12 minutes at 65''F. (i8°C.).
variable density sound negatives * J. I.
"Improvements Crabtree.
J.
in
it is
6 to 8 minutes at
Laboratory Apparatus" by C. E. Ives, A. -iO (193')-
Soc. Mot. Picl. Hug. 17.
For
65°F. (i8°C.). J.
Miller,
and
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
304
Pyro Tray Developer
[D-90]
(For General Use)
Sodium Sulphite, desiccated. Sodium Bisulphite
make
to
ounces 145 grains
2
Stock Solution B Sodium Carbonate, desiccated
ounces
1.0 liter
23^ ounces 15 grains
Potassium Bromide Water to make
grams
73.0
1.0 gram 1.0 liter
ounces
32
grams grams grams
70.0 17.0 20.0
grains grains
245 290 32
Pyro
Water
Metric
Avoirdupois
A
Stock Solution
Dissolve chemicals in the order given.
For normal use take
i
part A,
i
part B, and
2
parts water.
Develop
4 to 6 minutes at 65°F. (i8°C.).
For greater contrast take For
less contrast
take
i
i
part A,
part A,
i
i
part B, and
i
part water.
part B, and 4 parts water.
Note : This developer has been used for many years at the Kodak Research Laboraand represents a satisfactory pyro developer. It was derived originally from the British Journal Almanac. Like all pyro developers, however, it is subject to rapid tories
deterioration because of oxidation.
P-aminophenol (Kodelon) Tropical Developer
[D-91]
Avoirdupois
Water (about 125° F.) (52° C.) Para-aminophenol Hydrochloride (Kodelon
24 ounces 100 grains
)
Sodium Sulphite, desiccated Sodium Carbonate, desiccated. Cold water to
ounce 2S0 grains ounce 290 grains 32 ounces 1
.
1
.
make Dissolve chemicals
Average time of development: 3 to 4 minutes at
in
7 to
7.0 50.0 50.0
grams grams grams
1.0 liter
the order given.
9 minutes at 65°F. (i8°C.)
and
8o°F. (26.7'^C.).
temperature of the solution
If the
Metric 750.0 cc
is
8o°F. (26.5°C.) or above, add
i^ ounces desiccated sodium sulphate to 32 ounces of solution (45 grams per liter).
Rinse, harden,
DK-15, page
[DK-93]
fix,
and wash
as
recommended
for
Formula
284.
P-aminophenol (Kodelon) -Hydroquinone-Kodalk Film and Plate Developer Avoirdupois
Water (about 125° F.) (52° C.) Para-aminophenol Hydrochloride (Koi.»elon)
Sodium
Sulphite, desiccated
Hydroquinone Kodalk Potassium Bromide Cold water to
make
16
ounces
Metric 500.0 cc
73 grains
5.0
ounce
30.0
1
36 grains 290 grains 7
grains
32 ounces
Dissolve chemicals in the order given.
2.5
20.0 0.5
grams grams grams grams
gram
1.0 liter
FORMULARY Develop at
roll film in
305
trays about 8 minutes or in tanks about lo minutes
65°F. (i8°C.).
Develop professional and cut
film in tanks
about
7
minutes and in
trays about 5^ minutes at 65°F. (i8°C.).
SPECIAL DEVELOPERS HAVING LIMITED USE Pyro Stain Developer (For Producinjl a Stain Imajie with a
Minimum
[SD-l]
of General Stain)
Metric
Avoirdupois
Sodium
Sulphite, desiccated
20 40 75 32
Pyro
Sodium Carbonate, desiccated Water
to
make
grains grains grains
1.4 (irams 2.8 grams 5.3 grams 1.0 liter
ounces
Dissolve chemicals in the order given.
Use without dilution. Develop about 6 minutes at 65 "^F. (i8°C.), and fix in a plain hypo bath. Reference: Chapter XI, page 244.
rinse,
Two-Bath Development Development
in
MI, page
Chapter
two successive baths
Two-Bath Developers Parker,
Jr.,
offers certain
129; also following papers:
advantages (see
"Some
Properties of
Motion Picture Film," J. I. Crabtree, H. /. Soc. Mot. Pict. Eng. 21, 21-53, (July Rapid Processing Methods," H. Parker, Jr., and J. I. Crabfor
and H. D. Russell,
1933) and " tree, Amer. Phot. 30, 67 et seq. (Feb. 1936).
Two- Bath Developer (For
Solution Elon
— First Bath
A
Sodium
Avoirdupois
Sulphite, desiccated.
..
.
Hydroquinone to
Solution B
make
— Second
Metric
grams grams grams grams grams
5
pounds pounds pounds pounds pounds
120
gallons
1.0 liter
10 100
pounds pounds pound
10.0 grams 100.0 grams 0.5 gram 0.01 gram
5 2
100 100
Sugar, granulated Sodium Bisulphite
Water
[SD-4]
Panchromatic Motion Picture Negative Film) 5.0 2.0 100.0
100.0 5.0
Bath
Sodium Carbonate, desiccated Sodium Sulphite, desiccated. .. Potassium Bromide .
Potassium Iodide Water to make Dissolve chemicals
.
.
Ji
70 120 in
each bath
Average time of development:
grains gallons in the
1.0 liter
order gi\en.
4 minutes in each bath at 65 °F.
(i8°C.).
The sugar and bisulphite in the first bath serve to restrain development and prevent the appearance of the image. The gelatin absorbs the solution and when the film is moved into the second bath, the alkali
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
306
in this
bath acts on the absorbed developing agent and causes fairly
rapid development, which stops as soon as the absorbed developer
is
Reference should be made to the paper cited above for
used up. complete
details.
Two- Bath Developer
[SD-5]
(For Variable Density
Sound Records)
Solution A — First Bath
7 10 2
Sodium Sulphite, desiccated Sodium Bisulphite Sugar, granulated
Water
to
Metric
Avoirdupois
Elon
make
pounds pounds pounds pounds
7.0 10.0 2.0
100 120 gallons
100.0
pounds pounds
25.0 10.0
B — Second Bath Sodium Sulphite, desiccated Sodium Carbonate, desiccated ....
grams grams grams grams
1.0 liter
Solution
Water
to
120 gallons
Dissolve chemicals
Develop about
25 10
make
each bath
in
in the
3 minutes in the first bath
grams grams
1.0 liter
order nven.
and
2
to 3 minutes in the
second bath at 65°F. (i8°C.). Reference should be
made
to the
paper cited above for complete
details.
Rapid Two-Bath Developer
[SD-6]
(For Press Photography)
Bath (No. Water (about
First
125° F.) (52° C.)
24 44 365 88
Elon
Sodium
Sulphite, desiccated
...
Hydroquinone
Sodium Sulphate, desiccated Sodium Carbonate, desiccated Cold water to
.
grains grains grains
3.0 25.0 6.0 100.0 20.0
ounces
Sodium
1000 solution) (1 Sulphite, desiccated .... :
Potassium Bromide Water to make
drams
5
fluid
1
ounce 290 grains
20.0 cc 50.0 grams 2.0 grams 1.0 liter
grains
30 32
ounces
B
Formalin (37'; solution) Water to make
6'
2
32
ounces ounces in the
the No.
bath and treat for
i
i
Develop
i
1.0 liter
order given
the second bath, take equal parts of
Directions for Use:
200.0 cc
fluid
Dissolve chemicals in each bath
2 6.5°C.") in
1.0 liter
2)
Phenosafranine
To make
grams grams grams grams grams
A
Solution
Solution
750.0 cc
grains
290 32
.
ounces
ounces 145 grains
3
.
.
make
Second Bath (No.
Metric
Avoirdupois
1)
A
and B.
minute at 65° to 8o°F.
(18° to
bath, then transfer without rinsing to the
minute with thorough agitation.
No.
2
Rinse a few sec-
water or an acid rinse bath (Formula SB-i, page 307), and fix until clear in an acid hardening fixing bath (Formula F-5, page 310).
onds
in
For rapid
fixing, use
36% hypo
in the
F-5 formula or use the F-24
FORMULARY
307
hypo-bisulphite bath to which has been added
Wash
2^% ammonium
running water and dry rapidly with
briefly in
Reference should be
made
to the article cited
warm
above
chloride.
air.
for
complete
details.
RINSE (STOP) BATHS AND HARDENING BATHS Acetic Acid Rinse Bath for Papers Avoirdupois 32 ounces
Water Acetic Acid (28% pure) *
To make 28%
Ij
o
fluid
[SB-l]
Metric 1
ounces
.0 liter
48.0 cc
acetic acid from glacial acetic acid, dilute 3 parts of glacial acetic
acid with 8 parts of water.
Rinse prints for at least
seconds.
5
With a I to 2 seconds drain, the equivalent of approximately twentyfive 8 by lo-inch prints may be processed in i quart (i liter) of this bath before
it
becomes alkaline and should be discarded.
Acetic Acid Rinse Bath
[SB-la]
(For Use with Films, Plates, and Papers for Photo-Mechanical Processes)
Avoirdupois
Water Acetic Acid *
To make 28%
(28' c
pure)
acetic acid
Metric
32 ounces 4 fluid ounces
from
glacial
1.0 liter
128.0 cc
acetic acid, dilute
3
parts of glacial
acetic acid with 8 parts of water.
The
action of this bath checks development instantly, preventing
uneven spots and streaks when negatives are immersed
in the fixing
solution.
Hardener-Rinse Bath for Films and Plates
[SB-3]
(For Use at 65째 to 75째 F. (18째 to 24째 C.)
Metric
Avoirdupois
Water Potassium Chrome Alum
This bath
is
32 ounces 1
1
ounce
.0 liter
30.0
grams
intended for use in hot weather after development and
before fixation in conjunction with Formula F-5.
Agitate the negatives for several seconds
hardener and allow to remain
maximum
hardening.
in
when
first
immersed
in
the
the solution for 3 to 5 minutes to secure
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
308
Important: The bath should be renewed frequently and tendency for scum to form on the bing with cotton.
films,
it
if
there
is
any
should be removed by swab-
The bath should be skimmed each day
before use.
Tropical Hardener Rinse for Films and Plates
[SB-4]
(For Use at 75° to 95° F. (24° to 35° C.)
Water Potassium Chrome Alum *Sodium Sulphate, desiccated
Avoirdupois
Metric
32 ounces
1.0 liter
1
2
ounce ounces
30.0 60.0
grams grams
* If crystalline sulphate is preferred instead of the desiccated, use (140 grams) in the above formula.
After development in a concentrated developer such as
4^
ounces
DK-15, page
more than i second and then immerse minutes. Omit the water rinse above 85 °F.
284, rinse the film in water for not
SB-4 bath
in the
for 3
(29.4°C.) and transfer directly to the hardener bath for 3 minutes. tate for 30 to 45 seconds immediately after
immersing
Agi-
hardener
in the
or streakiness will result.
The hardening bath is a violet-blue color by incandescent light (clear when freshly mixed, but it ultimately turns to a yellow-green with
bulb) use;
then ceases to harden and should be replaced with a fresh bath.
it
An unused
bath
will
a partially used bath
keep indefinitely but the hardening properties of
fall off
rapidly on standing for a few days.
Non-swelling Acid Rinse Bath for Roll Film
[SB-5]
Water *Acetic Acid (28^; pure) tSodium Sulphate, desiccated
Water *
Avoirdupois
Metric
gallons
500.0 cc 32.0 cc 45.0 grams
5
to
40
acetic acid
from
ounces
3^ pounds
.
make
To make 28%
fluid
10
gallons
glacial
acetic
1.0 liter
acid,
dilute
3
parts of glacial
acetic acid with 8 parts of water. t
If
it is
desired to use sodium sulphate crystals instead of the desiccated sulphate,
use 14 ounces per gallon (105 grams per
Agitate the films
liter).
when immersed
in the
bath and allow to remain
about 3 minutes before transfer to the fixing bath. This bath (SB-5) is satisfactory for use to 8o°F. (26.5''C.). It should be replaced after processing about 100 rolls per gallon provided about
3 quarts of developer
by 100
rolls.
When
acid.
working at temperatures below 75° F. (24°C.), the
acid rinse bath in
have been carried into the acid rinse bath
The bath should not be revived with
may
life
of the
be extended by giving the films a few seconds' rinse
running water previous to immersion
in the acid rinse bath.
)
FORiMULARY
309
FIXING SOLUTIONS Acid Hardening Fixing Bath
[F-l]
(For All Grades of Papers)
Sodium Thiosulphate Water to make
When
(hypo).
Sodium
Metric
ounces ounces
240.0 liratns
32
dissolved completely, add Water (about
Avoirdupois 8
.
all
of the following hardener solution:
2M
125° F.) (52° C.)..
Sulphite, desiccated. pure) ;
ounces ounce fluid ounces ounce
J^
.
Acetic Acid (28< Potassium Alum
1.0 liter
1}4 J4
80.0 cc 15.0 grams 48.0 cc 15.0 ftrams
Dissolve chemicals in the order given, following the instructions given after the stock hardener (Formula F-ia). *
To make 28%
acetic acid
from
glacial
acetic acid,
dilute
3
parts of glacial
acid with 8 parts of water.
Cool the hardener solution after mixing and add it slowly to the cool hypo solution while stirring the hypo solution rapidly. The F-i fi.xing bath, prepared as instructed, will fix approximately sixty 8 by lo-inch prints per gallon (4 liters) or their equivalent in other sizes, if a water rinse is used or approximately one hundred twenty 8 by 1 0-inch prints per gallon (4 liters) if the acid rinse bath (Formula
SB-i)
is
used between development and fixation.
