PlasticsTechnology Handbook
ManasChanda
CRCPress
Taylor&FrancisGroup
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LibraryofCongressCataloging-in-PublicationData
Names:Chanda,Manas,1940-author.
Title:Plasticstechnologyhandbook/ManasChanda.
Description:Fifthedition.|BocaRaton,FL:CRCPress,Taylor&Francis,2018.|Series:Plastics engineeringseries|Includesbibliographicalreferences.
Identifiers:LCCN2017035500|ISBN9781498786218(hardback:acid-freepaper)|ISBN 9781315155876(ebook)
Subjects:LCSH:Plastics. Classification:LCCTA455.P5C462018|DDC668.4–dc23 LCrecordavailableathttps://lccn.loc.gov/2017035500
VisittheTaylor&FrancisWebsiteat http://www.taylorandfrancis.com
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DedicatedtothehallowedmemoryofmyfatherandmentorNarayanChanda (1911–2005),arenownedauthorandadecoratedteacher,whoshowedbyexample thevalueofdedicationandperseveranceinacademicpursuits.
http://taylorandfrancis.com
CharacteristicsofPolymersandPolymerizationProcesses
1.1WhatIsaPolymer?....................................................................................................................................1
1.2MolecularWeightofPolymers.............
1.2.1Number-AverageMolecularWeight(
1.2.1.1End-GroupAnalysis.....................................................................................................3
1.2.1.2Ebulliometry(Boiling-PointElevation)................
1.2.1.3Cryoscopy(Freezing-PointDepression).................
1.2.2Weight-AverageMolecularWeight(
1.2.2.1Light-ScatteringMethod..............................................................................................7
1.2.2.2Low-AngleLaserLightScattering(LALLS)...........
1.2.3Viscosity-AverageMolecularWeight(
1.2.4PolydispersityIndex...............
1.2.4.1GelPermeationChromatography............
1.4.1ProcessCharacteristics..............
1.4.1.1Bulk,Solution,andSuspensionPolymerization.......
1.4.1.3MicroemulsionPolymerization.............
1.4.2IndustrialPolymerization...............
1.4.2.1HeatRemoval..............................................................................................................49
1.4.2.2ReactorAgitation...............
1.4.2.3ResidenceTime...............
1.4.2.4IndustrialReactors.....................................................................................................51
1.5Con
1.10.2RegionsofViscoelasticBehavior..............
1.10.3FactorsAffecting T
1.10.3.1ChainFlexibility......................................................................................................70
1.10.3.2StericEffects.............
1.10.3.3ConfigurationalEffects...........................................................................................71
1.10.3.4EffectofCross-Linking..........................................................................................71
1.10.4.3Tacticity.................
1.10.4.4Branching,ChainFlexibility,andMolecularWeight.....................................74
1.10.5Relationbetween
1.11DesigningaPolymerStructureforImprovedProperties........
1.16.1ChemicalDeterioration..............
1.17.1AntioxidantsandRelatedCompounds..............................................................................109
1.17.2ChemicalStructuresofAntioxidants..................................................................................110
1.17.3StabilizationofSelectedPolymers............
1.17.3.1Polypropylene.........................................................................................................112
1.17.3.2Polyethylene............................................................................................................114
1.17.3.3Polystyrene..................
1.17.3.4Acrylonitrile
1.17.3.6Nylons..............
1.17.3.7ThermoplasticElastomers...................................................................................116
1.17.3.8Polyacetal.................................................................................................................117
1.17.3.9Poly(VinylChloride).................
1.17.3.10Rubber......................................................................................................................118
1.18MetalDeactivators..................................................................................................................................119
1.19.1.4Free-RadicalScavengers..................
1.20LightStabilizersforSelectedPlastics.................................................................................................128
1.20.8Polyurethanes................
1.20.9Polyamides................................................................................................................................131
1.24.3.3AntistaticAgentsContainingSulfur.................................................................146 1.24.3.4Betaine-TypeAntistaticAgents..........................................................................147 1.24.3.5NonionicAntistaticAgents...............
1.25.3Halogen–AntimonySynergeticMixtures...........................................................................149
1.25.4IntumescentFlameRetardants.............................................................................................150
1.29.1PlasticDevicesinPharmacyandMedicine.......................................................................153
1.29.1.1Packing....................................................................................................................153
1.29.1.2TubingsandBloodBagAssemblies...........
1.29.1.3Implants...................................................................................................................154
1.29.1.4Adhesives.................................................................................................................154
1.29.2BiodegradablePlasticsandBioplastics..........
1.29.3Oxo-BiodegradablePlastics...................................................................................................156
1.29.4ToxicityofPlasticCombustionProducts..........................................................................157
1.29.5ToxicityTesting...............
2 FabricationProcesses
2.1TypesofProcesses...............
2.2ToolingforPlasticsProcessing............................................................................................................161 2.2.1TypesofMolds..............
2.2.2TypesofDies..............
2.3CompressionMolding................
2.3.1OpenFlash.................
2.3.2FullyPositive............................................................................................................................165
2.3.3Semipositive............
2.3.4ProcessApplicability.............
2.4.1EjectionofMolding..................
2.4.2HeatingSystem.................
2.4.3TypesofPresses.......................................................................................................................169
2.4.4Preheating...............
2.4.5Preforming..............
2.4.6FlashRemoval...........................................................................................................................170
2.5InjectionMoldingofThermoplastics..............
2.5.1TypesofInjectionUnits................
2.5.2ClampingUnits........................................................................................................................172
2.5.3Molds.................
2.5.3.1MoldDesigns................
2.5.3.2NumberofMoldCavities......................................................................................175
2.5.3.3Runners..............
2.5.3.4Gating..............
2.5.3.5ValveGates...............................................................................................................178
2.5.3.6Venting..............
2.5.3.7PartingLine..................
2.5.3.8Cooling.......................................................................................................................179
2.5.3.9Ejection..............
2.5.3.10StandardMoldBases................
2.5.4StructuralFoamInjectionMolding.....................................................................................180
2.5.5Co-Injection(Sandwich)Molding............
2.5.6Gas-AssistedInjectionMolding................
2.6InjectionMoldingofThermosettingResins.....................................................................................182
2.6.1Screw-InjectionMoldingofThermosettingResins.........
2.7Extrusion...............
2.7.1ExtruderCapacity....................................................................................................................186
2.7.2ExtruderDesignandOperation.............
2.7.2.1TypicalScrewConstruction.............
2.7.2.2ScrewZones..............................................................................................................
2.7.2.5ScrewDesign...............
2.7.3Multiple-ScrewExtruders.....................................................................................................189
2.7.4Blown-FilmExtrusion...........................................................................................................190
2.7.5FlatFilmorSheetExtrusion.............
2.7.6PipeorTubeExtrusion........................................................................................................194
2.8.1ExtrusionBlowMolding.................
2.9Calendering..............
2.11ElectrospinningofPolymerNano
2.12.3MechanicalForming.............................................................................................................210 2.13CastingProcesses..................................................................................................................................210 2.13.1SimpleCasting.................
2.13.2PlastisolCasting.....................................................................................................................210
2.13.2.1DipCasting..........................................................................................................212
2.13.2.2SlushCasting..............
2.13.2.3RotationalCasting..............................................................................................213
2.14ReinforcingProcesses...........................................................................................................................213
2.14.1MoldingMethods...............
2.14.1.1HandLay-UporContactMolding................................................................214
2.14.1.2Spray-Up..............................................................................................................215
2.14.1.3MatchedMetalMolding............... ...........215
2.14.1.4Vacuum-BagMolding.......................................................................................216
2.14.1.5Pressure-BagMolding.......................................................................................216
2.14.1.6FilamentWinding.............. ........217
2.14.1.7Pultrusion.............................................................................................................
