NLGI
SPOKESMAN
Serving the Grease Industry Since 1933 – VOL. 80, NO. 2, MAY/JUNE 2016
In this issue . . . 7 NLGI 83rd Annual Meeting Sponsors 8 New 2016 NLGI Members 10 Effect of MoDTC and MoDTP on Frictional and Antiwear Properties of Overbased Calcium Sulfonate Complex Greases 26 Calcium Sulfonate Complex Greases Using Calcium Hydroxyapatite as a HydroxideContaining Basic Reactant
SAVE THE DATE
NLGI 84th Annual Meeting June 10th –13th, 2017 Resort at Squaw Creek ~Lake Tahoe~ Squaw Creek, CA
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Registered and pending trademarks appearing in these materials are those of R.T. Vanderbilt Holding Company, Inc. or its respective wholly owned subsidiaries. For complete listings, please visit this location for trademarks, www.rtvanderbiltholding.com.
ACTING PRESIDENT:
TREASURER:
David Como Dow Corning Corp. P.O. Box 0994 Midland, MI 48686
Joe Kaperick Afton Chemical Corporation 500 Spring St. Richmond, VA 23218-2158
SECRETARY:
EXECUTIVE DIRECTOR:
Kim Smallwood Citgo Petroleum Corp. 1293 Eldridge Pkwy. Houston, TX 77077
Kimberly Hartley NLGI International Headquarters 249 SW Noel, Suite 249 Lee’s Summit, MO 64063
PAST-PRES./ADVISORY: Chuck Coe Grease Technology Solutions LLC 7010 Bruin Ct. Manassas, VA 20111
DIRECTORS Barbara Bellanti Battenfeld Grease & Oil Corp. of NY P.O. Box 728 • 1174 Erie Ave. N. Tonawanda, NY 14120-0728 Richard Burkhalter Covenant Engineering Services 140 Corporate Place Branson, MO 65616 Faith Corbo King Industries, Inc. Science Road Norwalk, CT 06852 Gary Dudley Exxon Mobil Corporation 3225 Gallows Road Room 7C1906 Fairfax, VA 22037 Gian L. Fagan Chevron Lubricants 100 Chevron Way Room 71-7338 Richmond, CA 94802-0627 Jim Hunt Tiarco Chemical 1300 Tiarco Drive Dalton, GA 30720 Tyler Jark Lubricating Specialties Co. 8015 Paramount Blvd. Pico Rivera, CA 90660 Dr. Anoop Kumar Royal Manufacturing Co., LP 516 S, 25th West Ave. Tulsa, Oklahoma 74127 Wayne Mackwood Chemtura 199 Benson Rd. Middlebury, CT 06749
Dennis Parks Texas Refinery Corp. One Refinery Place Ft. Worth, TX 76101 Tom Schroeder Axel Americas, LLC P.O. Box 12337 Kansas City, MO 64116 Raj Shah Koehler Instrument Co. 85 Corporate Dr. Holtsville, NY 11716-1796 Dr. Huafeng “Bill” Shen Bel-Ray Co. P.O. Box 526 Farmingdale, NJ 07727 Terry Smith Lubrication Engineers, Inc. P.O. Box 16447 Wichita, KS 67216 Thomas W. Steib The Elco Corporation 1000 Belt Line Street Cleveland, OH 44109 Lisa Tocci Lubes ’n’ Greases 6105 Arlington Blvd., Suite G Falls Church, VA 22044 Mike Washington The Lubrizol Corporation 29400 Lakeland Blvd. Mail Drop 051E Wickliffe, OH 44092 Ruiming “Ray” Zhang R.T. Vanderbilt Company, Inc. 30 Winfield St. Norwalk, CT 06855
TECHNICAL COMMITTEE CO-CHAIRS:
CHAIR, SESSION PLANNING:
Chad Chichester Dow Corning Corporation 2200 W. Salzburg Rd., C40C00 Midland, MI 48686
Wayne Mackwood Chemtura 199 Benson Rd. Middlebury, CT 06749
David Turner 22110 Stone Cross Court Katy, TX 77450
SERVICE INDUSTRY ASSISTANCE COMMITTEE CHAIR: J im Hunt Tiarco Chemical 1300 Tiarco Drive Dalton, GA 30720
EDITORIAL REVIEW COMMITTEE Joe Kaperick Afton Chemical Corporation 500 Spring St. Richmond, VA 23218-2158
SPOKESMAN
Serving the Grease Industry Since 1933 – VOL. 80, NO. 2, MAY/JUNE 2016
4 President’s Podium 7 NLGI 83rd Annual Meeting Sponsors 8 New 2016 NLGI Members 10 Effect of MoDTC and MoDTP on Frictional and Antiwear
Properties of Overbased Calcium Sulfonate Complex Greases Mihir K. Patel, Ruiming “Ray” Zhang, Ronald J. Hiza and Steven G. Donnelly
23 Blast from the Past Cartoons 24 NLGI Member Spotlight 26 Ask the Expert 26 Calcium Sulfonate Complex Greases Using Calcium
Hydroxyapatite as a Hydroxide-Containing Basic Reactant J. Andrew Waynick
Dwaine (Greg) Morris Shell Lubricants 526 S. Johnson Drive Odessa, MO 64076
CHAIR:
NLGI
OFFICERS
50 NLGI Industry News 53 Advertiser’s Index ON THE COVER Save the Date! NLGI 84th Annual Meeting ~ Lake Tahoe! June 10th-13th 2017! Published bi-monthly by NLGI. (ISSN 0027-6782) KIMBERLY HARTLEY, Editor NLGI International Headquarters 249 SW Noel, Suite 249, Lee’s Summit, MO 64063 USA Phone (816) 524-2500, FAX: (816) 524-2504 Web site: http://www.nlgi.org — E-mail: nlgi@nlgi.org One-year subscriptions: U.S.A. $65.00; Canada $80.00; International $109.00; Airmail $147.00. Claims for missing issues must be made within six months for foreign subscribers and three months for domestic. Periodicals postage paid at Kansas City, MO. The NLGI Spokesman is indexed by INIST for the PASCAL database, plus by Engineering Index and Chemical Abstracts Service. Microfilm copies are available through University Microfilms, Ann Arbor, MI. The NLGI assumes no responsibility for the statements and opinions advanced by contributors to its publications. Views expressed in the editorials are those of the editors and do not n ecessarily represent the official position of NLGI. Copyright 2015, NLGI. Postmaster: Send address corrections to the above address.