The temperature
of
the bath should be kept as near 70° F. (2i°C.) as possible.
Acid Hardener Stock Solution (For
Water (about
Preparing Formula
125° F.) (52°
Sodium
C).
Sulphite, desiccated *Acetic Acid (28' c pure)
.
.
...
Potassium Alum Cold water to make
*
To make 28%
acetic acid
Avoirdupois
Metric
56 ounces 8 ounces 24 fluid ounces 8 ounces
1700.0 cc 240.0 grams 750.0 cc 240.0 grams
1
Dissolve chemicals
from
[F-la]
F-1
in
gallon
4.0 liters
the order given.
glacial
acetic acid,
dilute
3
parts of glacial
acid with 8 parts of water.
To make up the hardener dissolve the chemicals in the order given. The sodium sulphite should be dissolved completely before adding the acetic acid.
After the sulphite-acid solution has been mixed thoroughly,
add the potassium alum with constant stirring. When dissolved make up to the final volume with cold water. A fixing bath is made quickly by adding i part of this hardener to
:
.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
310
4 parts of I
25%
hypo
cool
solution, or 32 ounces (i liter) of hardener to
gallon (4 liters) of cool
hypo solution containing
2
pounds
of
hypo
to the gallon of water.
Acid Hardening Fixing Bath
[F-5]
(For Films
and
Plates)
Metric
Avoirdupois
Water (about
Sodium Sodium
125째 F.) (52째 C). Thiosulphate (hypo).
Sulphite, desiccated. *Acetic Acid (28^( pure) fBoric Acid, crystals
.
.
.
80
ounces
2
pounds
2
2
ounces ounces ounce ounces
1
gallon
.
...
2.5 liters
6 fluid 1
Potassium Alum Cold water to make
960.0 grams 60.0 grams 190.0 cc 30.0 grams 60.0 grams 4.0 liters
Dissolve chemicals in the order given. *
To make 28%
acetic acid
glacial acetic acid, dilute 3 parts of glacial acid
from
with 8 parts of water. t Crystalline boric acid
with great difficulty and
Films or plates should be fixed properly 5
Powdered boric
should be used as specified. use should be avoided.
acid dissolves
its
lo minutes (cleared in
in
The bath need not be discarded
minutes) in a freshly prepared bath.
becomes excessive, that is, and hardens well throughone hundred 8 by ten-inch films or
until the fixing time (twice the time to clear)
The
over 20 minutes.
out
its
useful
solution remains clear
About eighty
life.
to
plates (or their equivalent in other sizes)
The F-5
may
be fixed per gallon.
bath has the advantage over the older type of fixing baths, which do not contain boric acid, that it gives much better hardfixing
ening and has a lesser tendency to precipitate a sludge of aluminum sulphite throughout
its
useful
The hardener may
life.
also be
mixed separately as a stock solution as
follows
Stock Hardener Solution
[F-5a]
(For Preparing
Formula
F-5)
Avoirdupois
Water (about
125째 F.) (52째 C.)
Sodium
Sulphite, desiccated *Acetic Acid (28'~f pure) tBoric Acid, crystals
Potassium Alum Cold water to make
.
.
.
80 ounces
.
.
10
ounces
30 fluid ounces 5 10 1
Metric 2.5 liters
ounces ounces gallon
300.0 grams 940.0 cc 150.0 grams 300.0 grams 4.0 liters
Dissolve chemicals in the order given. *
To make 28%
acetic acid
from
glacial acetic acid, dilute 3 parts of glacial acid
with 8 parts of water. t Crystalline boric acid should be used as specified.
with great difficulty and
its
use should be avoided.
Powdered boric acid
dissolves
FORMULARY A
fixing bath similar to
F-5
made by adding
is
hardener solution to 4 parts of cool
hypo per gallon
A
line developers
especially satisfactory for use with highly alka-
is
such as
part of cool stock
i
hypo solution (2^ pounds the hypo rapidly.
t,o'^(
of water) while stirring
fixing bath that
311
D-19
or
D-ii
is
the following:
Acid Hardening Fixing Bath
[F-IO]
(For Use with Highly Alkaline Developers)
Metric
Avoirdupois
Water (about
125째 F.) (52째 C.)
ounces
64
Sodium Thiosulphate (hypo) Sodium Sulphite, desiccated
2^4
Kodalk
4
Acetic Acid
1
pure)
i28''t
Potassium Alum Water to make DissoKe chemicals
9 3
ounces fluid ounces ounces
1
ftallon
in
2.0 liters
pounds ounce
tlie
1320.0 30.0 120.0 285.0 90.0
ftrams ftrams ftrams cc
ftrams
4.0 liters
order given.
Fix for twice the time to clear the film of
its
milky appearance.
Wash
thoroughly and wipe each negative carefully before drying.
minimum
sludging
Fixing Bath for Films and Plates
[F-16]
This bath has good hardening characteristics and a
tendency throughout
Chrome Alum
its
useful
life.
A Sodium Thiosulphate (hypo). Sodium Sulphite, desiccated ..
Avoirdupois
Metric
2
pounds
2
ounces ounces
960.0 ftrams 60.0 (irams
Solution
Water
to
Solution
B
.
.
.
make
96
Water
32
Potassium Chrome Alum Sulphuric Acid (pure, cone.)
2 ...
I4
Pour Solution B slowly into Solution
Use water
3.0 liters
ounces ounces fluid ounce
A
1.0 liter
60.0 ftram 8.0 cc
while stirring
A
rapidly.
at a temperature not higher than i25째F. (52째C.)
dissolving the
chrome alum or the hardening properties
Rinse films thoroughly before
Important:
A
will
when
be impaired.
fixing.
fresh bath should be prepared frequently because this
formula rapidly loses
its
hardening properties with use, when it should With an old bath, there is a tendency for
be replaced by a fresh bath.
scum to form on the surface of the film. Any such scum should be moved by swabbing with cotton before drying.
Fixing Bath for Motion Picture Film
Chrome Alum Solution
Avoirdupois
A
Sodium Sodium Water
*
A
Thiosulphate (hypo)
2
Sulphite, desiccated
to
make
96
bath which fixes more rapidly
centration in the above formula to
1
2^/2
pounds ounce 290 grains ounces
re-
[F-23]
Metric 240.0 lirams 12.5 ftrams 750.0 cc
be obtained by increasing the hypo conpounds per gallon (300 grams per liter).
may
.
312
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS Solution B
Water
Sodium
20
Sulphite, desiccated.
Sulphuric Acid, 5"^^ solution. Potassium Chrome Alum .... Water to make
FORMULARY
313
Dissolve the hypo in one-half the total volume of water and then add the remaining chemicals in the order given after dissolving in a small
volume
of water (about i25°F. {52°C.).
Dilute with water to the re-
quired volume.
Revival
is
unnecessary with the above fixing bath as the hardening
properties are maintained and the bath will not sludge throughout useful
The
life.
solution
may
its
be used until exhausted with 400 feet per
when it should be replaced by a fresh bath. Formula F-25 may be prepared conveniently from a concentrated
gallon
stock hardener as follows:
Work
Stock Hardener for Motion Picture (For Preparing
Formula
Metric
Avoirdupois
Water (about
—
125° F.) (52° C.)
Sodium
Sulphite, desiccated Glacial Acetic Acid tBorlc Acid, crystals
25
500.0 cc 25.0 ftrams 50.0 grams
pounds
6 gallons 25 pounds 50 pounds 120 gallons
Potassium Alum Cold water to make
[F-25a]
F-25)
25.0 50.0
grams grams
1.0 liter
Dissolve chemicals in the order given. *
A
fixing bath prepared with the above solution will not sulphurize within a
period of 3 to 4 weeks at 70°F. (21 °C.). If the temperature 70°F. (21 °C.) the quantity of sulphite should be doubled. t
Use
crystalline
acid as
boric
specified
;
is
apt to rise above
powdered boric acid dissolves with
great difficulty.
For use add cool
hypo
i
part of cool stock hardener solution to 4 parts of a
30%
solution.
HYPO TEST FOR THOROUGHNESS OF WASHING Very small traces
of
hypo retained
the rate of fading of the image. quantities of prints
may
It is
hypo but the following
in films or prints greatly accelerate
extremely
difficult to test for
test will indicate
when
small
the film or
be considered reasonably free from hypo.
If prints give
a negative reaction by the following
antee that the prints
may
not ultimately fade.
test, it is
no guar-
For example,
if
the
hypo complexes would remain washing and would not be detected by this test.
prints were fixed insufficiently, insoluble in the prints after
Sodium Thiosulphate (Hypo) Test Solution (For Films, Plates,
and Papers)
Avoirdupois Distilled water
Potassium Permanganate Sodium Hydroxide (caustic
Water
(distilled) to
make
soda)..
Metric
6 ounces 4 grains 8 grains
180.0 cc 0.3 gram
8 ounces
250.0 cc
0.6
gram
[HT-la]
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
314
Films or Plates: Take 8 ounces (250 cc) of pure water
and add \ dram
film (No. 118 or 5
by
in a clear glass
HT-ia. Then take a 6 or 8 exposure equivalent (one 8 by lo-inch film; two
cc) of solution
i
(
No. 116) or
7-inch films, etc.) and allow the water to drip for 30 seconds into
the glass of test solution. violet color will turn
If a small
orange
percentage of hypo
present, the
is
about 30 seconds, and with larger concen-
in
trations the orange color will change to yellow.
In either case, the nega-
wash water and allowed to wash until a produces no change in color, which indicates that the hypo
tive should be returned to the
further test
content has been reduced to a safe margin, thereby insuring satisfactory
permanency under normal keeping conditions. Papers: Take 4 ounces (125 cc) of pure water in a clear glass and add (i cc) of solution HT-ia. Pour ^ ounce (15 cc) of this diluted dram ^ solution into a clean i-ounce graduate or similar container.
Then take
(4 by 5-inch or the equivalent) from the wash water and allow water from them to drip for 30 seconds into the ^ ounce of test
six prints
If a small
solution.
I
percentage of hypo
is
present, the violet color will
about 30 seconds and become colorless in about In either case the prints should be returned to the wash
change to orange minute.
in
water and allowed to wash, until a further color,
test results in
no change
which indicates that the hypo content has been reduced
in
to a safe
margin, thereby insuring satisfactory permanency under normal keeping conditions.
Note: Oxidizable organic matter if present in the water reacts with the permanganate solution and changes the color in the same manner as hypo. The water should therefore be tested as follows
When
:
made with
negatives or prints from the wash w'ater a similar should be made with the tap water. Add a volume of tap w-ater, equal to the wash water drained from the negatives or prints to a second test solution prepared as above from pure water. If the sample to which tap water has been added remains a violet color, this indicates the absence of organic matter and it will be unnecessary the
first test is
test
to repeat the test.
If the color
is
changed
slightly
by the tap water, the presence of
be shown by the relative color change of the two samples. For example, if the tap water sample turned pink and the wash water sample became yellow, it would indicate the presence of hypo, while if both samples remained the
hypo
in the prints will
same shade,
this
would indicate the absence of hypo.
Special Formalin Hardener
[SH-l]
(For Films
and
Plates)
Avoirdupois
Metric
Formalin (37% formaldehyde solution)
2}^
Sodium Carbonate, Water
to
make
desiccated
....
73 32
drams grains
ounces
10.0 cc 5.0 grams 1.0 liter
FORMULARY
315
This formula is recommended for the treatment of negatives which would normally be softened considerably by a chemical treatment in the removal of several types of stains, or by intensification or reduction. After treatment for 3 minutes in the hardening solution, films or plates
should always be rinsed and immersed for
5
minutes
a fresh acid fixing
in
bath and well washed before giving any further chemical treatment.
Special Supplementary Hardener (For
Solution
125째 F.) (52째
C).
.
Potassium Alum Water to make
Solution B Hot water (about 160째 F.) Borax, granular to
dissolved,
ounces 114 ounces fluid ounces 2 4J^ ounces ounces 64
45.0 grams 64.0 cc 135.0 grams
1
ounces ounce
500.0 cc 30.0 grams
64
ounces
32
.
Sodium Sulphite, desiccated .... Acetic Acid (28' o pure)
When
Metric
Avoirdupois
A
Water (about
[SH-2]
Bromide Papers)
(71째 C.)
16
1.0 liter
2.0 liters
add cold water
make
Cool Solution B and add
it
slowly to Solution
2.0 liters
A with constant
If these directions are followed, a clear solution will
the borax solution, while
still
warm,
is
added
stirring.
be obtained but
to Solution A,
if
an insoluble,
white precipitate will form.
This solution
is
recommended
overcome the tendency
for
bromide papers when necessary
to stick to the belts of
to
heated dryers.
Fix prints in the regular fixing bath, wash thoroughly, and place in the above hardener for 5 or lo minutes.
move
Then wash thoroughly and
re-
surplus water before drying.
Warning: This bath should not be used if prints are to be toned by the hypo-alum or redevelopment method because it has a detrimental effect
upon the
tone.
INTENSIFYING AND REDUCING NEGATIVES If
negatives need intensification or reduction,
it is
best to give
them
such treatment immediately after they have been washed. Much time is saved and the negatives, when dry, are ready for finishing. Precautions: Stains are sometimes produced during intensification or reduction unless the following precautions are observed: i. The negative
should be fixed and washed thoroughly before treatment and be free of scum or stain. 2. It should be hardened in the formalin hardener
(SH-i) before the
intensification or reduction treatment.
negative should be handled at a time and
oughly during the treatment.
it
3.