2.14.1.8PrepregMolding.................................................................................................220
2.14.2FibrousReinforcements.............. ...223
2.14.2.1GlassFibers..........................................................................................................223
2.14.2.2Graphite/CarbonFibers,theBeginning........................................................224
2.14.2.3ManufactureofGraphite(Carbon)Fibers......... ........225
2.14.2.4Graphite/CarbonFibersandFabrics.............................................................227
2.14.2.5Graphite/CarbonFiber-ReinforcedPlastics.................................................229
2.14.2.6ManufactureofCFRPParts................. ........230
2.14.2.7ApplicationsofCFRPProducts......................................................................231
2.14.2.8AramidFibers.....................................................................................................234
2.14.2.9Applications.........................................................................................................235
2.14.2.10Extended-ChainPolyethyleneFibers.............................................................235
2.15ReactionInjectionMolding................
2.15.1Machinery...............................................................................................................................238
2.15.2Polyurethanes.........................................................................................................................239
2.15.3Nylons................
2.16StructuralReactionInjectionMolding..............................................................................................240
2.16.1Applications............................................................................................................................241
2.17ResinTransferMolding................
2.18FoamingProcesses..................................................................................................................................242
2.18.1RigidFoamBlowingAgents...............................................................................................244
2.18.2PolystyreneFoams..............
2.18.2.1ExtrudedPolystyreneFoam.............................................................................244
2.18.2.2ExpandablePolystyrene....................................................................................245
2.18.2.3StructuralFoams.............
2.18.3PolyolefinFoams...................................................................................................................246
2.18.4PolyurethaneFoams.............................................................................................................251
2.18.4.1FlexiblePolyurethaneFoams...........
2.18.4.2RigidandSemirigidFoams..............................................................................254
2.18.5FoamedRubber.....................................................................................................................255
2.18.6EpoxyResins...............
2.18.7Urea-FormaldehydeFoams.................................................................................................256
2.18.8SiliconeFoams.......................................................................................................................257
2.18.9PhenolicFoams................
2.18.10Poly(VinylChloride)Foams..............................................................................................258
2.18.11SpecialFoams........................................................................................................................261
2.19RapidPrototyping/3DPrinting..................
2.20RubberCompoundingandProcessingTechnology.......................................................................265
2.20.1CompoundingIngredients..................................................................................................265
2.20.1.1ProcessingAids..............
2.20.1.2Fillers....................................................................................................................269
2.20.2MasticationandMixing......................................................................................................270
2.20.2.1OpenMill...............
2.20.2.2InternalBatchMixers.......................................................................................271
2.20.3ReclaimedRubber.................................................................................................................272
2.20.4SomeMajorRubberProducts..............
2.20.4.1Tires.......................................................................................................................274
2.20.4.2BeltingandHoses...............................................................................................276
2.20.4.3CellularRubberProducts..............
2.21MiscellaneousProcessingTechniques................................................................................................278
2.21.1CoatingProcesses..................................................................................................................278
2.21.1.1FluidizedBedCoating...............
2.21.1.2SprayCoating......................................................................................................280
2.21.1.3ElectrostaticSpraying........................................................................................280
2.21.1.4SmartCoatings.............
2.21.1.5ElectrograftedCoatings.....................................................................................285
2.21.2PowderMoldingofThermoplastics.................................................................................287
2.21.2.1Static(Sinter)Molding..............
2.21.2.2RotationalMolding............................................................................................287
2.21.2.3CentrifugalCasting............................................................................................288
2.21.3AdhesiveBondingofPlastics............................................................................................288
2.21.3.1SolventCementing............................................................................................289
2.21.3.2AdhesiveBonding..............
2.21.3.3JoiningofSpecificPlastics...............................................................................292
2.21.4Welding..................................................................................................................................294
2.21.4.1Hot-GasWelding...............
2.21.4.2FusionWelding..................................................................................................295
2.21.4.3FrictionWelding................................................................................................295
2.21.4.4High-FrequencyWelding...............
2.21.4.5UltrasonicWelding...........................................................................................296
2.21.5JoiningPolymer
2.22DecorationofPlastics..................
2.22.1Painting..................................................................................................................................299
2.22.2Printing..................................................................................................................................300
2.22.2.1GravurePrinting..............
2.22.2.2Flexography........................................................................................................300
2.22.2.3ScreenProcessPrinting....................................................................................300
2.22.2.4PadPrinting................
2.22.2.5FlexPrinting.......................................................................................................301 2.22.3HotStamping.......................................................................................................................301 2.22.4In-MoldDecorating..............
3.2.1StressandStrain..............
3.2.2Stress
3.2.3ViscoelasticBehaviorofPlastics...........................................................................................313
3.2.3.1ModulusandCompliance.............
3.2.4Stress
3.2.4.1TheWLFEquations................................................................................................316
3.2.5CreepBehavior................
3.2.6MaxwellModel................
3.2.6.1Stress
3.2.6.2GeneralizedMaxwellModel...............
3.2.7KelvinorVoigtModel..................
3.2.7.1Stress
3.2.8Four-ElementModel...............
3.2.9ZenerModel...............
3.2.10SuperpositionPrinciple...........................................................................................................326
3.2.11IsometricandIsochronousCurves..............
3.2.12PseudoelasticDesignMethod.................
3.2.13EffectofTemperature..............................................................................................................330
3.2.14Time–
3.2.15DynamicMechanicalProperties...............
3.2.16RheologicalBehavior..............................................................................................................334
3.2.16.1ClassificationofFluidBehavior.........................................................................335
3.2.16.2EffectofShearRateonViscosity...........
3.2.16.3EffectofMolecularWeightonViscosity.........................................................338
3.2.16.4EffectofTemperatureonPolymerViscosity..................................................339
3.2.16.5EffectofPressureonViscosity...............
3.2.16.6WeissenbergEffects...............................................................................................340
3.2.16.7IrregularFloworMeltFracture.........................................................................340
3.2.17MeasurementofViscosity.................
3.2.17.1RotationalViscometers........................................................................................342
3.2.17.2CapillaryRheometers...........................................................................................343
3.2.18PlasticsFractures.............
3.2.19ImpactBehaviorofPlastics...................................................................................................345
3.2.20FatigueofPlastics....................................................................................................................348
3.2.21Hardness..............
3.2.22IndentationHardness.............................................................................................................351
3.2.22.1BrinellHardnessNumber...................................................................................351
3.2.22.2VickersHardnessNumber.............
3.2.22.3KnoopHardnessNumber...................................................................................352
3.2.22.4RockwellHardnessNumber...............................................................................352
3.2.22.5BarcolHardness..............
3.2.22.6DurometerHardness............................................................................................353
3.2.23ReboundHardness..................................................................................................................354
3.2.24ScratchHardness.............
3.2.25StressCorrosionCrackingofPolymers.............................................................................356 3.3ReinforcedPlastics..................................................................................................................................356
3.3.1TypesofReinforcement.................
3.3.2TypesofMatrix........................................................................................................................357
3.3.3AnalysisofReinforcedPlastics.............................................................................................357
3.3.3.1ContinuousFibers............
3.3.3.2DiscontinuousFibers..............................................................................................360
3.3.3.3FiberLengthLessthan
3.3.3.4FiberLengthEqualto
3.3.3.5FiberLengthGreaterthan
3.3.4DeformationBehaviorofFiber-ReinforcedPlastic..........................................................364
3.3.5FractureofFiber-ReinforcedPlastics..........
3.3.5.1Tension......................................................................................................................365
3.3.5.2Compression.............................................................................................................
3.3.5.3FlexureorShear..............
3.3.6FatigueBehaviorofReinforcedPlastics..............................................................................366
3.3.7ImpactBehaviorofReinforcedPlastics..............................................................................366
3.4ElectricalProperties.............
3.4.1DielectricStrength...................................................................................................................367 3.4.2InsulationResistance...............................................................................................................368
3.4.3ArcResistance................
3.4.4DielectricConstant..................................................................................................................370
3.4.4.1PolarizationandDipoleMoment........................................................................372
3.4.4.2DielectricConstantversusFrequency............
3.4.4.3DielectricConstantversusTemperature............................................................374
3.4.4.4DielectricLosses.......................................................................................................375
3.4.4.5DielectricLossesofPolarPolymers....................................................................376
3.5OpticalProperties................
3.5.1OpticalClarity..........................................................................................................................377
3.5.2IndexofRefraction..................................................................................................................378
3.5.3PipedLightingEffect................