PRESIDENT’S PODIUM
2015 NLGI GREASE PRODUCTION SURVEY The 2015 NLGI Grease Production Survey (GPS) is almost complete and will be available after the June 11th-14th Annual Meeting in Hot Springs, VA. This year’s survey results will be loaded with all of the important data upon which you’ve come to rely, and NLGI is now offering the data in an Excel format! NLGI members and survey participants will continue to receive the PDF survey results at no cost; additionally, those looking to customize the data will greatly appreciate the time-saving Excel file format available for purchase on the NLGI website. How much grease was manufactured in 2015? Do lithium and lithium complex greases continue to represent the primary grease thickener type manufactured globally? Has the use of synthetic base fluids grown again during 2015? The NLGI GPS has the answers. The NLGI Production Survey counts the global production of grease, providing a snapshot of growth (by thickener type and base oil type) and demographic (by thickener type, base oil type, and global region). Both provide an opportunity to stand up and be counted, to make a difference, to have your voice (or your production) be heard. Has grease continued to lubricate the global economy? The GPS has the answers! The NLGI Grease Production Survey continues to be the single most comprehensive global report on grease production. The 2014 survey identified a global decline of over 3% compared to 2013. Will 2015 show
Tyler F. Jark, Chair
a reversal into growth again? Last year’s 2014 survey reflected another increase in lithium complex, anhydrous calcium and calcium sulfonate greases while polyurea and conventional lithium greases saw a slight decline. Not surprisingly, conventional mineral oils still represent the primary fluid used globally to produce greases, but alternatives are growing. This is just the tip of the information iceberg contained in the NLGI Grease Production Survey. The Grease Production Survey continues to be one of the most important member benefits provided by the NLGI to its membership. The information in the Grease Production Survey Report is a valuable source of past results and can be used as an indicator of future trends. This makes the Grease Production Survey Report a very useful strategic management and production tool. The Grease Production Survey Report data for 2015 will be categorized by primary thickener types, base fluid types, and geographical region. These classifications can provide answers to many questions you may have regarding the grease industry: •W hat tonnage of lithium soap grease is produced in my region of the globe? •W hat base fluid type represents the greatest percentage of grease production? •W hich region of the globe demonstrated the greatest year on year growth? The NLGI Grease Production Survey has the answers. It is a wealth of useful information, structured and
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organized to assist in executing successful strategic decisions within the grease industry. The value and accuracy of the NLGI Grease Production Survey requires your participation and accurate reporting; we need your support. Through your active participation in next year’s 2016 survey, we hope to attain a 100% participation rate, thereby reflecting the entirety of global grease production. Consequently, if you have not yet had the opportunity to participate in the NLGI Grease Production Survey, please contact Grease Technology Solutions at the address below:
Grease Technology Solutions LLC 7010 Bruin Court Manassas, VA 20111-4374 USA Phone: 1-703-335-1978 Fax: 1 703-335-1979 Email: chuckcoe@grease-tech.com Please note that the information received from individual companies is held in strict confidence by Grease Technology Solutions LLC. The NLGI Grease Production Survey Report is a valuable member benefit and your participation is integral to its continued success. Tyler F. Jark, Chair
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A BIG THANKS TO THE 2016 SPONSORS OF THE NLGI 83RD ANNUAL MEETING!