Only one
should be agitated thor-
Following the treatment, the negative
should be washed thoroughly and wiped
off carefully
before drying.
:
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
316
INTENSIFYING SOLUTIONS Mercury
[in-l]
The mercury is
If
Intensifier
recommended where extreme intensification desired but where permanence of the resulting image is not essential. permanence is essential either the chromium or silver intensifiers intensifier
is
should be used. After hardening in Formula
SH-i (page 314) and washing, bleach
the negative in the following solution until the image turns white; then
wash thoroughly
% %
Mercuric Chloride
The
Metric
Avoirdupois ounces 32
Water Potassium Bromide
1.0 liter
ounce ounce
22.5 22.5
negative can be redeveloped or blackened with
D-16;
or
or with lo^c
ammonia (28%
cone,
These solutions give progressively greater contrast
To
io% sodium
D-72 ammonia
phite solution; or with a developer such as Formula
grams grams sul-
(diluted 1:2)
diluted 1:9).
in the order listed.
increase contrast considerably, treat with the following solution:
Solution
Avoirdupois
A
Water
Sodium Solution
or Potassium Cyanide.
Metric
J^
ounces ounce
500.0 cc 15.0 grams
%
ounces ounce
500.0 cc 22.5 grams
16
B
Water
16
Silver Nitrate, crystals
* Cyanide is a deadly poison and should be handled with extreme care. Use rubber gloves and don't expose yourself to its fumes. Cyanide reacts with acid to form When discarding a solution containing cyanide, poisonous hydrogen cyanide gas. always flush it out of the sink quickly with water.
To
prepare the intensifier, add the silver nitrate Solution
potassium cyanide Solution
A
until a
permanent precipitate
is
B
to the
just pro-
allow the mixture to stand a short time and filter. This is called Monckhoven's intensifier. Redevelopment cannot be controlled as by the chromium method (Formula In-4) but it must go to completion.
duced
;
Note: See precautions on handling negatives, page 315.
[ln-4]
Chromium
Intensifier
Stock Solution Avoirdupois
Water to make Potassium Bichromate Hydrochloric Acid, cone
32 ounces 3 2
ounces fluid ounces
Metric 1.0 liter
90.0 grams 64.0 cc
FORMULARY For
use, take
the negative
317
the formalin hardener (SH-i, page 314).
thoroughly at 65° to yo^'F. (18° to 2i°C.) then wash redevelop in
Harden
part of stock solution to lo parts of water.
i
first in
5
Bleach
minutes and
daylight (not direct sunlight) in either
artificial light or
Nepera solution 1:4
or in the Elon-hydroquinone developer
D-72)
any rapid non-staining developer which does not sulphite. The time of redevelopment varies from
(Formula
diluted 1:3, or
contain an excess of
3 to 10 minutes at 65° to 70' F.
(
18"^ to
Then
2i°C.) depending on the degree
and immerse in a fixing bath (Formula F-i, page 309, or similar bath) for 5 minutes and wash thor-
of intensification desired.
rinse
oughly.
The
Greater intensification can be secured by repeating the process.
degree of intensification can also be controlled by varying the time of
redevelopment.
as
Warning: Developers containing a high concentration of sulphite such Formula D-76 are not suitable for redevelopment because the sul-
phite tends to dissolve the bleached image before the developing agents
have time Xotc
:
on
to act
it.
See precautions on liandling negatives, page 315.
Silver Intensifier
The
following formula
is
[ln-5]
the only intensifier
known
that will not
change the color of the image on positive film on projection. proportional intensification and of treatment. film.
The formula
is
easily controlled
is
by varying
equally suitable for positive and negative
Films should preferably be hardened in the formalin hardener
(Formula SH-i, page 314) before treating Stock Solution Stock Solution
Sodium Water
to
60.0 ftrams
make
ounces ounces
60.0
33^ ounces
lO.S.O
32
1.0 liter
2 .
.
make
2
32
Stock Solution 3 Sodium Thiosulphate (hypo)..
Water
Metric
ounces ounces
2
Sulphite, desiccated
to
in the intensifier solution.
Avoirdupois
1
Silver Nitrate Distilled water to
make
1
ounces
32
1
Sodium
Sulphite, desiccated
.
Water Store
in
350 96
make
Arams
.0 liter
grams
ounce
l.S.O
grains
24.0 grams 3.0 liters
ounces
a brown bottle.
Prepare the of Solution
to
3^
.
Elon
grams
.0 liter
Stock Solution 4
*
It gives
the time
intensifier solution for use as follows:
No.
2
to
i
obtain thorough mixing.
part of Solution No.
The white
i,
Slowly add
i
part
shaking or stirring to
precipitate which appears
is
then
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
318
dissolved
by the addition
of
part of Solution No. 3.
i
/\llow the re-
Then add, with
sulting solution to stand for a few minutes until clear.
No. 4. The intensifier is then ready for use and the negative should be treated immediately. The mixed intensifier stirring, 3 parts of Solution
is
stable for approximately 30 minutes at 70째F. (2i째C.).
The degree
of intensification obtained depends
ment which should not exceed 25 minutes. merse the film or plate
for 3
minutes
upon the time
of treat-
After intensification im-
in a plain
30% hypo
solution
and
then wash thoroughly. Note: See precautions on handling negatives, page 315.
Redevelopment
A
Intensifier
simple method of intensification for negatives consists of bleaching
and bromide bleach used for sepia toning (Formula T-ya, page 331) and blackening in the sodium sulphide bath exactly as in the ferricyanide
in print toning.
PHOTOGRAPHIC REDUCERS Photographic reducers
may
be classified into three types as follows:
A. Subtractive or cutting reducers which remove equal quantities of silver
from the high, intermediate, and low densities respectively.
have the
effect of clearing
up the highlights and therefore appear
crease the image contrast but they do not change
They to in-
They
gamma.
are
useful for treating fogged or overexposed images.
B. Proportional reducers which remove density in an is
They
proportional to the original density.
also visual contrast
and correct
for
C. Super-proportional reducers
which bear a greater proportion
therefore lower
gamma and
overdevelopment.
which remove density increments
to the original density as the
They
of the original density increases.
densities without destroying
amount which
shadow
magnitude
therefore reduce the highlight
detail
and are useful
for treating
overdeveloped negatives of contrasty subjects.
A.
SUBTRACTIVE REDUCERS Acid Permanganate Reducer
[R-2]
(For General Use)
Stock Solution
Avoirdupois
A
Water Potassium Permanganate.
32 ..
.
IJ^
Metric
ounces ounces
52.5
ounces fluid ounce
32.0 cc
1.0 liter
grams
Stock Solution B
Water Sulphuric Acid, pure cone
32 1
1.0 liter
FORMULARY
319
Harden the negative first in the special formalin hardener (Formula SH-i, page 314). The negative must be washed thoroughly to remove of hypo before it is reduced. For use, take i dram (4 cc) of drams (8 cc) of B, and 8 ounces (250 cc) of water. When the
all traces
A,
2
negative has been reduced sufficiently, place
(Formula F-i or similar type) stain.
it
bath
in a fresh acid fixing
few minutes to remove the yellow
Then wash thoroughly. add more water.
If reduction is too rapid,
as a stain remover as
it
Formula S-6, page 335 If
for a
one treatment
is
will attack the is
Do
recommended
R-2
not use Formula
image before removing the
stain.
for stain removal.
insufficient the process
may
be repeated, but
it is
necessary to wash thoroughly, otherwise the retained hypo will reduce the permanganate forming an objectionable stain. Note : If a scum forms on the top of the permanganate solution or a reddish curd appears in the solution, it is because the negative has not been sufficiently washed to remove all hypo, or because the permanganate solution has been contaminated by hypo. The separate solutions will keep and work perfectly for a considerable time The two solutions should if proper precautions against contamination are observed. not be combined until immediately before they are to be used.
They
will not
keep
long in combination.
A
close observance of the foregoing instructions
wise an iridescent
scum
after they are dry;
and
will
is
important.
Other-
sometimes appear on the reduced negatives
this is difficult,
if
not impossible, to remove.
Note: See precautions on handling negatives, page 315.
Farmer's Reducer (For
Solution
Avoirdupois
A
Water Potassium Ferricyanlde Solution
[R-4]
Amateur Use) 1
ounce
15 grains
Metric 32.0 cc 1.0
gram
B i2 ounces
Water
Sodium Thlosulphate (hypo)
1
ounce
10 30.0
liter
grams
Note: See precautions on handling negatives, page 315.
Add A
to
B and immediately pour
over the negative to be reduced,
been treated with the special formalin hardener solution (SH-i, page 314). The reducer solution decomposes rapidly after mixing the A and B solutions and therefore should be used at once. When
which has
first
wash thoroughly before dryLocal areas may be reduced with this reducer by applying the
the negative has been reduced sufficiently, ing.
solution with a cotton pad.
This formula
is less
active than
Formula R-4a given below.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
320
Farmer's Reducer
[R-4a]
(For Professional Use)
Stock Solution
Stock Solution B Sodium Thiosulphate (hypo).
Water
.
.
make
to
Metric
Avoirdupois
A
Water Potassium Ferricyanide
16 1}4
ounces ounces
500.0 cc 37.5 grams
16
ounces ounces
480.0
64
grams
2.0 liters
Harden the films or plates first with the special hardener (Formula SH-i, page 314). Then take stock Solution A, i ounce (32 cc), stock
make
Solution B, 4 ounces (128 cc), water to
A
to B, then
which preferably should be contained tive
32 ounces (i liter).
add the water and pour over the negative
When
in a white tray.
Add
to be reduced,
the nega-
has been reduced sufficiently, remove and wash thoroughly.
may
Farmer's reducer
also be used as a two-solution formula
ing the negative in the ferricyanide solution
by
treat-
and subsequently
Almost proportional reduction
the hypo solution.
method.
first
is
in
obtained by this
See Formula R-4b, page 322.
Note: See precautions on handling negatives, page 315.
Modified Belitzski Reducer
[R-8]
and Motion Picture Use)
(For Professional
This reducer well in a tank.
is
the only
known
single solution reducer
recommended
It is especially
which keeps
for treatment of dense,
contrasty negatives. Metric
Avoirdupois
Water (about
125° F.) (52° C.) Ferric Chloride, crystals
.
2'
Sodium
Sulphite, desiccated Citric Acid Sodium Thiosulphate (hypo) to
.
Sodium
6^ ounces
make
Treat the negative
in
1.0 liter
the order given.
used because
it
slows up the rate of reduction.
in the special formalin
page 314) and wash thoroughly.
mum
ounces
32
citrate should not be
ounces ounce grains
290
Dissolve chemicals *
2
1
.
750.0 cc 25.0 grams 75.0 grams 30.0 grams 20.0 grams 200.0 grams
grains
365
*Potassium Citrate
Water
ounces
24
.
hardener (Formula SH-i,
Use the reducer
full
strength for maxi-
reduction.
Immerse the negatives 70°F. (18° to 2i°C.). sired, dilute
I
for
i
to 10
minutes in the reducer at 65° to
Then wash thoroughly.
part of the solution with
i
If slower action is de-
part of water.
For motion picture work, the exhaustion
life
of the solution
150 feet per gallon. Note: See precautions on handling negatives, page 315.
is
about
FORMULARY
321
Iodine-Cyanide Reducer This reducer images because
is it
particularly suitable for extreme reduction of print
does not leave a residual stain. Metric
Avoirdupois
Sodium
or Potassium Cyanide.
.
Water
to
make
5.0 firams
73
tiralns 1}4 fluid ounces
Iodine stock solution
40.0 cc
ounces
32
1.0 liter
Cyanide is a deadly poison and sliould be handled with rul)I)er gloves in a room having good ventilation. The hands should always be washed carefully after use. *
Do not discard this solution into a sink containing acid, or the highly poisonous liydrogen cyanide gas will be formed. Flush it out of the sink (juickly with water.
Iodine Stock Solution Metric
Avoirdupois
Water Potassium Iodide
5
Iodine Crystals Dissolve chemicals
sufficient to
prepare
160.0 cc
i
8.0 8.0
grams grams
the order given.
in
This volume of iodine stock solution is
ounces
110 grains 110 grains
will
keep
for several
months and
gallon (4 liters) of the reducer solution.
After hardening the film with the formalin hardener (Formula SH-r,
page 314) immerse
in the iodine-cyanide solution.
The
reducer acts
similarly to other subtractive formulas but tends to attack the densest
The mixed
solution
and should be used as soon as minute at 65째F. (i8째C.).
possible.
portions slightly faster than the less dense areas. deteriorates rapidly after mixing
Average bleaching time, about Xolc
:
i
See precautions on handling negatives, page 315.
B.
PROPORTIONAL REDUCERS
Persulphate-Permanganate Reducer
[R-5]
(For Professional Use)
Avoirdupois
Stock Solution A
Water Potassium Permanganate Sulphuric Acid Stock Solution
(lO'/r
ounces
1.0 liter
4
grains
0.3 gram 16.0 cc
solution),
yi fluid
ounce
B
Water
Ammonium
Metric
32-
96
Persulphate
3
ounces ounces
3.0 liters
90.0
grams
Treat the negative first in the special formalin hardener (Formula SH-i, page 314) and wash thoroughly. Then take i part of Solution A to 3 parts of Solution B of Formula R-5. When sufficient reduction is secured, the negative should be cleared in a 1% solution of sodium bisulphite.
Wash
the negative thoroughly before drying.
does not keep well enough for motion picture work. Note: See precautions on handling negatives, page 315.