3.5.4Stress-OpticalCharacteristics................................................................................................380
3.6ThermalProperties................................................................................................................................381
3.6.1Speci
3.6.2ThermalExpansion.................................................................................................................382
3.6.3ThermalConductivity.............................................................................................................382
3.6.4TransitionTemperaturesandTemperatureLimitations.................
3.6.5StandardPropertiesofPlastics.............................................................................................384
3.7IdentificationofCommonPlastics.....................................................................................................384
3.7.1BehaviorsonHeatingandIgnition...........
3.7.2TestsforCharacteristicElements.........................................................................................395
3.7.3Specifi
3.8PlasticsAnalysisbyInstrumentalMethods............
3.8.1IRSpectroscopy........................................................................................................................402
3.8.1.1MethodsofMeasurement......................................................................................403
3.8.1.2Instruments................
3.8.1.3SamplePreparation.................................................................................................404
3.8.1.4FourierTransformIRSpectroscopy....................................................................406
3.8.1.5QualitativeAnalysis............
3.8.1.6QuantitativeAnalysis..............................................................................................415
3.8.2NMRSpectroscopy..................................................................................................................417
3.8.2.1GeneralPrinciples............
3.8.2.2ChemicalShift..........................................................................................................421
3.8.2.3ShieldingMechanisms............................................................................................423
3.8.2.4Spin–SpinCoupling...............
3.8.2.5ApplicationsinPolymerAnalysis.......................................................................426
4 IndustrialPolymers
4.1Introduction.............................................................................................................................................433
4.2PartI:AdditionPolymers................
4.2.1Polyole
4.2.1.1Polyethylene..............................................................................................................435
4.2.1.2Polypropylene..................
4.2.1.3Polyallomer................
4.2.1.4Poly(VinylChloride)..............................................................................................448
4.2.1.5Poly(VinylideneChloride)................
4.2.1.6PolytetrafluoroethyleneandOtherFluoropolymers.................
4.2.1.7Polyisobutylene........................................................................................................461
4.2.1.8Polystyrene.................
4.2.1.9Polybutadiene(ButadieneRubber)...............
4.2.1.10Polyisoprene..............................................................................................................463
4.2.1.11Polychloroprene................
4.2.2OlefinCopolymers...................................................................................................................464
4.2.2.1Styrene–ButadieneRubber....................................................................................464
4.2.2.2NitrileRubber............... 465
4.2.2.3Ethylene–PropyleneElastomer.............................................................................465
4.2.2.4ButylRubber............................................................................................................. 467
4.2.2.5ThermoplasticElastomers................
4.2.2.6Fluoroelastomers......................................................................................................470
4.2.2.7Styrene–AcrylonitrileCopolymer........................................................................472
4.2.2.8Acrylonitrile–Butadiene–StyreneTerpolymer.............. ........472
4.2.2.9Ethylene–MethacrylicAcidCopolymers(Ionomers)......................................474
4.2.3Acrylics.......................................................................................................................................475
4.2.3.1Polyacrylonitrile................
4.2.3.2Polyacrylates.............................................................................................................476
4.2.3.3Polymethacrylates....................................................................................................477
4.2.3.4Polyacrylamide................ ........479
4.2.3.5Poly(AcrylicAcid)andPoly(MethacrylicAcid)..............................................480
4.2.3.6AcrylicAdhesives....................................................................................................481
4.2.4VinylPolymers.................
4.2.4.1Poly(VinylAcetate).................................................................................................482
4.2.4.2Poly(VinylAlcohol)................................................................................................483
4.2.4.3Poly(VinylAcetals).............
4.2.4.4Poly(VinylCinnamate)..........................................................................................485
4.2.4.5Poly(VinylEthers)...................................................................................................485
4.2.4.6Poly(VinylPyrrolidone)................. ........486
4.2.4.7Poly(VinylCarbazole)............................................................................................486
4.3PartII:CondensationPolymers..........................................................................................................486
4.3.1Polyesters............. ...................487
4.3.1.1Poly(EthyleneTerephthalate)...............................................................................487
4.3.1.2Poly(ButyleneTerephthalate)...............................................................................488
4.3.1.3Poly(DihydroxymethylcyclohexylTerephthalate).......... ........490
4.3.1.4UnsaturatedPolyesters...........................................................................................491
4.3.1.5AromaticPolyesters................................................................................................497
4.3.1.6WhollyAromaticCopolyester............ ........499
4.3.1.7Polycarbonates.........................................................................................................500
4.3.2Polyamides.................................................................................................................................503
4.3.2.1AliphaticPolyamides............. ........503
4.3.2.2AromaticPolyamides..............................................................................................511
4.3.2.3Polyimides.................................................................................................................513
4.3.3FormaldehydeResins............... ......519
4.3.3.1Phenol–FormaldehydeResins...............................................................................519
4.3.3.2Urea–FormaldehydeResins...................................................................................524
4.3.3.3Melamine–FormaldehydeResins............... ........527
4.3.4Polyurethanes............................................................................................................................529
4.3.4.1PolyurethaneRubbersandSpandexFibers.......................................................529
4.3.4.2FlexiblePolyurethaneFoam............. ...........534
4.3.4.3RigidandSemirigidPolyurethaneFoams.........................................................535
4.3.4.4PolyurethaneCoatings...........................................................................................536
4.3.5EtherPolymers................. ............537
4.3.5.1Polyacetal...................................................................................................................538
4.3.5.2Poly(EthyleneOxide)..............................................................................................540
4.3.5.3Applications..............................................................................................................541
4.3.5.4Poly(PropyleneOxide)...........................................................................................544
4.3.5.5EpoxyResins................. 545
4.3.5.6Poly(PhenyleneOxide)...........................................................................................557
4.3.6CellulosicPolymers.................................................................................................................559
4.3.6.1RegeneratedCellulose............
4.3.6.2CelluloseNitrate......................................................................................................560
4.3.6.3CelluloseAcetate......................................................................................................561
4.3.6.4OtherCelluloseEsters................. ........562
4.3.6.5CelluloseEthers........................................................................................................562
4.3.7SulfidePolymers.......................................................................................................................563
4.3.7.1Polysulfides...............................................................................................................563
4.3.7.2Poly(PhenyleneSulfide).........................................................................................564
4.3.8Polysulfones...............................................................................................................................565
4.3.8.1Properties.................
4.3.9PolyetherKetones....................................................................................................................567
4.3.10Polybenzimidazole...................................................................................................................569
4.3.11SiliconesandOtherInorganicPolymers...............
4.3.11.1Silicones...................................................................................................................570
4.3.11.2Polyphosphazenes.................................................................................................576
4.3.11.3Polythiazyl................
4.3.12Polyblends..................................................................................................................................577
4.3.12.1PredictionofPolyblendProperties...................................................................581
4.3.12.2SelectionofBlendComponents...............
4.3.12.3CompatibilizationofPolymers...........................................................................584
4.3.12.4IndustrialPolyblends............................................................................................586
4.3.12.5Nanoblends.................
4.3.13InterpenetratingPolymerNetworks....................................................................................587
4.3.13.1IndustrialIPNs.......................................................................................................589
5 PolymersinSpecialUses
5.1Introduction..............
5.2High-TemperatureandFire-ResistantPolymers.................
5.2.1Temperature-ResistantPolymers.........................................................................................594
5.2.2Fire-ResistantPolymers..............
5.3LiquidCrystalPolymers.................
5.3.1ThermotropicMain-ChainLiquidCrystalPolymers......................................................603
5.3.2Side-ChainLiquidCrystalPolymers...........
5.3.3ChiralNematicLiquidCrystalPolymers...............
5.3.4PropertiesofCommercialLCPs...........................................................................................609
5.3.5Applications.................
5.4ConductivePolymers.............
5.4.1FilledPolymers.........................................................................................................................612
5.4.1.1EMIShielding..................
5.4.1.2ConductiveCoating............
5.4.1.3SignatureMaterials..................................................................................................617
5.4.2InherentlyConductivePolymers..........................................................................................618
5.4.2.1Doping.......................................................................................................................620
5.4.2.2ConductingMechanisms..................