PLATINUM SPONSORS
Afton Chemical Corporation Monday Continental Breakfast Co-Sponsor Closing Festival Decor Co-Sponsor Industry Speaker Sponsor Welcoming Reception Co-Sponsor Axel Americas, LLC Final Program Guide Sponsor Battenfeld Grease and Oil Corp. of NY Keynote Speaker Co-Sponsor Saturday Evening Reception Co-Sponsor Daubert Chemical Company Closing Festival Entertainment Co-Sponsor Emery Oleochemicals LLC Preliminary Program Sponsor Saturday Evening Reception Co-Sponsor Closing Festival Dinner Co-Sponsor FMC-Lithium Division Fun Run Sponsor Welcoming Reception Co-Sponsor Saturday Evening Reception Co-Sponsor Loadmaster Lubricants Hotel Key Card Sponsor Lubes’n’Greases Monday Continental Breakfast Co-Sponsor Saturday Evening Reception Co-Sponsor Lubrication Engineers, Inc. Monday & Tuesday Lunches Co-Sponsor Conference Bags Co-Sponsor Lubrizol Corporation Mobile Meeting App Sponsor Saturday Evening Reception Co-Sponsor Closing Festival Dinner Co-Sponsor Tiarco Chemical Saturday Evening Reception Co-Sponsor Golf Breakfast Co-Sponsor Golf Tournament Co-Sponsor Vanderbilt Chemicals, LLC Saturday Evening Reception Co-Sponsor Closing Festival Dinner Co-Sponsor Opening Entertainment Co-Sponsor Welcoming Reception Co-Sponsor
GOLD SPONSORS
Acme-Hardesty Company Meeting Central Co-Sponsor Calumet Packaging Meeting Central Co-Sponsor Calumet Specialty Products Partners, L.P. Meeting Central Co-Sponsor CITGO Petroleum Corporation Golf Tournament Co-Sponsor Covenant Engineering Services, LLC Instructor Gifts Sponsor Dow Chemical Company Meeting Central Co-Sponsor Dow Corning Corporation Education Course Student Luncheon Co-Sponsor Welcoming Reception Co-Sponsor Elco Corporation Golf Breakfast Co-Sponsor Education Course Student Luncheon Co-Sponsor Exploiter Molybdenum Co., Ltd Conference Bag Co-Sponsor ExxonMobil Fuels, Lubricants & Specialties Marketing Company Education Course Binders FedChem LLC Meeting Central Co-Sponsor Lubricating Specialties Company Saturday Evening Reception Co-Sponsor Closing Festival Dinner Co-Sponsor
SILVER SPONSORS Chemtura Closing Festival Dinner Co-Sponsor
Chevron Global Lubricants Saturday Evening Reception Co-Sponsor NLGI Author Award-Application Sponsor Cross Oil Refining & Marketing, Inc. Saturday Evening Reception Co-Sponsor Functional Products Closing Festival Dinner Co-Sponsor Grease Technology Solutions LLC Saturday Evening Reception Co-Sponsor Inolex Chemical Company Closing Festival Dinner Co-Sponsor King Industries, Inc. Monday & Tuesday Lunches Co-Sponsor Koehler Instrument Co., Inc. First Time Attendee Reception Co-Sponsor
BASF Corporation Welcoming Reception Co-Sponsor Climax Molybdenum Marketing Corp. Welcoming Reception Co-Sponsor Evonik Oil Additives Welcoming Reception Co-Sponsor H.L. Blachford Ltd. General Meeting Co-Sponsor Harrison Manufacturing Co. Pty Ltd. General Meeting Co-Sponsor Lubriplate Lubricants Company General Meeting Co-Sponsor Martin Lubricants Welcoming Reception Co-Sponsor Monson Companies - Koda Distribution Group Welcoming Reception Co-Sponsor Nator Lubrication Co., Ltd Welcoming Reception Co-Sponsor Petro-Canada Lubricants Welcoming Reception Co-Sponsor
NYCO America LLC Tuesday Continental Breakfast Co-Sponsor
Pigging Solutions, LLC General Meeting Co-Sponsor
Nynas USA Closing Festival Dinner Co-Sponsor Palmer Holland, Inc. Closing Festival Dinner Co-Sponsor
Patterson Industries Canada, A Div. of All-Weld Company Ltd. Closing Festival Cocktails Co-Sponsor
Royal Mfg. Co., LP Closing Festival Dinner Co-Sponsor NLGI Author Award-Development Sponsor
Shell Canada Products Meeting Central Co-Sponsor Shell Lubricants Award
Axxess Chemicals, LLC General Meeting Co-Sponsor
Kyodo Yushi Company, Ltd. First Time Attendee Reception Co-Sponsor
NSF International First Time Attendee Reception Co-Sponsor
Rockwood Lithium Closing Festival Cocktails Co-Sponsor Clarence E. Earle Memorial Award Sponsor
BRONZE SPONSORS
Soltex Inc. Saturday Evening Reception Co-Sponsor Texas Refinery Corp. Saturday Evening Reception Co-Sponsor Triboscience & Engineering, Inc. Saturday Evening Reception Co-Sponsor
Primrose Oil Company General Meeting Co-Sponsor Sea-Land Chemical Company Welcoming Reception Co-Sponsor Shamrock Technologies Welcoming Reception Co-Sponsor SQM North America Corp. Welcoming Reception Co-Sponsor STRATCO, Inc. Welcoming Reception Co-Sponsor Summit Lubricants, Inc. Welcoming Reception Co-Sponsor Tribotecc GmbH Closing Festival Reception Co-Sponsor Warren Oil Company Closing Festival Reception Co-Sponsor
Welcome our new 2016 NLGI members!
New 2016 NLGI Members
Note: If your company is an NLGI member, you may login to our website’s ‘Member’s Area’ and obtain direct contact information for all NLGI members. You can also sort our directory by membership category. AMSOIL Inc. - Marketing
Axxess Chemicals – Supplier
Doug Sturm 925 Tower Ave Superior, WI 54880 USA 715-399-6334 www.amsoil.com
Jay Lynn 522 Highway 9 North, Unit 110 Manalapan, NJ 07726 USA 732-851-1010 www.axxesschemicals.com
AMSOIL INC. specializes in developing synthetic lubricant technology designed for those who demand the best. Our full line of synthetic lubricants deliver superior wear protection, allowing customers to harness the full potential of their cars, trucks, motorcycles, industrial machinery and anything else they ride, drive or operate. By maximizing vehicle and equipment performance, reducing wear and increasing fuel efficiency, AMSOIL synthetic lubricants help millions of people worldwide get the most out of their vehicles and equipment while saving time and money.