The
solution
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
322
Two
[R-4b]
Solution Farmer's Reducer
(For Professional
and Motion Picture Use)
This formula gives almost proportional reduction and corrects for overdevelopment.
The
which begins
solution,
Solution
solutions also keep to
much
better than the single
decompose almost immediately.
B Sodium Thlosulphate
Metric
Avoirdupois ounces 32
A
Water Potassium Ferrlcyanlde
14,
1.0 liter
ounce
7.5
grams
200.0
grams
Solution
(hypo)
..
6 Ji
.
Water
32
ounces ounces
1.0 liter
After hardening in the special formalin hardener (Formula SH-i,
page 314) and washing thoroughly, the negatives should be immersed in Solution A for i to 4 minutes with uniform agitation 65° to yo^F. (18° to 21° C). Then immerse in Solution B for 5 minutes and wash
The
thoroughly.
process
may
For the reduction of general
be repeated
if
dilute
i
fog,
more reduction
is
part Solution
A
desired.
with
i
part of water.
The
ferricyanide solution will keep indefinitely
daylight.
hypo
If
is
is
shielded from strong
The exhaustion
ferricyanide solution will be shortened.
ricyanide
if
introduced by alternate treatments, the life
life
of the
of the fer-
approximately 300 feet of motion picture film per gallon.
Note: See precautions on handling negatives, page 315.
Ferric
[R-7]
(For
When film
Alum Reducer
Motion Picture Work)
using the following reducer,
it
is
very important to keep the
under the solution surface during reduction as well as during sub-
sequent washing or stains will result. Metric
Avoirdupois
Water Sulphuric Acid, pure cone Ferric Ammonium Sulphate ric
ammonium
Water
When solution
ounces 1)4 fluid ounces
64
to
make
alum)
500.0 cc 10.0 cc
(fer-
2
ounces
1
gallon
15.0
grams
1.0 liter
mixing the solution, be careful to add the acid to the water
and not vice versa or the water
will boil
with explosive violence.
Films should be hardened with the alkaline hardener solution (For-
mula SH-i, page 314) and washed before treatment with the reducer solution. Use the reducer full strength at 65° to 70°F. (18° to 2i°C.).
Wash
thoroughly after treating with the reducer.
FORMULARY
323
The solution keeps indefinitely and has an average exhaustion life of 250 feet per gallon. Care should be taken to avoid contamination with hypo, which reacts with the solution and decreases its keeping life. Note: See precautions on handling negatives, page
315.
SUPER-PROPORTIONAL REDUCERS
C.
Persulphate Reducer
[R-l]
(For Overdeveloped Negatives of Contrasty Subjects)
Stock Solution
Water
Avoirdupois
Metric
ounces ounces
1.0 liter
32
Ammonium
Persulphate Sulphuric Acid, pure cone
2
%
grams
60.0
dram
3.0 cc
Treat the negative in the special formalin hardener (Formula SH-i, page 314) and wash thoroughly. Then take i part stock solution R-i and 2 parts water. When reduction is complete, immerse in an acid fixing bath (F-5, page 310) for a few minutes and wash thoroughly before drying.
If reduction is
too rapid, dilute the solution with a
further volume of water.
Note: See precautions on handling negatives, page 315.
TONING BATHS A. Toning Baths for Lantern Slides, Transparencies, and tion Picture Prints Three distinct methods of toning are possible: 1. Toning by direct development. 2. Toning by replacement of the silver image with inorganic
Mo-
salts
(metal tones). 3.
Toning with dyes (dye tones). I.
The by the
Toning by Direct Development
color of the silver
image produced by development
size of the silver particles
is
composing the image, and
to control the size of these particles
determined
it is
possible
and therefore the color of the image
by modifying the nature of the developer. The developer (Formula D-32) on page 287
will give pleasing
warm
black tones.
The range
of colors obtainable, however,
usually easier and color either
by
more
delicate
is
not very great and
it
is
certain to produce such slight modifications of
dye tinting or by giving a short immersion
of the diluted toning baths.
in
one
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
324
Toning by Replacement
2.
oÂŁ the Silver
Image with
Inorganic Salts Since most toning processes intensify the original silver image,
commence with
best to
the thin side.
a slide or positive print which
is
it
is
somewhat on
Experience will dictate the most suitable image quality
which yields the best
results with the various toning processes.
Stability of Solutions.
â&#x20AC;&#x201D;
All toning baths containing potassium
ferricyanide are sensitive to light, the ferricyanide being reduced to fer-
rocyanide, with the resulting formation of a sludge of the metallic ferro-
When
cyanide.
not in use, tanks should be covered to prevent exposure
and small volumes should be placed in dark brown bottles. also very important that no metallic surface, however small,
to daylight It is
should come in contact with the solutions.
Wooden
with hard rubber faucets should be used.
Motion picture
or stoneware tanks film should
be wound on wooden racks, free of metal pegs. details on toning motion picture film are given in the book and Toning Eastman Positive INIotion Picture Film." *
Complete " Tinting
Uranium Toner
[T-9] (For
Brown
to
Red Tones on
Slides or Films)
Metric
Avoirdupois
Small Scale
Larfte Scale
Uranium
2K pounds
(uranyl) Nitrate
Potassium Oxalate Potassium Ferricyanide
2]^ 1
Ammonium Alum
Hydrochloric Acid,
Water
6 10*^1
solution.
make
to
Dissohe
The
is
fluid
15
85
is
grains grains grains grains
IM drams
ounces
32
gallons
ounces
2.5 grams 2.5 grams 1.0 gram 6.0 grams 5.0 cc 1.0 liter
cliemicals in the order given.
and pale yellow
however, and should he stored
degree of toning
from brown It
77 120
pounds pound pounds
solution should be perfectly clear
light sensitive,
mum
.
35 35
produced
in
in color.
in the dark.
//
is
The maxi-
about lo minutes, the tone passing
to red during this time.
convenient to keep
io%
stock solutions of the constituent chemi-
compounding of a new bath. For motion picture work, 120 gallons of the above bath will tone about 12,000 feet of film without any appreciable change in the tone. A vol-
cals of the
ume
above toning bath
of acid
may
for quick
then be added equal to that originally used, when a may be toned. After toning the second quantity of
further 12,000 feet film, the
bath should be discarded.
After toning, wash for about 10
minutes, though the washing should not be prolonged, especially
water *
is
slightly alkaline since the toned
image
Motion Picture Sales Dept., Eastman Kodak
is
soluble in alkali.
Co., Rochester,
N. Y.
if
the
FORMULARY
325
Sulphide Toner (For Sepia
Potassium Ferricyanide Potassium Bromide Water to make
phite) to
13
grains
0.9 ftram
32
ounces
1.0 liter
1 .0
liter
(not sul-
three times the (|uaiUity of crystal sodium sulphide.
film
for 5 minutes,
(slide)
thoroughly bleached
is
and immersed
until thoroughly toned.
The
oughly
for 10 to 15
tone
much improved by
is
32
make
The well-washed washed
30.0 ftrams 15.0 grams
'2
B
Water
Use
Metric
ounce ounce ounces
1
Sodium Sulphide, fused *
Slides)
Avoirdupois
Solution A
Solution
[T-IO]
Tones on Lantern
in
Solution
B
for
in Solution
about
film (slide) should then be
the addition of a
say, 64 grains per 32 ounces or 4.5
minutes
2
washed thor-
The transparency
minutes before drying.
hypo
little
grams per
A,
of the
to Solution B,
liter.
Sulphide Toner
[T-lOa]
(For Sepia Tones on Motion Picture Film)
Solution
Avoirdupois
.\
Metric
20 pounds 5 pounds 120 gallons
Potassium Ferricyanide Potassium Bromide Water to make
B *Sodium Sulphide, fused
20.0
grams
5.0 grams 1.0 liter
Solution
(not
sulphite)
Water *
Use
to
1
make
ounces
1.7 grams 1.0 liter
positive should be bleached thoroughly after
4 minutes treatment so that the
the film. is
10 V2
three times the quantity of crystal sodium sulphide.
The well-washed
film
pound
120 gallons
in Solution
A
2
to
at 65째 to 7o째F. (18째 to 2i째C.),
image appears uniformly yellow on looking at the back of
Then wash
5
minutes and immerse
thoroughly toned.
A
in Solution
do no harm provided the solution
is
sulphide allowed to settle before use.
boiled
B
until the
sodium sulphide
trace of iron in the
and the precipitated
Wash
will
iron
10 to 15 minutes after
sulphiding and before drying.
[T-U]
Iron Toner (For Blue
Tones on Slides or Films) Metric
Avoirdupois Small Scale Large Scale
Ammonium
impound
Persulphate Iron and .\mmonium Sulphate (ferric
alumj
1
Oxalic Acid
3
Potassium Ferricyanide
1
Ammonium Alum
Hydrochloric Acid, 10%
Water
to
make
pound b}4 ounces pounds pound pounds
5 ISJ^ fluid ounces gallons 120
7
grains
0.5
gram
20
grains grains grains grains
1.4 3.0
grams grams gram grams
45 15
75
M dram 32
Dissolve chemicals in the order given.
ounces
1
.0
5.0 1.0 cc 1.0 liter
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
326
The method
of
compounding
this
bath
very important.
is
Each
of
the soHd chemicals should be dissolved separately in a small volume of
water, the solutions then mixed strictly in the order given, and the whole diluted to the required volume.
bath
will
be pale yellow
Immerse the
If these instructions are followed, the
and perfectly clear. from 2 to 10 minutes at 70°F. (2i°C.)
in color
slides or films
Wash
until the desired tone
is
obtained.
highlights are clear.
A
very slight permanent yellow coloration of the
minutes until the
for 10 to 15
clear gelatin will usually occur, but should be too slight to
on projection.
If the highlights are stained blue,
be detectable
then either the slide
was fogged during development, or the toning bath was
(film)
stale or
not mixed correctly. Since the toned image
soluble in alkali, washing should not be car-
is
ried out for too long a period, especially
if
the water
Life of the Bath for Motion Picture Work.
newed
after toning each 5,000 feet, the bath
feet per
120 gallons (480
is
is
slightly alkaline.
—
If the acid is re-
capable of toning 36,000
liters) of solution.
Mixed Iron and Uranium Tones.
— By mixing the uranium (T-9,
page 324) and iron (T-ii, page 325) toning solutions in different proportions, tones ranging from reddish-brown to chocolate are produced.
Analogous
results
may
be obtained by immersing
in
each solution suc-
cessively for varying times.
Dye Toning
3.
It is
not possible to obtain more than a limited
compounds owing
the use of colored inorganic of such
compounds
available.
number
by number
of tones
to the limited
Certain inorganic compounds, however,
such as silver ferrocyanide can be used as mordants for basic dyes such as Victoria green, safranine, etc.
If,
therefore, a silver
image
is
con-
verted more or less to a silver ferrocyanide image and then immersed in a solution of a basic dye, a
mordanted dye image
is
produced.
Immersion of a silver image in an acid solution of potassium ferricyanide will produce a satisfactory mordant image of silver ferrocyanide but,
if
the image
is
left too
mordanting action of the incorporating uranium
ferrocyanide
is
long in the acid ferricyanide bath, the
silver ferrocyanide
(uranyl)
nitrate
in
image
is
the bath,
destroyed.
By
brown uranyl
deposited along with the silver ferrocyanide which serves
as a signal to indicate
when
the film should be
removed from the mor-
FORMULARY When
danting bath.
brown,
image
if
will not
it
prolonged so that the
is
mordant as
well.
Uranium Mordanting Bath (Uranyl) Nitrate. Oxalic Acid Potassium Ferricyanide
Water
.
.
make
to
[T-17]
Avoirdupois
Stock Solution
Uranium
Directions for Mixing:
Metric
Large Scale
Small Scale
8 pounds 4 pounds 4 pounds 120 gallons
116 58 58 32
The uranyl
and should not contain an excess
to turn
has been formed to mordant basic
the time of immersion
appreciably colored,
is
commences
the black silver image just
sufficient silver ferrocyanide
dyes strongly but,
327
8.0 grams 4.0 grams 4.0 grams 1.0 liter
grains grains grains
ounces
nitrate should be of
of free nitric acid.
chemical separately in a small volume of water.
good quality
First dissolve each
Then add
the oxalic
acid solution to the uranyl nitrate solution and finally add the ferri-
cyanide solution.
If the
brown
ferricyanide, a
uranyl nitrate
readily in the oxalic acid.
and perfectly
clear.
is
added directly
to the
potassium
precipitate will be obtained which will not dissolve
The
After mixing, the bath should be light yellow solution should not be exposed to light
any
more than necessary. For use take
Time to
of
part stock solution and 4 parts water.
i
Mordanting: Immerse the
film (slide) at 65° to 70°F. (18°
2i°C.) until a very slight chocolate colored tone
move
at once.
If
ferior tones will
i^ to
The
2
mordanting
be produced.
minutes but the time
solution
may
is
prolonged
With
will
a
is
obtained and re-
much beyond
new bath
this point, in-
this will require
from
need to be increased as the bath ages.
be revived at intervals by adding a
little
of the con-
centrated stock solution.
Life of Bath.
— For motion picture work,
the bath should be dis-
carded after mordanting 10,000 feet of film per 50 gallons of solution.
Time
of
Washing after Mordanting.
— Wash
until the highlights
are free from yellow stain which usually takes about 10 to 15 minutes.