5.4.2.3Applications..............................................................................................................627
5.4.3PhotoconductivePolymers....................................................................................................635
5.5ElectroactivePolymers..............
5.5.1IonicEAPs.................................................................................................................................636
5.5.1.1Polymer
5.5.1.2IonicPolymerGels.................
5.5.1.3CarbonNanotubes..................................................................................................637
5.5.1.4ConductivePolymers..............................................................................................639
5.5.2ElectronicEAPs................
5.5.2.1FerroelectricPolymers............................................................................................640
5.5.2.2PolymerElectrets.....................................................................................................640
5.5.2.3ElectrostrictivePolymers................
5.5.2.4DielectricElastomers..............................................................................................642
5.6PolymersinFiberOptics......................................................................................................................644
5.7PolymersinNonlinearOptics..............
5.8Langmuir–BlodgettFilms......................................................................................................................648
5.9Piezo-andPyroelectricPolymers.......................................................................................................650
5.9.1Applications.................
5.10PolymericElectrolytes............................................................................................................................653
5.11PolymersinPhotoresistApplications................................................................................................656
5.11.1NegativePhotoresists...............
5.11.2PositivePhotoresists...............................................................................................................661
5.11.2.1Near-UVApplication..........................................................................................661
5.11.2.2Mid-andDeep-UVPhotoresists...............
5.11.3ElectronBeamResists.............................................................................................................667
5.11.4Plasma-DevelopablePhotoresists.........................................................................................667
5.12PhotoresistApplicationsforPrinting...........
5.12.1PrintingPlates..........................................................................................................................669
5.12.1.1RelieforRaised-ImagePlates............................................................................669
5.12.1.2Photolithography/PlanographicPlates.................
5.12.1.3Photogravure.........................................................................................................670
5.12.2Photoengraving........................................................................................................................671
5.12.3PrintedCircuits.............
5.12.4CollotypeandProofingSystems..........................................................................................671
5.13OpticalInformationStorage.................................................................................................................672
5.14PolymersinAdhesives.................
5.14.1Solvent-BasedAdhesives........................................................................................................674
5.14.2Water-BasedAdhesives..........................................................................................................675
5.14.3HotMeltAdhesives..............
5.14.4Radiation-CurableAdhesives................................................................................................677
5.15DegradablePolymers.............................................................................................................................678
5.15.1PackagingApplications..............
5.15.2MedicalandRelatedApplications.......................................................................................680
5.15.2.1SyntheticPolymers...............................................................................................680
5.15.2.2ControlledReleaseAgents.............
5.15.2.3TissueEngineering...............................................................................................683
5.16IonicPolymers.........................................................................................................................................685
5.16.1PhysicalPropertiesandApplications..................................................................................686
5.16.1.1IonicCross-Linking.............
5.16.1.2Ion-Exchange..........................................................................................................687
5.16.1.3Hydrophilicity........................................................................................................689
5.16.2Ionomers..............
5.16.2.1PolyethyleneIonomers.........................................................................................691
5.16.2.2ElastomericIonomers...........................................................................................694
5.16.2.3IonomersBasedonPolytetrafluoroethylene.................
5.16.2.4IonomersBasedonPolysulfones.......................................................................696
5.16.3Polyelectrolytes.........................................................................................................................697
5.16.3.1Ion-Exchangers...............
5.16.3.2Polycarboxylates....................................................................................................705
5.16.3.3IntegralPolyelectrolytes.......................................................................................706
5.17SyntheticPolymerMembranes................
5.17.1MembranePreparation...........................................................................................................707
5.17.1.1Wet-ExtrusionProcess.........................................................................................708
5.17.1.2HollowFiberMembranes...............
5.17.2MembraneModules................................................................................................................712
5.17.3Applications...............................................................................................................................713
5.18HydrogelsandSmartPolymers...............
5.18.1SmartPolymers........................................................................................................................716
5.19DendriticPolymers.................................................................................................................................722
5.19.1Applications................
5.20ShapeMemoryPolymers......................................................................................................................725
5.21Microencapsulation................................................................................................................................727
5.21.1ProcessesforMicroencapsulation.............
5.21.1.1ComplexCoacervation.........................................................................................728
5.21.1.2Polymer
5.21.1.3Interfacialand InSitu Polymerization..................
5.21.1.4SprayDrying..........................................................................................................733
5.21.1.5Fluidized-BedCoating..........................................................................................733
5.21.1.6Co-ExtrusionCapsuleFormation...............
5.21.1.7OtherProcesses......................................................................................................734
5.21.2Applications...............................................................................................................................735
5.22NanosizePolymers.................
5.22.1PolymerNanoparticles...........................................................................................................737
5.22.2PolymerNanospheres.............................................................................................................738
5.22.3PolymerNanofibers.................
5.22.4PolymerNanowires,Nanotubes,andNanorods..............................................................740
5.23PolymerNanocomposites.....................................................................................................................742
5.24Polymer–ClayNanocomposites..................
5.25Polymer–CarbonNanocomposites.....................................................................................................746
5.25.1Graphite-BasedPNCs.............................................................................................................747
5.25.2CNT-BasedPNCs...............
5.25.2.1NanotubeFunctionalization...............................................................................747
5.25.2.2NanocompositeFabricationMethods...............................................................748
5.25.2.3NanotubeAlignmentinComposites............
5.25.2.4PropertiesofNanocomposites...........................................................................751
5.25.3Graphene-BasedPNCs........................................................................................................753
5.25.3.1TechnicalProductionofGraphene...............................................................754
5.25.3.2PreparationofNanocomposites.................
5.25.3.3PropertiesofGraphene–PNCs.......................................................................762
5.26Microfibrillar/NanofibrillarPolymerComposites.........................................................................764
5.26.1Microfibrillar/NanofibrillarPolymer–PolymerComposites..........
5.26.1.1ManufacturingSteps.........................................................................................766
5.26.1.2PropertiesandApplications............................................................................768
5.26.2Microfibrillar/NanofibrillarSPCs..............
5.26.2.1ManufacturingSteps.........................................................................................770
5.26.2.2PropertiesandApplications............................................................................771
5.27Wood–PolymerComposites............
5.27.1WPCFeedstocks....................................................................................................................775
5.27.1.1Wood....................................................................................................................775
5.27.1.2Plastics..............
5.27.1.3CompoundedPellets.........................................................................................776
5.27.1.4Additives..............................................................................................................
5.27.2ManufactureofWPCProducts..............
5.27.2.1Compounding....................................................................................................777
5.27.2.2Extrusion.............................................................................................................777
5.27.3PropertiesofWPCProducts.............
6 RecyclingandDisposalofWastePlastics
6.1Introduction.............................................................................................................................................795
6.2OutlineofRecyclingMethods..............
6.3RecyclingofPoly(EthyleneTerephthalate)...........
6.3.1DirectReuse..............................................................................................................................804
6.3.2ReuseafterModi
6.3.2.1Glycolysis.................
6.3.2.2Methanolysis.............................................................................................................808
6.3.2.3Ammonolysis.............
6.3.2.4Hydrolysis..................
6.3.2.5DepolymerizationinSupercriticalFluids...........................................................809
6.3.2.6EnzymaticDepolymerization..............
6.3.3Incineration.............
6.4RecyclingofPolyurethanes..................................................................................................................811
6.4.1ThermopressingProcess...............
6.4.2KneaderProcess.................
6.4.3Hydrolysis..................................................................................................................................812
6.4.3.1Glycolysis.................
6.4.3.2Ammonolysis.............
6.5RecyclingofPoly(VinylChloride)....................................................................................................815
6.5.1CharacterizationofUsedPVC............
6.5.2In-LinePVCScrap.............
6.5.3PVCFloorCoverings..............................................................................................................818
6.5.4PVCRoofingSheets.................
6.5.5Post-ConsumerPVC...............