Apex Grease (Shanghai) Co., Ltd - Marketing Estelle Zhu 5F, 58 Xiangcheng Rd, Pudong New District Shanghai 200122 CHINA 86-139-1786-4477 http://www.apexgrease.com/
Apex Grease is a marketing and branding division based in Shanghai, China with a global network providing food grade lubricants and industrial specialties. 100% manufacturing in Europe and the US, we are rooted in Chinese market with a strong distributing network and local know-how by seeking business opportunities worldwide.
Axxess Chemicals, founded in 2009, is a valueadded global distributor of Molybdenum Disulfide, Polybutene, Base Oils, Transformer Oils and many other specialty chemicals. Although the grease and lubricant market remains the largest markets we service, Axxess Chemicals also services the needs of the Industrial, Pharmaceutical, Steel, Automotive, PTFE, Cosmetics and Adhesives industries.
Biederman Enterprises- Supplier Pete Avery 2975 Long Lake Rd St. Paul, MN 55113 USA 314-440-7472 http://www.biederman.ca/
Grease cartridge supplier - HDPE with aluminum end. Biederman Enterprises Inc. has a long history of achieving excellence in quality products, services and business relationships. As a manufacturer of plastic cartridge tubes for greases, Biederman continues to gain momentum in the global marketplace. As a market leader for plastic grease cartridge tubes with metal ends, our tubes offer uncompromised stability on grease fill production lines, transport, and display shelves. Complete with an easy to open metal pull-tab removal, there is virtually no tearing and no tools are required, eliminating end-user frustration and product waste.
-8VOLUME 80, NUMBER 2
dtb2 LLC - Technical
As a member of the Canadian Association of Chemical Distributors we value the protection of health, safety and environment and ethical business practices.
Derek Benedyk 500 West Bradley Road, A#219 Fox Point, WI 53217 USA 312-206-4819 www.dtbtwo.com
Thompson Creek Metals Co., USA – Supplier
dtb2 LLC is a research and development company, dedicated to providing solutions for; unique lubricant formulations and applications, as well as, technical field service support and analysis of lubrication applications and processes.
Runningland Metrology & Testing (Shanghai) Co., Ltd - Technical David Ahou 128 Xiangyin Rd, Ste 101, Bldg C Shanghai, 200433 CHINA 0086-21-6530-1818 www.runningland.cn
Runningland Metrology & Testing (Shanghai) Co., Ltd is a certified and accredited independent third party laboratory for instruments metering, calibration and testing in the petrochemical industries. Runningland undertakes products testing for petrochemical products and equipment condition monitoring. The company operates two professional labs in Shanghai for: • Instruments Metering, Calibration & Testing • Petroleum Oil Testing • Condition Monitoring 3rd Party, ISO 17025 certificated, Oil, Grease fluid testing lab in China and Asia Pacific Region. We offer analysis, condition monitoring and instruments metrology. Our samples testing turn around time is very quick.
Thames River Chemical – Supplier Andy McGivern 5230 Harvester Road Burlington, ON L7L 4X4 Canada 905-220-2321 www.trc-corp.com
Mark Wilson 26 West Dry Creek Circle, Suite 810 Littleton, CO 80120 USA 303-761-8801 www.thompsoncreekmetals.com
Molybdenum Producer - Thompson Creek Metals Company Inc. is a North American mining company engaged in the full mining cycle, which includes acquisition, exploration, development, and operation of mineral properties. In the past several years, we have evolved from being a major primary molybdenum producer to becoming a copper and gold mining company with the construction and development of the Mount Milligan open-pit copper-gold mine and concentrator in British Columbia, Canada. In addition to Mount Milligan Mine, we own and operate a metallurgical facility in Pennsylvania, USA, at which it roasts molybdenum concentrate and other metals.
The Unami Group, LLC - Technical Bill Tuszynski 27 S Vassar Drive Quakertown, PA 18951 USA 267-374-1631 www.unamigroup.com
The Unami Group, LLC is a consulting organization providing strategic, commercial and technical support to help clients identify and develop profitable business opportunities in the chemical, lubricant, materials and adjacent segments.