Do
not prolong the washing for more than 20 minutes or some of the
mordant
An
will
be washed out.
alternative mordanting bath
L. Chalkley, Jr.*
image *
"
is
The
practically colorless
Two
the following formula suggested
by
mordanted
and highly transparent.
Color Transparencies " by
raphy. 43, 23-31 (1929).
is
solution has the advantage that the
Lyman
Chalkley, Jr.
Amcr. Annttal of Photog-
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
328
Metric
Avoirdupois
Copper Sulphate Potassium Citrate, neutral ...
1 ounce 145 grains 8 ounces 165 grains
Glacial Acetic Acid
1
Ammonium
Thiocyanate .... potassium thiocyanate) Water to make (or
fluid
40.0 ftrams 250.0 grams 30.0 cc 25.0 grams
ounce
365 grains (424 grains)
(29.0
32 ounces
1
grams)
.0 liter
Dissolve the copper sulphate, potassium citrate, and acetic acid in
about 8oo cc (26 ounces) of water. in
Dissolve the thiocyanate separately
50 cc (i^ ounces) of water and add to the other solution.
Dilute to
volume.
months without deterioration and may be used With continued use a white flocculent premay appear, but this does no harm. When it begins to work too
This bath
will
keep
for
over again several times. cipitate
slowly,
it
should be discarded.
The Dye Bath
[T-17a]
Avoirdupois Small Scale Large Scale
tDye
1
JAcetic Acid, 10'^ Or Acetic Acid, glacial
Water
it
to
t
For methyl
t
To
make
â&#x20AC;&#x201D;
ounce
140 grains
ounces dye given
in the formula.
grains
â&#x20AC;&#x201D;
drams
1}4,
3}4 fluid ounces 50 gallons
32
violet use one-quarter the quantity of
convert glacial acetic acid into
10%
Metric 0.2 gram 5.0 cc (1.4 cc) 1.0 liter
3
acetic, take
i
part glacial acid and add
slowly to 9 parts water.
Thoroughly dissolve the dye in distilled hot water, dilute to volume with cold water.
and
The
following dyes are suitable for toning:
Safranine
A
filter,
add the acid
:
FORMULARY
329
image does not mordant sufficient wash thoroughly, immerse again in the
after dyeing lo minutes, the
If,
dye, remove the
fihii
(slide),
mordanting bath, wash, and re-dye.
Dye Tones.
Intermediate by mixing
â&#x20AC;&#x201D; Intermediate
the dye solutions or
either
For example,
successive baths.
if
colors
may
by immersing the
a reddish-orange tone
be obtained
film (slide) in is
desired, first
tone for a short time in the safranine bath and then in the chrysoidine bath, or the two baths
may
be mixed
in suitable
proportions and the tone
secured with a single treatment.
â&#x20AC;&#x201D;
It has been found that by omitting the ammonium Double Tones. alum from the iron toning formula, the half tones of the toned slide are white and the shadows blue. If this image is then immersed in any of the basic dye solutions as used for dye toning (Formula T-i7a) the dye is mordanted to the half tones while the shadows remain more or less ,
By
blue.
will.
Double Toning Bath
[T-18] Metric
Avoirdupois
Small Scale
Large Scale
Ammonium
Persulphate Iron and Ammoniuni Sulphate (ferric
J^
alum)
1
Oxalic Acid
3
Potassium Ferricyanide
1
to
The
pound pound 6 J^ ounces pounds pound
15J4 fluid ounces gallons 120
Hydrochloric Acid, lO'l
Water
make
(
Formula T- 1
1
,
grains
0.5
20 45 15
grains grains grains
1.4 grams 3.0 grams 1.0 gram 1.0 cc 1.0 liter
J^i
dram ounces
32
same
as for the iron
page 325).
Tone until the shadows are deep blue. minutes. Immerse in the basic dye solution used
Directions for Use: to 15
toning for tones
is
5 to 15
minutes until the desired depth of color
Wash
obtained.
5 to
The
of the iron toner
(Formula T-ii, page 325).
the double toning bath
Avoirdupois
Acetic Acid (glacial)
Water
to
make
The quantity
dye
in the half
is
the
same
Single Solution Dye Toner *Dye Acetone or Wood Alcohol Potassium Ferricyanide
Then for
10 minutes after dyeing until the high-
lights are clear.
life of
gram
7
instructions for preparing the bath are the
toning bath
wash ID
may
varying the dye solution used, the color of the half tones
be varied at
X
Hi
grains fluid
ounces
as that
[T-20] Metric x
grams
100.0 cc
gram
15 IJi
grains
1.
drams
32
ounces
5.0 cc 1.0 liter
of dye varies according to the dye used as follows
330
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS Tannin Heliotrope
:
FORMULARY B.
Toning Baths
331
for Papers
Hypo Alum Toning Bath (For
Amateur and
[T-la]
Professional Contact Paper)
Avoirdupois
Metric
90 ounces
2800.0 cc 480.0 drams
Cold water Sodium Thiosulphate (hypo)
16
ounces
Dissolve thoroughly, then add the following solution Hot water (about Potassium Alum
160° F. (71° C.))
.
20 4
.
ounces ounces
640.0 cc 120.0 (trams
the following solution (including precipitate), slowly to the
Then add
above hypo-alum solution while
stirring the latter rapidly.
Cold water
2
ounces
64.0 cc 4.2 ftrams 4.2 grams
60 grains 60 grains
Silver Nitrate, crystals Sodium Chloride (table salt)
After combining above solutions,
add water to make
1
gallon
4.0 liters
adding the sodium The and immediately afterwards the solution, including the milky white precipishould be added to the hypo-alum solution as directed.
Note
silver nitrate should be dissolved completely before
:
chloride, tate,
If boiling
changed, or
water if
is
used for mixing, or
the hypo-alum bath
bath
For
pour into a tray standing
use,
(49°C.).
and
way
proper manipulation technique
if
Never use
is
in
at a temperature
impairs the toning action of the used.
a water bath and heat to i20°F.
above i25°F. (52°C.), or
blisters
Prints will tone in 12 to 15 minutes depending
stains will result.
upon the grade
is
when adding the white black. The formation of
precipitate, the bath will turn a dirty gray or
a black precipitate in the bath in no
the order of mixing
if
not stirred
is
of paper.
The bath
will
be milky white
if
properly mi.xed.
Prints should be immersed thoroughly and separated occasionally, The especially during the first few minutes, to insure even toning. from developed and normal than black prints should be slightly denser
i^ to
2
minutes without forcing,
prints are toned, sponge off
one hour
in
running water.
to
any sediment
Soak dry
in
warm water and wash
prints in
Stock Bleaching Solution A Potassium Ferricyanide
*
Potassium Bromide Potassium Oxalate Acetic Acid (28', i Pure) Water To make 28% acetic acid from
8 parts of water.
for
water before toning.
[T-7a]
Sepia Redeveloper (For Chloride
After
produce good sepia tones.
and Bromide Papers) Avoirdupois 2J^ ounces 2 J^
ounces
6 J^ ounces \]4 fluid ounces
Metric "."^O 7.S.0 19.S.0
grams grams grams
40.0 cc 2.0 liters glacial acid with parts dilue acid, glacial acetic 3
64
ounces
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
332
Stock Redeveloping Solution B Sodium Sulphide (not sulphite)
Water To use, prepare
Bleaching Bath Stock Solution A
Water Redeveloper Stock Solution
B
Water
The
ounces ounces
45.0 grams 500.0 cc
16 16
ounces ounces
500.0 cc 500.0 cc
4 32
ounces ounces
125.0 cc
IJ^
will take
about
i
it
and the black
half tones are left
1.0 liter
washed thoroughly.
print to be redeveloped should be
bleaching bath and allow
in the
16
as follows:
Place
it
to remain until only faint traces of the
of the
This
shadows has disappeared.
minute.
Rinse thoroughly
in clean, cold water.
This
Place in redeveloping solution until original detail returns.
will
require about 30 seconds.
Give the print an immediate and thorough
water rinse; then immerse
for 5
minutes
in
a bath composed of F-ia
ounce (32 cc), water 16 ounces (500 cc). Remove the print from this bath and wash for one-half hour in running
hardener (page 309)
i
water.
The
color
and gradation
of the finished print will not be affected
by
the use of the hardener. Note : Do not use trays for bleaching that have any iron exposed. important as exposed iron may be a cause of blue spots.
(For Sepia
The advantage
may
Tones on Professional Contact and Enlarging Papers)
of this toning bath
is
brown
that a variety of excellent
be obtained by varying the time of toning.
The
prints
be removed from the bath at any time when a satisfactory color tained.
them
may
is
ob-
After fixing, wash the prints for a few minutes before placing
in the toning solution.
Metric
Avoirdupois Stock Solution A Warm water (about 130째 F.) (54째 C.) 1 gallon Sodium Thiosulphate (hypo) 2 pounds Ammonium Persulphate 4 ounces
Dissolve the hypo completely before adding the phate.
Stir the
phate.
If the
it
very
is
Nelson Gold Toning Bath
[T-21]
tones
This
bath vigorously while adding the
4.0 liters
960.0 120.0
grams grams
ammonium ammonium
persulpersul-
bath does not turn milky, increase the temperature until
does.
Prepare the following solution and add
it,
including precipitate, slowly
to the hypo-persulphate solution while stirring the latter rapidly.
bath must be cool when these solutions are combined.
The
FORMULARY Cold water
2
Silver Nitrate (crystals) Sodium Chloride (table salt)
Xotc
:
The
335
ounces
64.0 cc S.2 iJrams 5.2 (irams
75 tiralns 75 f^ralns
silver nitrate should be dissolved completely before
adding the sodium
chloride.
Stock Solution
B
Water
For
use,
8 ounces 15 grains
C^hloride
C,o\(i
add 4 ounces (125 cc)
of Solution
250.0 cc
'
1.0 ftrani
B
slowly to Solution
A
The bath should not be used until it and has formed a sediment. Then pour off the clear
while stirring the latter rapidly.
has become cold
Pour the clear solution into a tray standing
liquid for use.
in a
water
The temperature, when toning, should be between 100° and iio°F. (38° and 43°C.). Dry prints bath and heat to iio°F.
(43°C.).
should be soaked thoroughly in water before toning.
Keep
at
hand a black and white print
Prints should be separated at
desired tone
all
for
obtained, rinse the prints in cold water.
is
been toned, return them to the fixing bath I
hour
comparison during toning.
times to insure even toning.
When
After
for 5 minutes, then
all
the
have
wash
for
running water.
in
The bath should be revived at intervals by the addition of gold SoluThe quantity to be added will depend upon the number of prints toned and the time of toning. For example, when toning to a warm brown, add i dram (4 cc) of gold solution after each fifty 8 by 10tion B.
inch prints or their equivalent have been toned. solution
may
A
quantity of fresh
be added from time to time to keep the bath up to the
proper volume.
URANIUM, IRON, AND DYE TONES ON PRINTS Tones on paper may be obtained with uranium (Formula T-17) ranging from chocolate to brick red. as a
mordant bath
tinted unless
it
is
for
dye tones.
This formula
The paper
may
also be used
stock usually becomes
protected by squeegeeing temporarily to another
support coated with rubber cement.
Blue tones
may
be obtained with
an iron toning bath (Formula T-12).
Toned images obtained with these formulas are not absolutely permanent since they consist of a mixture of silver with one or more of the following compounds: silver ferrocyanide, dye, ferric, and uranyl ferrocyanides. On exposure to the atmosphere, which usually contains traces of hydrogen sulphide, the silver and uranyl ferrocyanides are converted to silver or uranyl sulphide which is usually apparent as a metallic
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
334
sheen on the surface of the toned print.
This sulphiding of the image
can be almost completely prevented by varnishing the prints with a nitrocellulose lacquer.
In
these processes, the final tone depends not only on the time of
all
toning but also on the density of the original print.
Iron Toning Bath for Blue Tones
[T-12]
Metric
Avoirdupois Ferric
Ammonium
Citrate
(green 58 58 58 32
scales)
Oxalic Acid, crystals Potassium Ferricyanide Water to make
Dissolve each chemical separately and
Immerse the well-washed print until the desired tone
is
4.0 4.0 4.0
ounces
1.0 liter
before mixing together.
filter
in the toning
obtained.
grams grams grams
grains grains grains
bath for lo to 15 minutes
Then wash
until the highlights are
clear.
Uranium Mordanting and Toning Bath
[T-17]
Stock Solution
Avoirdupois
Metric
116 grains 58 grains 58 grains 32 ounces
8.0 grams 4.0 grams 4.0 grams 1.0 liter
Uranium
Nitrate Oxalic Acid, crystals Potassium Ferricyanide
Water
to
make
Dissolve the uranium nitrate in a small volume of water Dissolve the oxalic acid separately and
i25°F.) (52°C.).
add the oxalic acid solution
to the
uranium
potassium ferricyanide separately;
uranium
and
nitrate
if
the solution
is
clear,
not clear,
If
then
Dissolve the
nitrate solution.
oxalic acid solution.
(about
filter;
add
it
filter
to the
before
mixing together.
For Use as lute
I
a
Toning Bath (Chocolate
part of the stock solution
toning time
is
2
to
The
may
For Use
as a
which usually requires from 10
Mordant for Dye Toning.
(T-17) with 4 parts
to
remove the yellow
i
part stock
minutes until the image turns a
2
Rinse for about stain
— Dilute
to
of water.
Treat the well-washed print about light chocolate color.
— Di-
As the brown and
be removed at any stage.
until the highlights are clean,
15 minutes.
solution
Brick Red).
parts of water.
increased, the tone changes from chocolate to
finally to brick red.