6.5.6VinyloopandTexyloopProcesses........................................................................................819
6.6RecyclingofCuredEpoxies................................................................................................................820
6.7RecyclingofMixedPlasticsWaste...................................................................................................821
6.7.1DirectReuse............... .............822
6.7.2HomogeneousFractions.......................................................................................................824
6.7.3LiquefactionofMixedPlastics............................................................................................825
6.8Post-ConsumerPolyethyleneFilms..................
6.9RecyclingofGroundRubberTires...................................................................................................826
6.10RecyclingofCarBatteries...................................................................................................................828
6.11PlasticRecyclingEquipmentandMachinery...............
6.11.1Plastocompactor.....................................................................................................................829
6.11.2DebalingandInitialSizeReduction..................................................................................829
6.11.2.1Shredder............ 830
6.11.2.2CutterorGuillotine...........................................................................................830
6.11.2.3ScrewShredder...................................................................................................830
6.11.2.4Granulators................
6.11.2.5FineGrinding......................................................................................................831
6.11.3CleaningandSelection.........................................................................................................831
6.11.3.1DrySeparation.............
6.11.3.2WetSeparation...................................................................................................834
6.11.3.3OtherMethods....................................................................................................834
6.11.4ResinDetectors:TypeandCon
6.11.5AutomaticSortation..............................................................................................................836
6.11.5.1PVC/PETandCommingledPlasticsSortation...........................................836
7.1Introduction..............
7.2.5High-BarrierFilms.............
7.2.6OxygenScavenger-BasedPackaging....................................................................................852
7.2.7PlasticBottles................
7.2.8ChemicalContainers...............
7.2.9DualOvenables.........................................................................................................................853
7.2.10Closures...............
7.2.11BiodegradablePackaging..............
7.2.12PharmaceuticsPackagingandNanomedicines.................................................................855
7.2.13Wood
7.3PolymersinBuildingandConstruction...........
7.3.1Roo
7.3.2Flooring...............
7.3.3Windows...............
7.3.4Pipes............................................................................................................................................859
7.3.5Insulation...................................................................................................................................859
7.3.6Polymer–ConcreteComposites.............................................................................................860
7.3.6.1Fiber-ReinforcedPolymerinConcrete.............. ........862
7.3.7Wood–PlasticComposites.....................................................................................................863
7.3.8SmartHealablePolymerComposites..................................................................................863
7.3.9BiodegradableComposites............... ..864
7.4PolymersinCorrosionPreventionandControl.............................................................................864
7.4.1FlueGasDesulfurization........................................................................................................865
7.4.2ChemicalResistantMasonry................ ........865
7.4.3PipingSystems..........................................................................................................................866
7.4.4BoilerandCoolingWaterTreatment.................................................................................866
7.4.5BiodegradableScaleInhibitor................. 866
7.4.6ReinforcingSteelinConcrete................................................................................................ 867
7.5PlasticsinAutomotiveApplications..................................................................................................868
7.5.1ExteriorBodyParts.................. ........868
7.5.2InteriorComponents...............................................................................................................869
7.5.3Load-BearingParts..................................................................................................................870
7.5.4Under-the-Bonnet(Hood)............... .870
7.5.5FutureTrends...........................................................................................................................871
7.5.6PolymerNanocomposites......................................................................................................871
7.5.7 “Green” Composites................. ........872
7.6PolymersinAerospaceApplications..................................................................................................873
7.6.1CarbonFibers...........................................................................................................................873
7.6.2Resins.................
7.7PolymersinElectricalandElectronicApplications........................................................................875
7.7.1WireandCableInsulation.....................................................................................................876
7.7.2PolymerInsulators..............
7.7.3PrintedCircuitBoards............................................................................................................877 7.7.4Connectors.................................................................................................................................877
7.7.5Enclosures...............
7.7.6OpticalFibers............................................................................................................................878
7.7.7InformationStorageDiscs.....................................................................................................879
7.7.8PolymericFETandLED.................. 880
7.7.9Polymer-BasedSolarCells.....................................................................................................881
7.8PolymersinAgricultureandHorticulture........................................................................................ 883
7.8.1PlasticFilm...............
7.8.2PlasticCrates.............................................................................................................................885
7.8.3Building......................................................................................................................................885
7.8.4PipesandHoses............
7.8.5Greenhouses..............................................................................................................................885
7.9PolymersinDomesticAppliancesandBusinessMachines..........................................................886
7.9.1LargeAppliances..............
7.9.2SmallAppliances......................................................................................................................888
7.9.3BusinessEquipment................................................................................................................888
7.9.4AirFilters................ ...................889
7.9.5SolarSystems............................................................................................................................889
7.10PolymersinMedicalandBiomedicalApplications........................................................................890
7.10.1MedicalPackaging..............
7.10.2NontoxicSterilizableItems....................................................................................................890
7.10.3BiodegradablePolymers.........................................................................................................892
7.10.4ConductingPolymerNanotubes..........................................................................................892
7.10.5BiomimeticActuators.............................................................................................................893
7.10.6DentalResinComposites.......................................................................................................894
7.10.7Appliances.................................................................................................................................894
7.10.8Disposables................................................................................................................................894
7.11PolymersinMarineandOffshoreApplications..............................................................................895
7.11.1Cables.........................................................................................................................................895
7.11.2Coatings.....................................................................................................................................895
7.11.3OtherApplications..................................................................................................................896
7.12PolymersinSport...................................................................................................................................896
7.12.1SyntheticSurfaces....................................................................................................................896
7.12.2Footwear....................................................................................................................................897
7.12.3Equipment.................................................................................................................................897
7.13RenewableSyntheticPolymers............................................................................................................898 References............................................................................................................................................................900
Appendices
A1 TradeNamesforSomeIndustrialPolymers................................................................903 A2
http://taylorandfrancis.com
Preface
Inanswertoaquestionaboutwhathethinkstobechemistry’sbiggestcontributiontoscienceandto society,LordTodd,presidentoftheRoyalSocietyofLondon,said(asquotedin
Chem.Eng.News 50,40, 1940): Iaminclinedtothinkthatthedevelopmentofpolymerizationis,perhaps,thebiggestthingchemistry hasdone,whereithashadthebiggesteffectoneverydaylife.Theworldwouldbeatotallydifferentplace withoutartificial fibers,plastics,elastomersetc.Eveninelectronicswhatwouldyoudowithoutinsulation? Andyoucomebacktopolymersagain. Polymersaremadeofmacromolecules,whicharelargemolecules madebyjoiningtogethermanysmalleroneswhileprocessablecompositionsbasedonpolymersare,by commonusage,calledplastics.Theterm plastics thusincludesallofthemanythousandsofgradesof commercialmaterials,ranginginapplicationfromsqueezebottles,breadwrappers,fabrics,paints, adhesives,rubbers,wireinsulators,foams,greases,oils,and filmstoautomobilesandaircraftcomponents, andmissileandspacecraftbodies.Asplasticsthustoucheverybody’slifeinmanydifferentways,inmany differentforms,andformanydifferentneeds,underdiverseconditionsofuseandapplications,acomprehensivesourceofinformationaboutdifferentaspectsofplastics,suchassynthesisandmanufacture, processingandfabrication,propertiesandtesting,stabilityanddegradation,orrecyclinganddisposalis needed. PlasticsTechnologyHandbook wasthusconceivedandpublished,inits firstedition,waybackin 1987,inrecognitionofthisneed.Astheplasticsworldhasprogressed,expanded,andchangedrapidlywith time,thishandbookalsohasbeenconstantlyrevised,expanded,andupdated,intunewiththischange,to reachthepresentstageof fifth edition,inwhich,however,thetextbook-styleapproachandobjective presentationoftheearliereditionshavebeenretained,whileenlarging,upgrading,andupdatingseveral areasofgreaterinterestandaddingmanynewtopicsofcurrentfocusandpotentialimportance.