Thames River Chemical Corp. distributes chemical products in specialized markets across North America. -9NLGI SPOKESMAN, MAY/JUNE 2016
Effect of MoDTC and MoDTP on Frictional and Antiwear Properties of Overbased Calcium Sulfonate Complex Greases Mihir K. Patel, Ruiming “Ray� Zhang, Ronald J. Hiza and Steven G. Donnelly Abstract In real grease application cases, there will always be the need and demand to achieve higher performance levels. Though the inherent superiority in antiwear and extreme pressure (EP) performance of calcium sulfonate complex grease is very obvious in both lab bench tests and real world applications, every now and then, there are complaints that the intrinsic EP performance offered by the base grease is not enough. This present paper reports the impact of certain anti-wear and EP additive chemistries on the performance of overbased calcium sulfonate complex greases. Frictional properties and energy efficiency of these additized greases were studied using Stribeck Curves generated using Mini Traction Machine (MTM). Film formation properties of these additives were further explored using Electrical Contact Resistance (ECR). 1. Introduction Calcium sulfonate complex grease since its development and introduction from the simple calcium sulfonate grease more than 20 years ago has gained significant commercial interest and popularity in recent years (1-9). It is the only grease thickener system which has enjoyed a more than 30% annual growth rate by a grease production survey couple years ago (10), albeit from a relatively small base. Expiration of certain key calcium sulfonate complex grease patents, and improved availability of key raw materials, i.e. high TBN Newtonian calcium sulfonate suitable for grease making, may explain partially the trend. However, the real driving force for the popularity of this relatively new grease thickener technology is the fact that the thickener system can also provide several key intrinsically superior grease performance functionalities
without any or with minimal use of additives. The thickener system for the calcium sulfonate complex grease probably can be considered as one of the most complex among all complex greases. It is believed that the main component of this thickener system, i.e. calcium sulfonate containing crystalline calcium carbonate in micelle form is the key to its inherent high load carrying or extreme pressure capability, excellent water resistance and rust inhibition performance. The pseudo particle nature of calcium sulfonate covered calcite micelle further explains its high temperature performance similar to most particle thickened greases like bentonite clay or fumed silica thickened greases. Nevertheless, in real grease application cases, there will always be the need and demand to achieve higher performance levels. Though the inherent superiority in anti-wear and extreme pressure (EP) performance of calcium sulfonate complex grease is very obvious in both lab bench tests and real world applications, every now and then, there are complaints that the intrinsic EP performance offered by the base grease is not enough. This present paper reports the impact of certain anti-wear and EP additive chemistries have on the performance of overbased calcium sulfonate complex greases. Further, the Mini Traction Machine (MTM) test method is employed to explore the influence of these additives on Stribeck curve, frictional coefficient, Electrical Contact Resistance (ECR) and Stribeck Friction Coefficient (SFC) which is related to grease energy efficiency through the whole tested Stribeck curve ranges, from EHL, mixed and boundary lubrication regime. 2. Grease Samples and Additives Three overbased calcium sulfonate complex base greases were obtained from three different regions. Base Grease
- 10 VOLUME 80, NUMBER 2
A is from North America, Base Grease C is from Asia Pacific and Base Grease S is from Europe. Three different EP additives and two antiwear additives/friction reducers were used in this study. The identities of these base greases and additives are listed in Table 1. Summary of the test formulations is described in Table 2.
3. Experimental Techniques In antiwear and EP performance evaluation, standard ASTM test methods and conditions were used. For four-ball wear test, ASTM D2266 test method was used. For four-ball EP test, ASTM D2596 test method was used. For Timken EP test, the Timken OK Load was measured according to ASTM D2509 test method. Rolling and sliding friction experiments were conducted using Mini Traction Machine (MTM). MTM consists of a rotating ½” (12.7 mm) diameter 52100 steel ball pressed against an independently rotating 52100 steel disc immersed in the grease. The operating conditions are set by independently controlling the rotational velocities of the shafts that drives the ball and the disc, in order to obtain a particular combination of rolling speed and slide to roll ratio, as well as by controlling the contact force and the oil bath temperature. All experiments were conducted at two temperatures 40 °C (low temperature) and 140 °C (high temperature). All experiments were carried out at 0.5 slide to roll ratio corresponding to 50% rollingsliding contact conditions. Slide-roll ratio is defined as the ratio of sliding speed to ub-ud mean speed, where ub and ud are speed of ball and disc respectively. These experiments were carried out at contact pressure of 1.5 GPa. Mean speed for each Stribeck curve were started at 1000 mm/s and decreasing in steps of 100 mm/s to 100 mm/s and finally decreased from 100 mm/s in steps of 10 mm/s to 10 mm/s. A comparison of the performance of each grease samples can be made by integrating the area under each Stribeck curve. The value of this integral, traction CoF.log(u), is known as the Stribeck Friction Coefficient (SFC). Lower values of SFC indicate that less energy will be absorbed by the lubricant under mixed and boundary and elastohydrodynamic lubrication (EHL) regimes. Lower values would therefore be expected to correlate with better performance in reducing frictional losses. The measurement of the electrical contact potential/electrical contact resistance (ECR) during the test was considered to be important data for us to capture in this study. The contact resistance is a function of contact area, electrical resistance of the materials in contact, and electrical resistance of the lubricants and the film thickness/asperity interaction including boundary layer film or tribofilm formed in contact area. In the context of stribeck curve, when the entrainment speeds are high (EHL lubrication regime), the surfaces in the contact are fully separated by the lubricant film. The electrical contact resistance (ECR) reading will be equal (or close) to 100%. As the speed and/or viscosity decrease, the film thickness decreases and the contact enters the mixed lubrication regime: where surface asperities are only separated by thin - 11 NLGI SPOKESMAN, MAY/JUNE 2016
surface boundary films. With increasing asperity/boundary film contact, the ECR reading drops. Variation in the contact resistance gives a qualitative assessment of the reduction in metallic contact due to the presence of either hydrodynamic or boundary lubrication films. The instantaneous measurement provides information on the lubrication regime and values can be used to assess the effectiveness of additives in forming protective tribofilm. MTM was used as described earlier and electrical current flow / electrical resistance between rubbing surfaces was measured using electrical circuit as shown in figure below.