Wash
T-17 with
i
minute or
from the highlights.
15 minutes in the following dye bath:
less in
running water
Then immerse
for 10 to
FORMULARY Dye Bath
335
for Papers
[T-17B]
Avoirdupois
Dye
1000 solution) (1 Acetic Acid, 1% Solution
z fluid 6Ji fluid
:
Water
make
to
Volumes 1
Red
2
Yellow
3
Orange
Tone No.
4
Blue
Tone No.
5
Brilliant
Dye Solution
Safranlne A .\uramlne
ounces
3,'4
cc
x
drams
25.0 cc
ounces
32
of 1: 1000
Tone No. Tone No. Tone No.
Metric
1.0 liter
for Various Colors fluid
314 fluid
ounces ounces
100.0 cc 100.0 cc
Use equal parts of Nos. 1 and 2; then add i'i fluid ounces (100 cc) of the mixed dye solution when preparing the acid dye bath. 100.0 cc 3]^ fluid ounces
Victoria Green
Green
3 '4
Use equal parts of Nos. 2 and 4; then add 3,'i fluid ounces (100 cc) of the mixed dye solution when preparing the acid dye bath. fluid ounces 100.0 cc
5'
fluid
Green
Tone No. Tone No.
6
Blue
7
Violet
Methylene Blue BB Methyl Violet
Mixtures of the
follovk^ing
may
2
drams
20.0 cc
also be used:
Victoria Green plus
Methyl Violet
Victoria Green plus Methylene Blue
Methyl Violet plus Auramine Methyl Violet plus Victoria Green The dye toned print should be washed in running water traneous color is removed from the highlights.
until all ex-
STAIN REMOVERS AND TRAY CLEANERS may
Developer or oxidation stain film for 2 or 3
minutes
be removed by
in the alkaline formalin
page 314), then washing
for 5
first
hardening the
bath (Formula SH-i,
minutes and bleaching
in the following:
Stain Remover for Films and Plates Stock Solution
A
Water Potassium Permanganate. Stock Solution B
..
.
Gold water Sodium Ghlorlde (table salt). Sulphuric Acid, pure cone. .
Water *
Add
to
make
32 75
ounces
1.0 liter
grains
5.2
16 2}4
ounces ounces fluid ounce ounces
H
.
32
the sulphuric acid slowly with stirring or the solution
[S-6]
Metric
Avoirdupois
grams
500.0 cc 75.0 grams 16.0 cc 1.0 liter
may
boil with explosive
violence and burn the hands or face.
For use take equal parts of Solutions
The
A
and B.
solutions should not be added together until ready for immedi-
ate use, since they do not keep long after mixing.
All particles of per-
manganate should be dissolved completely when preparing Solution A, since undissolved particles are likely to produce spots on the negative.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
336
Bleaching should be complete
The brown
minutes at 65째F. (i8째C.).
in 3 to 4
manganese dioxide formed best removed by immersing the negative in a i stain of
in the
%
bleaching bath
sodium bisulphite
is
solu-
Rinse well, expose to sunlight or arclight then develop with any
tion.
non-staining developer such as Formula D-51, page 289, or Formula
D-72
diluted
I
part to
water
parts
2
(page
Then wash
292).
thoroughly.
Warn'mg: Developers containing a high concentration of sulphite, such D-76, are not suitable for redevelopment because the sulphite tends to dissolve the bleached image before the developing agents act upon it.
as
Hand
[S-5]
Stain Remover
Water Potassium Permanganate Solution B Water
]4
amount
the hands with a small
rinse with Solution
A
16
more vigorous
as developer stains
B which stain is
will
1.0 liter
ounce ounces ounces
32
Sodium Bisulphite
Rub
Metric
Avoirdupois ounces 32
Solution A
grams
7.5
1.0 liter
480.0
grams
of Solution A, rinse in water; then
remove the
stains.
remover which acts on most ink stains as well
given in Chapter XII, page 266.
Tray Cleaner
[TC-1]
(For General Use)
Metric
Avoirdupois
Water Potassium Bichromate
32 ounces 3 ounces 3 fluid ounces
Sulphuric Acid, pure cone
Pour a small volume
of the tray cleaner solution in the vessel to be
cleaned.
Rinse the solution around
all parts,
then pour
it
times with water until solution will
some
remove
silver stains
in the vessel so that
it
has access to
out and wash the tray thoroughly six or eight all
traces of the cleaning fluid disappear.
stains caused
and dye
stains,
by oxidation products
and
is
This
of developers,
a very useful cleaning agent.
Tray Cleaner
[TC-2] (For
Solution
Removal
A
Water Potassium Permanganate Sulphuric Acid, pure cone
Add
1.0 liter
90.0 grams 96.0 cc
of Silver Stains)
Avoirdupois 32 73 2.V2
ounces grains
drams
Metric 1.0 liter 5.0 grams
10.0 cc
the sulphuric acid slowly while stirring the permanganate solu-
tion rapidly.
FORMULARY
337
B
Solution
Water
32 145
Sodium Bisulphite
For use pour Solution
A
ounces
1
.0 liter
10.0
(irains
Arams
and allow it to remain for a few Apply Solution B and wash thoroughly. remove most types of stains, but it is especially recinto the tray
minutes, then rinse with water.
This formula
ommended
will
removal of
for the
silver stains.
CLEANING DEEP TANKS Use hypochlorite solution or paste ter
as directed on page 265 of
Chap-
XII.
Reference should also be
made
to
Chapter XII, page 262,
on removal of special types of
tional information
for addi-
stains.
Kodalk Fine Grain Developer (For Use
Water (about
Avoirdupois 96 ounces
125° F.) (52° C.)
Elon
Sodium
grains 290 13J4 ounces grains 116
Sulphite, desiccated ....
Kodalk Potassium Sulphocyanate (Thiocyanate)
58 29
Potassium Bromide Cold water to make
1
Dissohe chemicals
Time
Plates)
Metric 750.0 cc
2.0
grams grams grams
1 .0
gram
5.0
100.0
grains grains gallon
0.5 gram 1.0 liter
in the order given.
of development, 15 to 25 minutes in a tank at 65°F. (18° C.)
Decrease the time about 2o^r for tray
according to the contrast desired. use.
[DK-20]
With Roll Films, Film Packs, Cut Films, and
Develop
underexposures fully for best results.
Replenisher Solution (For Use
[DK-20R]
With Formula DK-20) Metric
Avoirdupois
Water fabout
ounces ounce liH ounces
125° F.) (52° C.)
96
Elon
Sodium
1
Sulphite, desiccated
Kodalk Potassium Sulphocyanate (Thiocyanate)
2
Potassium Bromide Cold water to make
290
grains
ounces, 290
grains grains gallon
58 1
750.0 cc 7.5 100.0 20.0
grams grams grams
5.0 grams 1.0 gram 1.0 liter
Dissolve chemicals in the order given.
Add to the tank as Deep Tank Use.
necessary to maintain constant volume.
A
throughout the developer
given highlight density will be maintained life for
stant temperature provided the
a constant development time at a con-
volume of
repleni.sher
added
is
6 gallons per looo rolls of film (80,000 square inches) processed.
about
PART B. TABLE OF SOLUBILITIES OF PHOTOGRAPHIC CHEMICALS The
following table
ter to
given to serve as a guide
is
solutions of chemicals.
Since a solution
is
a temperature approximating 40° F.,
a stock solution stronger than
is
indicated
when preparing
stock
apt to become cooled in winit is
not advisable to prepare
by the
solubility of the chemi-
cal at this temperature.
Chemicals as supplied commercially under the designation
were used
"
for the determination of the solubility values.
Grams Substance
— Formula
in 100 cc of
Saturated Solution at 40° F. (4.4° C.)
70° F. (21.1° C.)
Acid, Acetic
(CH3COOH)
Mixes in
all
proportions
Acid, Citric
(CH2COOH)2.C(OH)COOH
75
85
Acid, Hydrochloric
HCl
Mixes in
all
proportions
Acid, Oxalic
(COOH)2.2H20
7
14
Acid, Sulphuric
Mixes in
HoSO^
all
proportions
Acid, Tartaric (dextro)
(CHOHCOOH)2.H20 Alum,
70
75
Ammonium
(NH4)2Al2(S04)4.24H20
Alum, Iron
6
15
46
57
6
11
15
20
(Ferric)
(NHj )2Fe2 (804)4. 24 H2O
Alum, Potassium K2AI2 (804)4. 24 HjO Alum, Potassium Chrome K2Cr2 (804)4. 24 H2O Amidol (See Diaminophenol Hydrochloride)
Ammonia NH4OH
Mixes in
Ammonium Bromide NHjBr
50
Ammonium
Carbonate (NH4)2C03.H20
Ammonium
Chloride
NHiCl
Ammonium
Iodide
NH4I
Ammonium
Oxalate (NH4)2C204.H20 Ammonium Persulphate (NH4)28208
Ammonium Thiocyanate or Ammonium Sulphocyanide NH4CNS
Ammonium
Thiosulphate, anhydrous
(NH4)28203
Athenon (para-oxyphenyl glycin) C6H4(OH)(NH.CH2COOH) Borax (Sodium Borate) Na2B4O7.10H,O Boric Acid
H3BO3
all
proportions
C.P."
TABLE OF SOLUBILITIES Grams Substance
— Formula
(See
40° F. (4.4° C.)
Potassium Hydroxide)
Caustic Soda
Sodium Hydroxide)
Copper Sulphate, crystal CuS04.5H,0 Dlaminophenol Hydrochloride (Amidol)
C6H3(OH)(NHO-HCI1, 2, 4) Elon (monomethyl para-aminophenol sulphate) CeH^fOHiiNHCHs .hH:S04(l. 4) Ferric Alum (See Alum, Iron) (Ferric) Ferric Ammonium Citrate
Ferric Chloride
FeCl3.6H;0 Ferrous Sulphate
FeS0,.7H;0 Formalin {ST^c Formaldehyde)
CHoO Glycln
Athenon) Gold Chloride AUCI3.2H0O Hydroquinone (See
CeH4(OH);(l, 4)
Hypo
(See
Iron and (See
Sodium Thlosulphate
Ammonium Alum, Iron)
Sulphate (Ferric)
Kodalk Kodelon (See Para-aminophenol Oxalate) Lead Acetate Pb(CH3C02)o.3H,0 Lead Nitrate
Pb(N03).
Mercuric Chloride HgCl, Para-aminophenol Oxalate (Kodelon) CfHi (OH)(NH,).H(COOH)2(l, 4) Para-oxyphenyl Glycin (See Athenon) Potassium Bichromate
Potassium Bromide
KBr Potassium Carbonate, anhydrous K,C03 Potassium Chloride KCl Potassium Citrate
CHjCOOK ),C. (OH)COOK. H2O Potassium Cyanide
KCN
Potassium Ferrlcyanlde K3Fe(CN),;
Potassium Ferrocyanlde K4Fe(CN)6-3HjO Potassium Hydroxide (Caustic Potash)
KOH
Potassium Iodide KI Potassium Metabisulphlte K.S^Os
Potassium Oxalate
(COOK),.H,0
In 100 cc of
Saturated Solution at
Caustic Potash
(See
339
25
70° F. (21.1° C.)'
340
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS Grams Substance
40° F. (4.4° C.)
Potassium Permanganate
KMnOi
3.25
Pyroftallol (Pyro)
C„H,(OH)3(l, Rochelle Salts (See
2, 3)
Sodium, Potassium Tartrate)
Silver Nitrate
AgNOi Sodium Acetate, anJiydrous
CHjCOONa
Sodium Acetate, crystal CHsCOONa.SH.O Sodium Bicarbonate
(triliydrate)
NaHCO,
Sodium Bisulphite NaHSOi{Na2S,05)
Sodium Borate (See Borax) Sodium Bromide NaBr Sodium Carbonate, anhydrous Na.CO,
Sodium Carbonate, monohydrated
NaXOj
HO
Sodium Carbonate,
crystal
NaoCOi.lOH.O
Sodium Chloride NaCl
Sodium Cyanide
NaCN
Sodium Hydroxide
(caustic soda)
NaOH
Sodium Phosphate, Na,HP0j.l2H,0 Sodium Phosphate,
dibasic, crystal tribasic crystal
NajPOj.liHoO Sodium, Potassium Tartrate (Rochelle NaKC4H^06.4H,0 Sodium Sulphate, anhydrous Na.SOi
Sodium Sulphate,
crystal
Na,SO4.10HoO
Sodium Sulphide, fused NaS Sodium Sulphide, crystal Na,S.9HoO Sulphite, anhydrous Na.SO, Sodium Thiosulphate, crystals (Hypo) Na.S.Oa-SH.O Thiourea
Sodium
N,H,CS Uranyl Nitrate UOo(NOi)2.6H,0 Wood Alcohol
CH,OH
in 100 cc of
Saturated Solution at
— Formula
Salts)
70° F. (21.1° C.)
PART
C. LIST OF MANUFACTURERS OF APPARATUS AND SUPPLIES*
Acid Resisting Paints, See Paints Agitators and Stirrers
New York, N. Y. Mixing Equipment Co., Inc., Rochester, N. Y. New England Tank & Tower Co., Everett, Mass. Alsop Engineering Corp.,
Air Conditioning Apparatus Carrier Engineering Corp., Newark,
N.
J.
Surface Combustion Corp., Toledo, Ohio.
Westinghouse Electric
& Mfg.
Co., E. Pittsburgh, Pa.