Startingwithbasicconcepts,definitions,andterminologiesofpolymerscience,theopeningchapterof thebookdescribesdifferenttypesofaveragemolecularweightsofpolymers,theoriesbehindthemand experimentalmethodsofdetermination,differenttypesofpolymerizationprocesses(addition,condensation,coordination,andsupramolecular),reactionmechanismsandkinetics,industrialmethodsof polymerization(bulk,solution,suspension,emulsion,andmicroemulsion),andpolymerizationreactors (batch-type,plug flow,cascading,etc).Molecularcharacteristicsandstructuralshapesofpolymermoleculesareanalyzed,focusingonpolymerconfigurationsandconformationswitheffectsonpolymer crystallinityandsolidstatemorphologythatgreatlyinfluencephysicalandchemicalpropertiesof polymermaterials.Thermaltransitions(glasstransitionandmelting)ofpolymersandtheirrelationto molecularstructureandmorphologyarerationalized.Viscoelasticbehavior,cross-linkingeffectsof polymerchains,polymersolubilityanditspredictability,aswellaseffectsofcorrosivesarediscussed. Otherfacetsofpolymercharacteristicsincludingthermalstability, flameretardationandablation,and thermal,chemical,andradiationdegradationareexplored.Chemicalmethodsofstabilizationofpolymers areexplained,focusingonallcommonpolymers,individually.Sincepolymersarenotusefulwithoutthe additionofadditives(i.e.,polymercompounding),variousadditives,namely, fillers,plasticizers,antistatic agents, flameretardants,smokesuppressants,colorants,andantimicrobials,arehighlighted.Toxicityof plasticsisalsodiscussedwithfocusonplasticdevicesusedinpharmacy,medicines,nanomedicines,drug delivery,andtoxicitytesting.
Beginningwithageneraldiscussionoftoolingforplasticsprocessing especiallymolds,dies,andtool design thesecondchapterofthebookpresents,inasimpleyetelaboratemanner,essentialfeaturesofthe mostcommonmethodsofprocessingthermosettingplastics(namely,compressionandtransfermolding) andthermoplastics(namely,extrusion,injection,blowing,andcalendering),besidesotherprocesses,such asthermoforming,slushmolding,andspinningwithpersistentfocusonfunctioningandmethodologyof theprocesses.Thesignificanceofnewdevelopmentsinmolddesigninrespectto runners and gates isdiscussed.Allimportantfabricationprocessesarefullyillustratedandlucidlyexplained.Theseincludeplunger
injectionmolding,screwinjectionmolding,foaminjectionmolding,blown filmextrusion, flat film extrusion,pipeextrusion,extrusionblowmolding,injectionblowmolding,calendering,conventional fiber spinning,electrospinning(ofnanofibers),thermoforming,andcastingprocesses.Allaspectsofreinforced plastics bothglass-reinforcedandgraphite/carbon-reinforcedplastics andtheirmoldingtechniquesare describedandillustratedwithdiagrams.Theprocessesofpultrusion,prepregmolding,reactioninjection molding,resintransfermolding,conventionalfoaming,andsyntacticfoamingarepresented.Rubber compoundingandprocessingtechnology,includingrubberreclamationandfabricationofrubber-based products,arediscussed,followedbyahostofotherprocessingtechniques,whichincludespraycoating, fluidizedbedcoating,electrostaticspraying,stimuli-responsivecoating,powdermolding,centrifugalcasting, adhesionbonding,high-frequencywelding,ultrasonicwelding,andplasticsdecorativeprocesses(e.g., gravureprinting, flexography,screenprinting,in-molddecorating,embossing,electroplating,andvacuum metallizing).Morerecentdevelopmentsinpolymerfabricationandprocessing,suchasjoiningpolymer–metalhybrids,smartcoatings,rapidprototyping/3Dprinting,and flexprinting,arealsopresented.
Besidestheremarkableeaseandscopeofplasticsfabrication,itisthewiderangeofpropertiesinherent inplasticsorimpartedbyvariousmeansthatgivesplasticsthedominantplaceamongallmaterials. Chapter3discussesplasticspropertiesunderfourmainheadings mechanical,electrical,optical,and thermal givingtheoreticalderivationswherenecessaryandrationalizingthemonmolecularand structuralbasis.Mechanicalpropertiesconsideredincludeelasticstress–strain,viscoelasticstress–straintime,creep(withmathematicalmodeling),pseudoelasticdesign,time–temperaturesuperpositionprinciple,dynamicmechanicalproperties,hardness,impactstrength,andstress–corrosioncrackingbehavior. Themechanicalbehaviorof fiber-reinforcedplasticsisseparatelydiscussedandmathematicallymodeled. Theelectricalbehaviorofplasticsisevaluatedintermsofthespecificproperties,suchasdielectric strength,dielectricconstant,insulationresistanceorresistivity,andarcresistance.Characteristicaspects oflighttransmittingabilityandopticalclarity,refractiveindex,andlightpiping,aswellasstress-optical behaviorofspecificplastics,arediscussed.Thermalpropertiesarehighlightedbycomparingdifferent plasticsinrespectofspecificheat,thermalexpansion,thermalconductivity,andthermaltransitionswith specificfocusonapplicationaspects.
Animportantfacetofmaterialsdevelopmentandpropermaterialsselectionistestingandstandardizationforvariousproperties.ThelatterpartofChapter3isdevotedtothisaspect.Anumberofstandard testmethodsforplasticsarepresentedschematically(insimplifiedform),highlightingtheprinciplesof thetestsandmethodsofmeasurements.Thelastpartofthechapterisdevotedtochemicalidentification andanalysisofcommonplastics.Alaymanyetsystematicprocedure,involvingheatingandignition, detectionofhetero-elements(N,S,halogens),solubilityobservation,andothertests,ispresentedfollowed byexactidentificationviaspecificchemicaltests.Instrumentalmethodsofplasticsanalysis,bothqualitativeandquantitative,arealsopresented,anelaborateandillustrativecoveragebeinggiventothemost commonlyusedmethods,namely,IRandNMRspectroscopy.
Industrialpolymers,thatis,thosethatareproducedonverylarge,large,andrelativelylargescales includingtheso-calledengineeringpolymersthatpossesssuperiormechanicalpropertiesforengineering applications arediscussedinChapter4.Thesepolymershavebeenclassifiedintothreebroadcategories additionpolymers (i.e.,chainsconsistingentirelyofC–Cbonds), condensationpolymers (i.e.,chainswith hetero-atoms,e.g.,O,N,S,Si,inthebackbonechain),and specialpolymers (i.e.,productswithspecial properties,suchastemperatureand fireresistance,photosensitivity,electricalconductivity,andpiezoelectricproperties).Furtherclassificationofaddition,condensation,andspecialpolymershasbeenmade onthebasisofmonomercomposition,andallimportantpolymersineachclasshavebeendiscussedin detailwithfocusonproductionmethods,characteristicproperties,andprincipalapplications.Themain classesthusconsideredarepolyolefins,acrylics,vinylpolymers,polyesters,polyamides,formaldehyde resins,polyurethanes,etherpolymers,cellulosicpolymers,andsulfidepolymers.Polysulfones,polyether ketones,polybenzimidazole,silicones,andotherinorganicpolymersareincludedunderthespecial polymerscategory.Blendpolymers,includingindustrialpolyblends,nanoblends,andinterpenetrating networkpolymers,arealsogivenduecoverage.
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Among the earliest particulars which Robert gave, was the fact that he was not alone in his confinement. Various others, all in antique garb, were in there with him—a corpulent middle-aged gentleman with tied queue and velvet knee-breeches who spoke English fluently though with a marked Scandinavian accent; a rather beautiful small girl with very blonde hair which appeared as glossy dark blue; two apparently mute Negroes whose features contrasted grotesquely with the pallor of their reversed-colored skins; three young men; one young woman; a very small child, almost an infant; and a lean, elderly Dane of extremely distinctive aspect and a kind of half-malign intellectuality of countenance.
This last named individual—Axel Holm, who wore the satin smallclothes, flared-skirted coat, and voluminous full-bottomed periwig of an age more than two centuries in the past—was notable among the little band as being the one responsible for the presence of them all. He it was who, skilled equally in the arts of magic and glass working, had long ago fashioned this strange dimensional prison in which himself, his slaves, and those whom he chose to invite or allure thither were immured unchangingly for as long as the mirror might endure.