- 12 VOLUME 80, NUMBER 2
The frictional properties of overbased calcium sulfonate Greases A, C & S were evaluated using Mini Traction Machine (MTM) as show in Figure 1. Typical Stribeck curves were generated through continuous rubbing test at 50% slide-roll ratio where friction is measured over a range of entrainment speeds at low and high temperature of 40 ⁰C and 140 ⁰C. As the test time progresses, it can be seen that friction increases when entrainment speed decreases for all three grease samples at 40 ⁰C and 140 ⁰C. Moreover, all overbased calcium sulfonate grease samples demonstrated noticeably different Stribeck curves. At 140 ⁰C overbased calcium sulfonate Grease S shows dramatic increase in the friction compared to Greases A and C as well as Grease S at 40 ⁰C at intermediate entrainment speed. Interestingly, at lower speed and at 140 ⁰C, all three grease samples demonstrated reduction in friction. At lower speed and higher temperature, Stribeck curve operates under boundary lubrication regime where an increased number of asperities contact would occur which leads to higher possibilities of wear and
friction. However, reduction in friction in the boundary lubrication regime indicates the formation of a friction reducing film by overbased calcium sulfonate grease. Figure 7 shows Stribeck friction coefficient (SFC) for overbased calcium sulfonate Greases A, C & S at 40 °C and 140 °C. Comparison of SFC values at 40 °C and 140 °C indicates frictional energy absorbed by the test samples in boundary, mixed and EHL lubrication regime as a function of temperature. Higher SFC values of Grease S at 140 °C than at 40 °C is indicative of higher energy absorption with increasing temperature which contributed to higher frictional energy losses during test. An analogous phenomenon was noticed with Grease C. Grease A, however, has a lower SFC value at 140 °C than at 40 °C indicating less energy absorption at 140 °C thereby suggestive of less frictional energy losses with increasing temperature.
- 13 NLGI SPOKESMAN, MAY/JUNE 2016
Antimony in combination with zinc dithiocarbamate was added to the grease samples and the rolling friction performance was measured. As shown in Figure 2, Stribeck curve at 40 °C shows analogous friction behavior at all entrainment speeds for all three greases which indicates less influence of metal dithiocarbamate (DTC) addition to overbased calcium sulfonate grease on the rolling friction compared to grease by itself. However, at higher temperature, a significant increase in the rolling friction was noticed with Grease S mixed with metal DTC. As shown in Figure 7, higher SFC values at 140 °C for Grease S mixed with metal DTC indicates higher energy absorption for all boundary, mixed and EHL lubrication regime which contributed to higher frictional dithiocarbamate energy losses. Similar frictional performance was observed with Grease S without addition of metal DTC (Figure 2).
Percent friction reduction of overbased calcium sulfonate grease due to addition of metal dithiocarbamate was calculated, as shown in Figure 8. Grease S mixed with metal DTC displays an improvement in the reduction of friction at 40 °C. This frictional benefit is completely lost at 140 °C where frictional losses increased by 4%. SFC values and frictional increases at 140 °C for Grease S indicate that addition of metal DTC does not contribute to the friction improvement of Grease S. On the contrary, at 140 °C, Grease sample C mixed with metal DTC shows 26% friction reduction compared to base grease itself. Similarly, Grease A mixed with metal DTC shows reduced friction at both temperatures. SFC values and percent friction reduction in tandem indicate that metal DTC shows synergistic effect to reduce frictional losses at higher temperature with Greases A and C, while it shows antagonistic effect with Grease S.
- 14 VOLUME 80, NUMBER 2
2,5-dimercapto-1,3,4-thiadiazole (DMTD) was evaluated for its rolling friction performance in overbased calcium sulfonate grease. As shown in Figure 3, Greases C and S mixed with DMTD exhibit typical Stribeck curve where rolling friction increased as entrainment speed reduced at 40 ⁰C and 140 ⁰C. However, Grease A mixed with DMTD shows contrasting friction performance at 40 ⁰C and 140 ⁰C. At 40 ⁰C, reduction in the friction is noticed with reduction in the entrainment speed indicative of formation of friction reduction film at lower temperature in mixed and boundary lubrication regime. At 140 ⁰C, Grease A mixed with DMTD shows increase in the friction at lower entrainment speed at higher temperature.
As shown in Figure 7, all greases mixed with DMTD exhibit lower SFC values with increased temperature. Percent friction reduction results, as shown in Figure 8, indicate that Greases C and S mixed with DMTD can reduce frictional energy losses by 23% and 73% respectively at 140 ⁰C. Only Grease A mixed with DMTD shows an increase in the friction compared to base grease at 40 °C and a slight increase in friction at 140 °C. SFC values and percent friction reduction results indicates that DMTD interacts synergistically with all overbased calcium sulfonate greases at higher temperature which contributes to lower frictional losses and improved rolling friction performance of overbased calcium sulfonate grease.