York Ice ^Machinery Corp., York, Pa. Alberene Stone Alberene Stone Co., New York, N. Y. Asphalt, See Flooring and Oxygenated Asphalt Johns Manville Sales Corp., New York, N. Y. Balances, See Weighing Equipment Barrels and Drums, Mixing Groca ]\Ianufacturing Co., Chicago,
Lee Metal Products Co., Lalanti
&
Grosjean
IVIfg.
Brick, Acid Resisting,
for
111.
Inc., Pittsburgh, Pa.
Co.,
Woodhaven, N. Y.
Tank Linings
â&#x20AC;&#x201D; See Stoneware
Cement, Waterproof B. F. Goodrich Co., Akron, Ohio (Plastikon)
Cooling Equipment, See Refrigeration Equipment Drums, Mixing, See Barrels
Dyes Bachmeier
&
Co., Inc.,
New
York, N. Y.
DuPont de Nemours Co., Wilmington, Eastman Kodak Co., Rochester, N. Y. E.
I.
Del.
New York, N. Y. New York, N. Y. & Chemical Co., New York,
General Dyestuffs Corp., Grasselli
Chemical Co.,
National Aniline
N. Y.
Enameled Ware Pfaudler Co., Rochester, N. Y.
Fans, See Ventilation * This list of apparatus
and supplies are known
manufacturers represents those firms whose equipment work. Manufacturers not
to be satisfactory for photographic
included are invited to submit details of their products to the authors for possible inclusion in future editions.
342
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
Faucets Crane Co., Chicago,
111.
Standard Sanitary Mfg. Co., Pittsburgh, Pa. Filters
Alsop Engineering Corp.,
Commercial Filtrine
New
York, N. Y.
Filters Corp., Boston,
Mass.
Manufacturing Co., Brooklyn, N. Y.
Jones Manufacturing Co., Boston, Mass. (Small Water Filters)
Karl Kieffer Co., Cincinnati, Ohio.
Wm.
& Sons Co., Oakmont, Pa. D. F. Sperry & Co., Batavia, 111. Flooring, Asphalt Mastic, Concrete, Etc. B. Scaife
Construction supply houses in
all cities.
Flow Meters and Controllers American Instrument Co., Washington, D. C.
Brown Instrument Crane
Co., Philadelphia, Pa.
Co., Chicago,
111.
Davis Regulator Co., Chicago,
111.
Fischer and Porter, Philadelphia, Pa.
Foxboro Instrument Co., Foxboro, Mass. Mason-Neilon Regulator Co., Boston, Mass. Schutte and Koerting, Philadelphia, Pa. Taylor Instrument Co., Rochester, N. Y. Gages, Temperature See Thermometers
—
Glassware Corning Glass Works, Corning, N. Y.
Kimble Glass
Co., Vineland,
N.
J.
Will Corporation, Rochester, N. Y,
Heat Exchangers (Water Heaters Operated by Steam) Elliott Co., Pittsburgh, Pa.
Whitlock Coil Pipe Co., Hartford, Conn.
Hose, Rubber
— See Rubber Equipment
Humidity Control, Hygrometers Newark, N. J. Foxboro Instrument Co., Foxboro, Mass. Carrier Engineering Corp.,
Taylor Instrument Co., Rochester, N. Y. Jars, Stoneware
— See Stoneware
Laboratory Supplies Central Scientific Co., Chicago,
111.
Fisher Scientific Co., Pittsburgh, Pa.
LIST OF A. H.
Thomas
MANUFACTURERS
343
Co., Philadelphia, Pa.
Will Corporation, Rochester, N. Y.
Lacquer, Nitrocellulose Eastman Kodak Co., Rochester, N. Y. (No. 51 19) Mats, Rubber See Rubber Equipment Nickel, Monel, Inconel International Nickel Co., New York, N. Y. Oxygenated Asphalt Standard Oil Company (Any city in the U. S.)
â&#x20AC;&#x201D;
Pails, Corrosion Resisting
N. Y. (Stainless Steel) B. F. Goodrich Rubber Co., Akron, Ohio (Rubber Lined Iron) Lalanti & Grosjean Mfg. Co., Woodhaven, N. Y.
Anti-corrosive ]\Ietal Products Co., Albany,
Paints, Corrosion Resisting
Eastman Kodak Co., Rochester, N. Y. (Kodacoat) Wolf & Dolan, San Francisco, Calif. (Probus) Paints, Rubber Colvulc Rubber Co., Norfolk Downs, Mass. B. F. Goodrich Rubber Co., Akron, Ohio. Piping American Hard Rubber Co., New York, N. Y. A. M. Byers Co., Pittsburgh, Pa. (Wrought Iron) Crane Co., Chicago, 111. (Black and Galvanized Mild Steel) B. F. Goodrich Rubber Co., Akron, Ohio (Rubber Lined Iron) Joseph Stokes Rubber Co., Trenton, N. Plastics, Synthetic,
J.
Laminated Bakelite Corp.,
New
York, N. Y.
Porcelain Equipment Coors Porcelain Co., Golden, Colo.
Pumps,
Corrosion Resisting
Allis-Chalmers Mfg. Co., Milwaukee, Wis.
American Hard Rubber Co., New York, N. Y. A. S. Cameron Steam Pump Works, New York, N. Y. Goulds Pumps, Inc., Seneca Falls, N. Y. Northern Pump Co., Minneapolis, Minn.
Rumsey Pump
Co., Seneca Falls,
N. Y.
Taber Pump Co., Buffalo, N. Y. Worthington Pump & Machinery Corp., New York, N. Y. Refrigeration Equipment Copeland Products, Inc., Mt. Clemens, Mich.
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
344
General Motors Corp., Detroit, Mich. General Electric Co., Schenectady, N. Y.
&
Kellogg Compressor
Manufacturing Corp., Rochester, N. Y.
Halsey W. Taylor Co., Warren, Ohio. Kelvinator Corp., Detroit, Mich.
Westinghouse Electric
&
Manufacturing Co., Pittsburgh, Pa.
Rubber, Equipment and Linings American Hard Rubber Co., New York, N. Y. B. F. Goodrich Rubber Co., Akron, Ohio. Goodyear Tire and Rubber Co., Akron, Ohio. U. S. Rubber Co., New York, N. Y. Scales, See Weighing Equipment Sinks, Laboratory Alberene Stone Co.,
New
York, N. Y.
M.
A. Knight, Akron, Ohio.
U.
S.
New
Stoneware,
York, N. Y.
Skid Platforms, Stackers, Trucks Lewis-Shepard Co., Boston, Mass.
Nutting Truck Co., Chicago,
Softeners, Water
— See ^
111.
Water Softeners
Stainless Steel Allegheny Steel Co., Brackenridge, Pa. Carpenter Steel Co., Reading, Pa. Crucible Steel Co., Syracuse, N. Y. Ingersoll Steel
Ludlum
&
Disc Co., Chicago,
111.
N. Y. Co., Youngstown, Ohio.
Steel Co., Watervliet,
Republic Steel
Midvale Co., Pittsburgh, Pa. U. Stills,
S. Steel
Corp., Pittsburgh, Pa.
Water
Barnstead
Still
&
Sterilizer Co., Inc., Boston,
Precision Scientific Co., Chicago,
Mass.
111.
F. J. Stokes Co., Philadelphia, Pa.
Stirrers, See Agitators
Stoneware, Corrosion Resisting General Ceramics Co.,
New
— Acid Resisting Brick York, N. Y.
Maurice A. Knight, Akron, Ohio. U. S. Stoneware Co., New York, N. Y. General Refractories Co., Philadelphia, Pa.
Alberene Stone Co.,
New
York, N. Y.
LIST OF INIANUFACTURERS
Tanks Metal
—
345
Downingtown Iron Works, Downingtown, Pa. Groen INIanufacturing Co., Chicago,
111.
(Stainless
Steel)
&
Lalanti
Grosjean Corp., Woodhaven, N. Y.
Lancaster Iron Works, Inc., Lancaster, Pa.
Rubber-lined
—
Struthers Wells Co., Warren, Pa. American Hard Rubber Co., New York, N. Y.
B. F. Goodrich Rubber Co., Akron, Ohio.
— Wood —
Stone
See Stoneware
Acme Tank Co., New York, N. Y. Atlantic Tank Co., North Bergen, N. J. Baltimore Cooperage Tank & Tower Co., more, Md. W. E. Caldwell Co., Louisville, Ky. Eagle Tank Co., Chicago, 111. Johnson-Carlson, Chicago,
Balti-
111.
Kalamazoo Tank & Silo Co., Kalamazoo, Mich. New England Tank & Tower Co., Everett, Mass.
Thermometers and Temperature Regulators Bristol Co., W^aterbury,
Brown Instrument
Conn.
Co., Philadelphia, Pa.
Foxboro Instrument Co., Foxboro, Mass. Taylor Instrument Co., Rochester, N. Y.
Trays Eastman Kodak
Co., Rochester,
N. Y.
& Grosjean Corp., Woodhaven, N. Y. Trucks for Moving Chemicals Lalanti
Xutting Truck Co.,
Inc.,
Chicago,
111.
Ventilation, See Air Conditioning Apparatus
Water Filters, See Filters Water Mixers and Temperature Regulators Foxboro Instrument Co., Foxboro, Mass. Fulton Sylphon Co., Knoxville, Tenn. Leonard Rooke Co., Inc., Providence, R. I.
Mason-Neilon Regulator Co., Boston, Mass. Taylor Instrument Co., Rochester, N. Y.
Water Softeners The Cochrane
Corp., Philadelphia, Pa.
346
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS The Permutit
Wm,
B. Scaife
Co.,
&
New
York, N. Y.
Sons Co., Oakmont, Pa.
Water Stills, See Stills Weighing Equipment Christian Becker, Inc., New York, N. Y. Eastman Kodak Co., Rochester, N. Y. (Laboratory Exact Weight Scale Co., Columbus, Ohio. Fairbanks, Morse & Co., Chicago, 111.
Fisher Scientific Co., Pittsburgh, Pa.
Toledo Scale Co., Toledo, Ohio.
Scales)
PART
D. CONVERSION TABLE OF FAHRENHEIT, CENTIGRADE, AND REAUMUR DEGREES F.
348
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS c-i
Si
CI
o
^ry^OO Ml-I
r^
ry!,
^
rt
P ^^
ro
ro
C)
ci
ci
ro
ci
p
w O O
'o
l-l
0|
iiiiWWiiiiM QPPPQPPPQQP
WW pp
II PQ
CI
ai VO^^OvOrl
11
'
c)
CO
O W
5,5,0,0^000
o,
o,
s^
<
<
I
a o > (U
Q
O
PL,
3
o X w Q
2:
I
INDEX OF FORMULAS BY PURPOSE
OO
CO
OOOOO o
fO
oi
Tf ro
00
o
<~<
M M
PQ
rD
OOOOO n M
COO^CC
llll PPPP
l|W II QPP PP
PI
M
CI
,:^
lll^lPM QPQ
Ih^
l^ ;^
349
»o
lo t^
—
n-(
I-
c^i
1-1-.
^ H -
^
-^
^
g
I I—
MMO^ CJs
ri
•>
-C
i
.s
w
w
>j
IH
<u
£
2
.£
,5
o
33 V <u
tfl
2 fc
„,
o
o
D.
-C
^
d:
<u
.S
o^
O
.S
?:;
;==
g-
>
'5
ex
^ Q
il
60
-a
>-.:;«
o
2:3
2 -y •^i5
^
.-
c2
m -
o!^E'
^
p ^ 2^^^-^M
5, iH
2 o
-S
o
^^--pO^^W
—
I.
o
-t:
«•£•!
350
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS OOOOOOO^OOOCOC^O^ CO
'^
^
CI
C)
CN
cj
(N
CM
cj
CT^ cs
C)
OOCOONCOrOrOC^ON C)
CI
CI
W W
H^
o»
ro
a.
W PPQQQPQQQ I
I
I
I
I
I
I
I
I
Q
CO
^
W W W QQQpQQQp I
CO
O
^bO
2S
t3 r-1
££
23
5
t<x-2foo5
o
wwffi;z;;z;i-i
)z;
no G O
,« ID
—
X
-
—
S
-^
t«
o<
c^
222'3 ooo,o :z;;z;;z;|;z; " '-w n3
o
O
>-•
^
=5
I
INDEX OF FORMULAS BY PURPOSE
<
351
352
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS CS
<N
Ol
C)
rO
M
O O C(
vO 00
CS
O
^
c3
:^
INDEX OF FORMULAS BY PURPOSE lO lo VO vO
o
rO
o o o
ro
ro
rO
t^ 00
353
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
354
tKii-ii-i>-it-ii-ii-ii-i "" CO
as
l-H
C
''O
fO
fO
rO
rO
fO
i-iOOr^ ^O
(^
INDEX OF FORMULAS BY PURPOSE iHi-Hi-iro
I
I
1 I
5
c
^5 ^5
H
>-ii-ir)r)<N
I
(i^
I
I
p^ p^
I
e«j
355
c<<NC>i
o
III
;z;
e< p^ pi
I
f^
I
o5
PHOTOGRAPHIC CHEMICALS AND SOLUTIONS
356
O
O^I-ll-IMrj.
S
P-lCl-Hl-ICI
MI^Cll-HMl-ll-l
xn
O
CO
03
pq bjO
O
™
•
o X
O)
c a?