Holm was born early in the seventeenth century, and had followed with tremendous competence and success the trade of a glassblower and molder in Copenhagen. His glass, especially in the form of large drawing-room mirrors, was always at a premium. But the same bold mind which had made him the first glazier of Europe also served to carry his interests and ambitions far beyond the sphere of mere material craftsmanship. He had studied the world around him, and chafed at the limitations of human knowledge and capability. Eventually he sought for dark ways to overcome those limitations, and gained more success than is good for any mortal.
He had aspired to enjoy something like eternity, the mirror being his provision to secure this end. Serious study of the fourth dimension was far from beginning with Einstein in our own era; and Holm, more
than erudite in all the methods of his day, knew that a bodily entrance into that hidden phase of space would prevent him from dying in the ordinary physical sense. Research showed him that the principle of reflection undoubtedly forms the chief gate to all dimensions beyond our familiar three; and chance placed in his hands a small and very ancient glass whose cryptic properties he believed he could turn to advantage. Once "inside" this mirror according to the method he had envisaged, he felt that "life" in the sense of form and consciousness would go on virtually forever, provided the mirror could be preserved indefinitely from breakage or deterioration.
Holm made a magnificent mirror, such as would be prized and carefully preserved; and in it deftly fused the strange whorlconfigured relic he had acquired. Having thus prepared his refuge and his trap, he began to plan this mode of entrance and conditions of tenancy. He would have with him both servitors and companions; and as an experimental beginning he sent before him into the glass two dependable Negro slaves brought from the West Indies. What his sensations must have been upon beholding this first concrete demonstration of his theories, only imagination can conceive.
Undoubtedly a man of his knowledge realized that absence from the outside world if deferred beyond the natural span of life of those within, must mean instant dissolution at the first attempt to return to that world. But, barring that misfortune or accidental breakage, those within would remain forever as they were at the time of entrance. They would never grow old, and would need neither food nor drink.
To make his prison tolerable he sent ahead of him certain books and writing materials, a chair and table of stoutest workmanship, and a few other accessories. He knew that the images which the glass would reflect or absorb would not be tangible, but would merely extend around him like a background of dream. His own transition in 1687 was a momentous experience; and must have been attended by mixed sensations of triumph and terror. Had anything gone
wrong, there were frightful possibilities of being lost in dark and inconceivable multiple dimensions.
For over fifty years he had been unable to secure any additions to the little company of himself and slaves, but later on he had perfected his telepathic method of visualizing small sections of the outside world close to the glass, and attracting certain individuals in those areas through the mirror's strange entrance. Thus Robert, influenced into a desire to press upon the "door," had been lured within. Such visualizations depended wholly on telepathy, since no one inside the mirror could see out into the world of men.
It was, in truth, a strange life that Holm and his company had lived inside the glass. Since the mirror had stood for fully a century with its face to the dusty stone wall of the shed where I found it, Robert was the first being to enter this limbo after all that interval. His arrival was a gala event, for he brought news of the outside world which must have been of the most startling impressiveness to the more thoughtful of those within. He, in his turn—young though he was— felt overwhelmingly the weirdness of meeting and talking with persons who had been alive in the seventeenth and eighteenth centuries.
The deadly monotony of life for the prisoners can only be vaguely conjectured. As mentioned, its extensive spatial variety was limited to localities which had been reflected in the mirror for long periods; and many of these had become dim and strange as tropical climates had made inroads on the surface. Certain localities were bright and beautiful, and in these the company usually gathered. But no scene could be fully satisfying; since the visible objects were all unreal and intangible, and often of perplexingly indefinite outline. When the tedious periods of darkness came, the general custom was to indulge in memories, reflections, or conversations. Each one of that strange, pathetic group had retained his or her personality unchanged and unchangeable, since becoming immune to the time effects of outside space.
The number of inanimate objects within the glass, aside from the clothing of the prisoners, was very small; being largely limited to the accessories Holm had provided for himself. The rest did without even furniture, since sleep and fatigue had vanished along with most other vital attributes. Such inorganic things as were present, seemed as exempt from decay as the living beings. The lower forms of animal life were wholly absent.
Robert derived most of his information from Herr Thiele, the gentleman who spoke English with a Scandinavian accent. This portly Dane had taken a fancy to him, and talked at considerable length. The others, too, had received him with courtesy and goodwill; Holm himself, seeming well-disposed, had told him about various matters including the door of the trap.
The boy, as he told me later, was sensible enough never to attempt communication with me when Holm was nearby. Twice, while thus engaged, he had seen Holm appear; and had accordingly ceased at once. At no time could I see the world behind the mirror's surface. Robert's visual image, which included his bodily form and the clothing connected with it, was—like the aural image of his halting voice and like his own visualization of myself—a case of purely telepathic transmission; and did not involve true inter-dimensional sight. However, had Robert been as trained a telepathist as Holm, he might have transmitted a few strong images apart from his immediate person.
Throughout this period of revelation I had, of course, been desperately trying to devise a method for Robert's release. On the fourth day—the ninth after the disappearance—I hit on a solution. Everything considered, my laboriously formulated process was not a very complicated one; though I could not tell beforehand how it would work, while the possibility of ruinous consequences in case of a slip was appalling. This process depended, basically, on the fact that there was no possible exit from inside the glass. If Holm and his prisoners were permanently sealed in, then release must come
wholly from outside. Other considerations included the disposal of the other prisoners, if any survived, and especially of Axel Holm. What Robert had told me of him was anything but reassuring; and I certainly did not wish him loose in my apartment, free once more to work his evil will upon the world. The telepathic messages had not made fully clear the effect of liberation on those who had entered the glass so long ago.
There was, too, a final though minor problem in case of success— that of getting Robert back into the routine of school life without having to explain the incredible. In case of failure, it was highly inadvisable to have witnesses present at the release operations— and lacking these, I simply could not attempt to relate the actual facts if I should succeed. Even to me the reality seemed a mad one whenever I let my mind turn from the data so compellingly presented in that tense series of dreams.
When I had thought these problems through as far as possible, I procured a large magnifying-glass from the school laboratory and studied minutely every square millimeter of that whorl-center which presumably marked the extent of the original ancient mirror used by Holm. Even with this aid I could not quite trace the exact boundary between the old area and the surface added by the Danish wizard; but after a long study decided on a conjectural oval boundary which I outlined very precisely with a soft blue pencil, I then made a trip to Stamford, where I procured a heavy glass-cutting tool; for my primary idea was to remove the ancient and magically potent mirror from its later setting.
My next step was to figure out the best time of day to make the crucial experiment. I finally settled on two-thirty A.M.—both because it was a good season for uninterrupted work, and because it was the "opposite" of two-thirty P.M., the probable moment at which Robert had entered the mirror. This form of "oppositeness" may or may not have been relevant, but I knew at least that the chosen hour was as good as any—and perhaps better than most.
I finally set to work in the early morning of the eleventh day after the disappearance, having drawn all the shades of my living-room and closed and locked the door into the hallway. Following with breathless care the elliptical line I had traced, I worked around the whorl-section with my steel-wheeled cutting tool. The ancient glass, half an inch thick, crackled crisply under the firm, uniform pressure; and upon completing the circuit I cut around it a second time, crunching the roller more deeply into the glass.
Then, very carefully indeed, I lifted the heavy mirror down from its console and leaned it face-inward against the wall; prying off two of the thin, narrow boards nailed to the back. With equal caution I smartly tapped the cut-around space with the heavy wooden handle of the glass-cutter.
At the very first tap the whorl-containing section of glass dropped out on the Bokhara rug beneath. I did not know what might happen, but was keyed up for anything, and took a deep involuntary breath. I was on my knees for convenience at the moment, with my face quite near the newly made aperture; and as I breathed there poured into my nostrils a powerful dusty odor—a smell not comparable to any other I have ever encountered. Then everything within my range of vision suddenly turned to a dull gray before my failing eye-sight as I felt myself overpowered by an invisible force which robbed my muscles of their power to function.
I remember grasping weakly and futilely at the edge of the nearest window drapery and feeling it rip loose from its fastening. Then I sank slowly to the floor as the darkness of oblivion passed over me.