- 15 NLGI SPOKESMAN, MAY/JUNE 2016
5,5-dithiobis(1,3,4-thiadiazole) (DMTD Dimer) was evaluated for its rolling friction performance in overbased calcium sulfonate grease. As shown in Figure 4, Greases C and S mixed with DMTD Dimer exhibit typical Stribeck curves where rolling friction increased as entrainment speed reduced at 40 °C and 140 °C. However, Grease A mixed with DMTD Dimer shows contrasting friction performance at 40 °C and 140 °C. At 40°C, reduction in the friction is noticed with reduction in the entrainment speed, indicative of formation of friction reduction film at lower temperature in mixed and boundary lubrication regime. At 140 °C, Grease A mixed with DMTD Dimer shows increase in the friction at lower entrainment speed. As shown in Figure 7, higher SFC values at 140 °C for Grease S mixed with DMTD Dimer indicates higher energy absorption for all boundary, mixed and EHL lubrication regime which contributed to higher frictional energy losses. Similar frictional performance was observed with Grease S without addition of metal DTC (Figure 2). While Greases A and C mixed with DMTD Dimer exhibit lower SFC values with increased temperature.
Figure 8 shows percent friction reduction of overbased calcium sulfonate Greases A, C & S mixed with DMTD Dimer at 40 °C and 140 °C compared to overbased calcium sulfonate grease by itself. Grease S mixed with DMTD Dimer shows 34% friction reduction at 140 °C, while Grease C mixed with DMTD Dimer shows 11% reduction in friction compared at 140 °C. Only Grease A mixed with DMTD Dimer shows increase in the friction compared to base grease at 40 °C and a slightly lower increase in friction at 140 °C. SFC values and percent friction reduction in tandem indicate that DMTD dimer shows synergistic effect to reduce frictional losses at higher temperature with Greases A and C, while it shows antagonistic effect with Grease S.
- 16 VOLUME 80, NUMBER 2
A combination of 2 mass% 5,5-dithiobis(1,3,4thiadiazole) (DMTD Dimer) and 1 mass% molybdenum dialkyl dithiocarbamate was evaluated for its rolling friction performance in overbased calcium sulfonate grease. Figure 5 shows that addition of molybdenum dialkyl dithiocarbamate (MoDTC) along with DMTD Dimer in Grease A significantly reduces rolling friction at 140째C. As shown in Figure 7, higher SFC values at 140 째C for Grease S mixed with MoDTC along with DMTD Dimer indicates higher energy absorption for all boundary, mixed and EHL lubrication regime which contributed to higher frictional energy losses. Similar frictional performance was observed with Grease S without addition of metal DTC (Figure 2). While Greases A and C mixed with MoDTC and DMTD Dimer exhibit lower SFC values with increased temperature. A combination of MoDTC and DMTD Dimer appears to activate at higher temperature which resulted in reduced friction at all entrainment speeds. SFC values validate this observation. This is distinctly contrasting to the Stribeck curve generated by grease sample mixed with DMTD Dimers but without MoDTC.
Interestingly, addition of molybdenum dialkyl dithiocarbamate to Grease S mixed with DMTD Dimer reduced friction by 35% compared to base grease. Similarly, Grease A and Grease C mixed with molybdenum dialkyl dithiocarbamate and DMTD Dimer reduced friction at higher temperature by 24% and 14%, respectively. SFC values and percent friction reduction results indicate that MoDTC and DMTD Dimer interact synergistically with all overbased calcium sulfonate greases at higher temperature which contributes to lower frictional energy losses and improved rolling friction performance of overbased calcium sulfonate grease. 4.1.6 Effect of DMTD Dimer & MoDTP A combination of 5,5-dithiobis(1,3,4-thiadiazole) (DMTD Dimer) and molybdenum dialkyl dithiophosphate was evaluated for its rolling friction performance in overbased calcium sulfonate grease. Figure 6 show that addition of molybdenum dialkyl dithiophosphate (MoDTP) along with DMTD Dimer in Grease A significantly reduces rolling friction at 140 째C.
- 17 NLGI SPOKESMAN, MAY/JUNE 2016
As shown in Figure 7, higher SFC values at 140 째C for Grease S mixed with MoDTP and DMTD Dimer indicate higher energy absorption for all boundary, mixed and EHL lubrication regime which contributed to higher frictional energy losses. Similar frictional performance was observed with Grease S without addition of metal DTC (Figure 2). While Greases A and C mixed with MoDTP and DMTD Dimer exhibit lower SFC values with increased temperature. This is distinctly contrasting to the Stribeck curve generated by grease sample mixed with DMTD Dimer but without MoDTP. Interestingly, addition of MoDTP to Grease S mixed with DMTD Dimer reduced friction by 28% compared to base grease. Similarly, Grease A and Grease C mixed with MoDTP and DMTD Dimer reduced friction at higher temperature by 7% and 19%, respectively. SFC values and percent friction reduction results indicate that MoDTP and DMTD Dimer interact synergistically with all overbased calcium sulfonate greases at higher temperature which contributes to lower frictional energy losses and improved rolling friction performance of overbased calcium sulfonate grease.
- 18 VOLUME 80, NUMBER 2
Electrical contact resistance was recorded at entrainment speed from 1000 mm/s to 10 mm/s using Grease A by itself and with DMTD dimer and combination of DMTD Dimer with MODTC as well as with MoDTP at 40 ⁰C (low temperature) and 140 ⁰C (high temperature). At 40 ⁰C (low temperature), DMTM dimer and DMTM dimer + MoDTC show 100 % ECR signal at all entrainment speed which indicative of completely separated surface due to film formation. While base grease by itself and combination of DMTD dimer and MoDTP shows lower ECR values at lower entrainment speed which is indicative of thinner film formation in the boundary lubrication regime. With increase in entrainment speed base Grease A by itself and combination of DMTD dimer and MoDTP shows higher ECR values indicative of transition from boundary to mixed or EHL lubrication regime. A completely opposite results were obtained at higher temperature where grease by itself exhibit good surface separation while DMTD dimer and combination DMTD dimer and MoDTC show thinner film which indicates the effect of temperature on film formation.