E
1>
'q. 'P
-^
C C
.b '^
'-'
(U
c
c
^
t*
^
m
INDEX OF FORMULAS BY PURPOSE VT)
vO vO VD
357
INDEX Acetone in developers, 223 Acid rinse and acid hardening baths,
Citric acid, substitution for acetic in fixing
baths, 227
145
Acids, precautions when handling, 272 Acids, substitution of, in fixing baths, 227 Activator or alkali in a developer, 117, 122 Aerial fog in developers, 141 Airbells, 143 Alberene stone and slate, 67 Alkali in developers, substitution of, 218220
Alkalis on the skin, effect of, 270 Alloys for construction materials, 56
Aluminum sulphite stains, 232-234 Alums in fixing baths, substitution
of, 225 in developers, 222 in developers, 223 alum in the fixing bath, 226 carbonate in developers, 223
Amines, organic,
Ammonia
Ammonium Ammonium
Apparatus, materials for processing, table of, 51, 74, 75
Apparatus and methods of use, 15 Apparatus and supplies, manufacturers
of,
341
Asphalt concrete flooring over
vi'ood or
con-
hints on, 48
Coated metals, chemical resistivity of, 58 Compressed air, use of, for conveying solutions, 204
Concentrated developers, mixing, Continuous flow systems, 210 Conversion, of formulas Avoirdupois to metric, 6
210
British imperial liquid to metric, 7 I liter: 120 gallon conversion, 8 U. S. liquid to metric, 6 Cooling solutions, methods of, 89 Corrosion, electrolytic, of metals, 53 Covers for tanks, 70 Cyanide, precautions on handling, 271 Cyanide stain remover formula, 246
The
Darkroom, layout of small, 49 Deliquescence, and deliquescent chemicals, 191,
195
129
of,
Balances, types of, 16-17 Benches, construction of laboratory, 46 Bichromate treatment for cleaning trays, hangers, etc., 264 Bisulphite in the fixing bath, 225 Bisulphite, metabisulphite and sulphite in developers, 117 Bisulphite, reaction of carbonate with, 215 Blisters on films and papers, 166 Blue-green chromium stain, 252
Blue stains,
255 in developers, 119, 222 Boric acid in acid hardening fixing baths, 152, 227 British imperial measure, 6-7 Bromide in developers, 120, 224 Brown silver sulphide scum, 248 Brown stains from adhesives, 254 Buckets, rubber, for chemicals, 66
Borax
Caking of chemicals, 23 Calcium salts in water, 100 Carbon dioxide, action of,
on
certain
chemicals, 194
Carbon tetrachloride, precautions on handling, 271-273
Carbonate, sodium, types of, zz'^, Carbonate, substitution of sodium for potassium, 219 Carbonates in developers, 118 Centigrade, conversion of Fahrenheit temperatures to, 79 Centigrade, Fahrenheit, Reaumur degrees, conversion tables, 347 Chemical mixing room, diagram of a, 199-
Developer and ink stains, removal from hands, 266-267 Developer or oxidation stain, 238 Developer stain, local and general, 238, 240 Developer stain, removal of, 241-242 Developer troubles, 137 Developers, general hints on mixing, 123 Developers, index of, by purpose, 348 Developers, mixing less than 5 gallons, 123
Developers, mixing 5 to 500 gallons, 125 Developers, mixing 500 or more gallons, 126 Developers, multiple solution, 128 Developing agent and preservative, technique of mixing, 121
Developing agents, properties of common, 216-217
Developing agents, substitution of, 214 Development, fine-grain, 285 Development, (above 75째 F.) (24째 C), 180 Dichroic fog or green stain, 168, 249 Diluting solutions to volume, i Direct-Flo cooler, 94-95 Dissolving chemicals, 20 Distillation of water, methods of, 106 Double coated films, processing of, in hot weather, 185 Drying photographic materials at high temperatures, 190
Duplicating stained negatives, 241
Dust from powdered chemicals, precautions regarding, 274
Dye Dye
solutions, mixing, 177 stains, 254, 265, 268
Earthenware, glazed, 62
201
Chemical names and abbreviations, 5 Chemical treatment for purification water,
127
Desensitizers, how to mix, 144 Developer components, varying proportions
crete, 44
Automatic processing machines,
Cleaning photographic apparatus, 262 Cleanliness in handling solutions, general
Efflorescence of
no
Chemicals having harmful effect on photographic materials, 192 Chemicals, solubility of photographic, 338 Chemicals, transportation of, 202
Chrome alum fixing baths, 153-158 Chrome alum for potassium alum, Chrome alum hardener bath, 183 Circulating systems, 209
154,
227
191.
and
efflorescent
chemicals,
19s
Electrolytic corrosion of metals, 53 Elon, precipitation of insoluble base, 122 Elon vs. hydroquinone, rates of develop-
ment,
115
Enameled
steel, 58
Fabric membranes for waterproof floors, 42 Fabrics, white and colored, removal of stains from, 267-269
INDEX
359
Fading
Mackie line effects, 135 Manometers, uses of, 213
Fahrenheit, conversion of Centigrade temperatures to, 79 Farmer's reducer, 172 Faucets, piping, pumps, construction mate-
Mastic, material for
of silver images, factors determining, 2j6
rials for, 72
Ferric alum proportional reducer, 172 Fibrous materials, impregnated, 60 Filtering and clarifying solutions, 31 Filters, types of. 32,(7 Filtration of water, methods of, 107
155.
i)oint test,
floor 156
construction, 43
Membranes,
fabric, for waterproof floors, 42 Mctabisulphite, quantities of alkalis re(juired to neutralize, 218
Metal samples, testing corrosion resistance of. 53
Metaphosphate
for prevention
of
calcium
precipitates in developers, loi
Mixers, water, 87 Mixing room, layout of solution, 40
Fine-grain development, 285
Fixing Fixing Fixing Fixing Fixing
Melting
bath, substitution in the, 225
Molybdenum-stainless
bath troubles. 164 baths, technique of mixing, 14S-157
Monckhoven intensifier, 173 Monohydrated sodium carbonate,
baths, testing, 159 baths, properties and useful life
Mottle produced in developers, in fixing of,
baths,
steel, 56
223
142, 169
160
Flash lamps and flash powders. 274 Floor construction for chemical mixing rooms and darkrooms, 41
Nitre cake or sodium bisulphate, 228 Non-hardening fixing baths, 148
Flow meters, types of, 212 Fog in developers, methods
Opalescent stains, 234 Outlet, hard-rubber for storage tank, 197 Oxidation or develojicr stains, 238, 240, 262 Oxygen, action of, on certain chemicals,
of prevention
of. i3--"39
Formaldehyde-sulphite reaction, 120, 182 Formalin as a hardening agent in developers, 182-183
Formalin, hardener formula, 234 Formalin, precautions on handling, 272 Formula index, by purpose, 348 Fungus, slime, mold, etc., removal from tanks, 265
271
Glass, apparatus made from, 60 Glass-enameled steel, 58 Green stain from chrome alum, removal
of,
183 clips,
cleaning with acetic acid,
264
Hardener rinse baths, 146 Hardener solutions, mixing.
157
Heater, low pressure steam water, 85-86
Hot weather troubles,
187
green stain, scum, 189 reticulation, blisters, sulphur
sludge,
188
Hydrolysis of alkalis, 218 Hydrometers, value of, for testing. 12 Hydroquinone sulphonates in developers, 133
Hydrosulphite as a fogging agent, Hypo, rate of fixation, 149 test solution,
141
cals, 228
Ink and dye stains, 255, 266 Ink eradicator, for stain removal.
269
Iodide as a restrainer in developers, 224 Iodine-cyanide reducer, 173 Iron toning bath, 176 in developers. 119-131, 222 tropical developer (DK-is), 182
Lead acetate
for
59
prevention of sulphide
fog, 102
Life of developers, without use, with use, 132, 134
Life, useful, of fixing bath, 160
stain. 242
Persulphate reducer, 170 pH. of various alkalis in developers, 118 Phosphate treatment for cleaning trays, hangers, etc., 264 Photofinishers' chemical mixing room, 199 Piping, pumps, faucets, construction materials for, 72
for.
224
Preservative in developers,
116, 215
Pumps, 206 Pumps, piping, faucets, construction materials for. 72 in negatives, 114
Pyro stain
Pyro-staining developer, 244 scale of temperature, conversion table, 79, 347
Ice, dry, for cooling purposes, 92 Impurities in developing and fixing chemi-
Lacquered and painted metals, Laminated metals. 60
Permanganate
Reaumur
159
Hypo-alum toning bath, 173 Hypochlorite treatment, 265
Kodalk Kodalk
Paraformaldehyde in developers, 223 Parts, meaning of, 11 Paste, brown stains caused by, 254 Percentage solutions, definition of, 8 Permanganate reducer, 171
Porcelain and glazed earthenware, 62 Potassium salts, substitution of sodium
fog. dichroic. 187
Hypo
for,
214
Paraffined wood. 62
Gases and liquids, precautions on handling,
Hangers or
193
Paddles, mixing. 26 Painted and lacquered metals, 59 Para-aminophenol, substituting Elon
Recirculating system for automatic processing machines, 20 Recording thermometers, 83-85 Reducing or developing agent, 1:4 Refrigerating equipment. Deep tanks of 10 to 150 gallons capacity, 95
Large machines of
100 to 500 gallon capacity, 98 of 5 to 10 gallon capacity, 94
Tanks
Refrigeration, mechanical, 93 Replenishment of developers, 136 Restrainer or bromide in developers, 120 Restraining effect of developer reaction products. 134 Reticulation of gelatin, :8o Rinse baths, acid, 145 Rubber buckets, 66 Rubber, nitrocellulose and asphaltum materials. 62
Rubber-lined tanks,
64, 201
INDEX
360 Saturated solution, Scales, types of, 15
Scum on
Sulphites and bisulphites in developers, in
i
fixing baths, 117, 225
developers, on fixing baths,
138,
Scum, removal 263
Silver intensifier, 174 Silver stain, yellow, 245 Silver stains, removal from hands, 266 Silver sulphide deposits, removal of, from apparatus, 263 Silvery-white opalescent stains, 235 Sinks, construction of laboratory, 46 Siphons, 208 Skin irritation from metol and amidol, 274, 275
Slate and alberene stone, 67 Sludge, suction device for removing from developer, 35 Sludging of the fixing bath, 164 Soapstone (alberene stone) tanks, 67 Sodas, desiccated and crystal, 223 Sodium salts, substitution of potassium for, 224
Solubility, definition of, Solute, definition of, i
i
Solution conveyance, 203 Solution storage, small volume, large vol-
ume.
hydroqui-
di.-)
Sunlight, action
of,
on certain chemicals,
195-198
Superhardener for bromide papers, 169 Swelling and contraction of films during processing, 179
Sylphon water mixer, 88 Systems of measurement-units volume, 2
rials for, 72
images, usefulness and control
of
mass and
Tank, cooling installation for a deep, 96 Tanks, deep, for motion picture and photofinishing work, 69
Temperature coefficient, 80 Temperature conversion table, 347 Temperature measurement and control, 79 Temperatures, handling solutions at high, 178.
Testing fixing baths for films, for prints, 159, 162
Testing a mixed developer, 132 Thermometers, types of, 82-84 Thiourea stain remover formula, 252 Transportation of chemicals, 202 Trays, small tanks, etc., materials for construction
of.
68
Trisodium phosphate,
196, 198
Solvent, definition of, i Solvent fog in developers, 141 Sprockets, tubes, idlers, construction mate-
131.
ttse
in
developers,
222
Troubles, fixing bath, 164
Troughs for reel development, Two-bath developers, 129
72
of,
Vegetable matter, stains from, 255
242-244
Stain
and
(mono-
Sulphur stains, 234
of, 40
Sea water, suitability of, for washing, 112 Silver deposits, removal of, from apparatus,
Stain
Sulphonates none, 133
108
removal from hands and clothing,
266-267
Stain, yellow in developers, 142 Stainless steel, 18-8 molybdenum mixing tanks, 205 Stainless steels, properties of, 56 Recommendation for various types of
equipment
Welds
in.
7;}.
(table), 74-75 76
Stains, classification table, 258 Steam water heater, 85-86 Stirring solutions, methods of, 24-28
tion, etc., on, 100-106 of a
338
181
140
Sulphite in developers, 116 Sulphite, sodium, types of. 224 Sulphite, solvent action of, 116
163
87
chemical analysis
of the. 112
Storage room for chemicals, rgi Substitution of chemicals, 214 Sulphate, use of sodivim, in developers.
Sulphide fog, prevention and removal,
Water mixers,
Waterproofing floors for chemical mixing rooms and darkrooms. 41 Water softening, methods of, 110 Water supply, effect of. development, fixa-
Water supply, value
Stirring, theory of, 28 Stock solutions. 13 Stock solutions of chemicals, solubility of,
Sulphide stain, yellow silver, 246 Sulphide test for fixation of prints, Sulphide toning bath, 176
Wash water temperature, importance of, 99 Water, impurities in, 100 Water heater, low pressure steam, 85-86
102,
Weighing devices, types of. 14 Weighing and measuring, 18 Welding stainless steels, 76 White stains, 232 Winchester measure, 7 Wood, as a construction material,
61
Yellow silver stain, 245 Yellow silver sulphide stain. 246 Yellow stain in developer, 142 Yellow stains on glossy prints, 253 Yellowish-brown iron rust stains.
248
Yellowish-white opalescent stains, 234 Yellowish-white stains, 236 Zeolite treatment for softening water, 110
,1,:;
!fii((!l';ii';;;;'vi|
'mm