When I regained consciousness I was lying on the Bokhara rug with my legs held unaccountably up in the air The room was full of that hideous and inexplicable dusty smell—and as my eyes began to take in definite images I saw that Robert Grandison stood in front of me. It was he—fully in the flesh and with his coloring normal—who was holding my legs aloft to bring the blood back to my head as the
school's first-aid course had taught him to do with persons who had fainted. For a moment I was struck mute by the stifling odor and by a bewilderment which quickly merged into a sense of triumph. Then I found myself able to move and speak collectedly.
I raised a tentative hand and waved feebly at Robert.
"All right, old man," I murmured, "you can let my legs down now. Many thanks. I'm all right again, I think. It was the smell—I imagine— that got me. Open that farthest window, please—wide—from the bottom. That's it—thanks. No—leave the shade down the way it was."
I struggled to my feet, my disturbed circulation adjusting itself in waves, and stood upright hanging to the back of a big chair. I was still "groggy," but a blast of fresh, bitterly cold air from the window revived me rapidly. I sat down in the big chair and looked at Robert, now walking toward me.
"First," I said hurriedly, "tell me, Robert—those others—Holm? What happened to them, when I—opened the exit?"
Robert paused half-way across the room and looked at me very gravely.
"I saw them fade away—into nothingness—Mr. Canevin," he said with solemnity; "and with them—everything. There isn't any more 'inside,' sir—thank God, and you, sir!"
And young Robert, at last yielding to the sustained strain which he had borne through all those terrible eleven days, suddenly broke down like a little child and began to weep hysterically in great, stifling, dry sobs.
I picked him up and placed him gently on my davenport, threw a rug over him, sat down by his side, and put a calming hand on his forehead.
"Take it easy, old fellow," I said soothingly.
The boy's sudden and very natural hysteria passed as quickly as it had come on as I talked to him reassuringly about my plans for his quiet restoration to the school. The interest of the situation and the need of concealing the incredible truth beneath a rational explanation took hold of his imagination as I had expected; and at last he sat up eagerly, telling the details of his release and listening to the instructions I had thought out. He had, it seems, been in the "projected area" of my bedroom when I opened the way back, and had emerged in that actual room—hardly realizing that he was "out." Upon hearing a fall in the living-room he had hastened thither, finding me on the rug in my fainting spell.
I need mention only briefly my method of restoring Robert in a seemingly normal way—how I smuggled him out of the window in an old hat and sweater of mine, took him down the road in my quietly started car, coached him carefully in a tale I had devised, and returned to arouse Browne with the news of his discovery. He had, I explained, been walking alone on the afternoon of his disappearance; and had been offered a motor ride by two young men who, as a joke and over his protests that he could go no farther than Stamford and back, had begun to carry him past that town. Jumping from the car during a traffic stop with the intention of hitchhiking back before Call-Over, he had been hit by another car just as the traffic was released—awakening ten days later in the Greenwich home of the people who had hit him. On learning the date, I added, he had immediately telephoned the school; and I, being the only one awake, had answered the call and hurried after him in my car without stopping to notify anyone.
Browne, who at once telephoned to Robert's parents, accepted my story without question; and forbore to interrogate the boy because of the latter's manifest exhaustion. It was arranged that he should remain at the school for a rest, under the expert care of Mrs. Browne, a former trained nurse. I naturally saw a good deal of him
during the remainder of the Christmas vacation, and was thus enabled to fill in certain gaps in his fragmentary dream-story.
Now and then we would almost doubt the actuality of what had occurred; wondering whether we had not both shared some monstrous delusion born of the mirror's glittering hypnotism, and whether the tale of the ride and accident were not after all the real truth. But whenever we did so we would be brought back to belief by some monstrous and haunting memory; with me, of Robert's dreamfigure and its thick voice and inverted colors; with him, of the whole fantastic pageantry of ancient people and dead scenes that he had witnessed. And then there was the joint recollection of that damnable dusty odor.... We knew what it meant: the instant dissolution of those who had entered an alien dimension a century and more ago.
There are, in addition, at least two lines of rather more positive evidence; one of which comes through my researches in Danish annals concerning the sorcerer, Axel Holm. Such a person, indeed, left many traces in folklore and written records; and diligent library sessions, plus conferences with various learned Danes, have shed much light on his evil fame. At present I need say only that the Copenhagen glass-blower—born in 1612—was a notorious Luciferian whose pursuits and final vanishing formed a matter of awed debate over two centuries ago. He had burned with a desire to know all things and to conquer every limitation of mankind—to which end he had delved deeply into occult and forbidden fields ever since he was a child.
He was commonly held to have joined a coven of the dreaded witchcult, and the vast lore of ancient Scandinavian myth—with its Loki the Sly One and the accursed Fenris-Wolf—was soon an open book to him. He had strange interests and objectives, few of which were definitely known, but some of which were recognized as intolerably evil. It is recorded that his two Negro helpers, originally slaves from the Danish West Indies, had become mute soon after their acquisition by him; and that they had disappeared not long before his own disappearance from the ken of mankind.
Near the close of an already long life the idea of a glass of immortality appears to have entered his mind. That he had acquired an enchanted mirror of inconceivable antiquity was a matter of common whispering; it being alleged that he had purloined it from a fellow-sorcerer who had entrusted it to him for polishing. This mirror—according to popular tales a trophy as potent in its way as the better-known Aegis of Minerva or Hammer of Thor—was a small oval object called "Loki's Glass," made of some polished fusible mineral and having magical properties which included the divination of the immediate future and the power to show the possessor his enemies. That it had deeper potential properties, realizable in the hands of an erudite magician, none of the common people doubted; and even educated persons attached much fearful importance to Holm's rumored attempts to incorporate it in a larger glass of immortality. Then had come the wizard's disappearance in 1687, and the final sale and dispersal of his goods amidst a growing cloud of fantastic legendry. It was, altogether, just such a story as one would laugh at if possessed of no particular key; yet to me, remembering those dream messages and having Robert Grandison's corroboration before me, it formed a positive confirmation of all the bewildering marvels that had been unfolded. But as I have said, there is still another line of rather positive evidence—of a very different character—at my disposal. Two days after his release, as Robert, greatly improved in strength and appearance, was placing a log on my living-room fire, I noticed a certain awkwardness in his motions and was struck by a persistent idea. Summoning him to my desk I suddenly asked him to pick up an ink-stand—and was scarcely surprised to note that, despite lifelong right-handedness, he obeyed unconsciously with his left hand. Without alarming him, I then asked that he unbutton his coat and let me listen to his cardiac action. What I found upon placing my ear to his chest—and what I did not tell him for some time afterward—was that his heart was beating on his right side.
He had gone into the glass right-handed and with all organs in their normal positions. Now he was left-handed and with organs reversed, and would doubtless continue so for the rest of his life. Clearly, the dimensional transition had been no illusion—for this physical change was tangible and unmistakable. Had there been a natural exit from the glass, Robert would probably have undergone a thorough rereversal and emerged in perfect normality—as indeed the colorscheme of his body and clothing did emerge. The forcible nature of his release, however, undoubtedly set something awry; so that dimensions no longer had a chance to right themselves as chromatic wave-frequencies still did.
I had not merely opened Holm's trap; I had destroyed it; and at the particular stage of destruction marked by Robert's escape some of the reversing properties had perished. It is significant that in escaping Robert had felt no pain comparable to that experienced in entering. Had the destruction been still more sudden, I shiver to think of the monstrosities of color the boy would always have been forced to bear. I may add that after discovering Robert's reversal I examined the rumpled and discarded clothing he had worn in the glass, and found, as I had expected, a complete reversal of pockets, buttons, and all other corresponding details.
At this moment Loki's Glass, just as it fell on my Bokhara rug from the now patched and harmless mirror, weighs down a sheaf of papers on my writing-table here in St. Thomas, venerable capital of the Danish West Indies—now the American Virgin Islands. Various collectors of old Sandwich glass have mistaken it for an odd bit of that early American product—but I privately realize that my paperweight is an antique of far subtler and more paleologean craftsmanship. Still, I do not disillusion such enthusiasts.
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