- 20 VOLUME 80, NUMBER 2
As shown in figure 10, Grease C exhibits lower values of contact resistance at the lower temperature for all entrainment speeds indicative of thinner film formation. Contact resistance values are reduced further at the higher temperature suggestive of deterioration of film formation properties at the higher temperature. Formulating Grease C with DMTD dimer and its combination with MoDTC and MoDTP seem to increase contact resistance at the lower temperature. Whereas DMTD dimer with MoDTC exhibits a higher contact resistance at all entrainment speeds and at low temperature which is indicative of fully formed film formation. In the case of Grease C, at the higher temperature, DMTD dimer with MoDTC retains higher contact resistance and hence film formation. Similarly, DMTD dimer exhibits lower contact resistance than its combination with MoDTC at the lower temperature but increasing values of contact resistance
are observed at the higher temperature. This indicates the effect of temperature on activating the DMTD dimer. While a combination of DMTD dimer and MoDTP exhibits similar contact resistance at both the low and high temperatures. Grease S shows very poor response for film formation as shown in Figure 11. Grease S by itself as well as with additives show lower contact resistances at all entrainment speeds at lower temperature indicative of very thin film formation in boundary and mixed lubrication regime. However, with increasing temperature and rubbing time, Grease S by itself and with additives seems to exhibit thinner films even at higher speed. This may be the result of the tribofilm’s inability to maintain surface separation for longer duration.
- 21 NLGI SPOKESMAN, MAY/JUNE 2016
7-10 MARCH 2017 FOUR SEASONS HOTEL, SINGAPORE As usual, the F+L Asia conference was a great success relative to the presentation content. As Teri [Kowalski] has mentioned in her presentations, F+L Asia is the conference to attend to get the most informative updates on what’s going on around the globe in the world of lubricants.
CALL FOR PAPERS
IS NOW OPEN DEADLINE FOR ABSTRACT SUBMISSION:
JIM LINDEN L I N D E N C O N S U LT I N G , L L C
SEPTEMBER 2016
SAVE THE DATE! F+L Week 2017
7-10 MARCH, 2017
FOUR SEASONS HOTEL, SINGAPORE - 22 VOLUME 80, NUMBER 2
Teri Kowalski presenting on “The continuing saga of ILSAC GF-6” during F+L Week 2016
A BLAST FROM THE PAST
NLGI MEMBER
SPOTLIGHT
Over 125 years of lubricating grease experience Company: AXEL Americas, LLC Member Category: Manufacturer Contact Name: Tom Schroeder Country: USA AXEL Americas LLC is a leading supplier of lubricating greases in the US market and a part of the AXEL Christiernsson Group (AXEL). During the last ten years, AXEL has expanded dramatically to become a leading global producer and supplier of lubricating greases, with state-ofthe-art ISO Certified manufacturing facilities in Sweden, France, the Netherlands, and the US. In 2011, AXEL acquired the assets of Jesco Resources and gained access to two grease production facilities in the US with an initial combined capacity of 16,000 MT/year. Axel Americas’ management, R&D staff, and original grease plant are located in North Kansas City, Missouri. AXEL products manufactured in Kansas include greases containing graphite and MoS, a whole range of lubricants for the mining industry, and calcium sulphonate complex products.
Address: 1 440 Erie St., PO Box 12337, North Kansas City, MO 64116 Telephone: (816)-471-4590 Email: tom.schroeder@axelch.com
AXEL’s main US manufacturing and warehousing facilities are in Rosedale, Mississippi about 110 miles south of Memphis. Built on a greenfield site and inaugurated in 1986, this ISO and TS certified plant has undergone a series of expansions to meet the growing customer demands for its industrial and automotive greases, which are supplied to multinational companies and large distributors in the Americas. The most recent multi-million dollar investment at the Rosedale facility is comprised of a new Calcium Sulfonate production line and an additional Polyurea production line. The expansion includes four new production kettles, a state-of-the-art PLC system, seven new bulk finished good storage tanks, and two new base oil storage tanks. In addition to the new production
“This investment will not only increase our flexibility and production capacity by more than 17.2 million pounds, it will also allow us to produce some of the more specialized grease technologies our customers are demanding. Our investment demonstrates our continued commitment to growing our presence in the US market and to providing our customers with world class solutions and innovative grease technologies.” Tom Schroeder, President, AXEL Americas - 24 VOLUME 80, NUMBER 2
lines, AXEL has also installed a new cartridge filling line that can fill 56,250 cartridges per shift.
AXEL’s Unique Customized Label™ Strategy
AXEL’s Customized Label™ Strategy means that it becomes a true partner on several fronts. The company provides over 125 years of grease expertise to help its customers grow their grease business. It manufactures grease to the highest standards, consistently and reliably across its five global ISO certified facilities, but also dedicates its resources to support its customers’ technical, R&D, sales and marketing efforts. The company works closely with its customers’ functional teams to deliver new and superior grease technologies, educate their sales forces, provide field support, and a host of marketing and business development services.
AXEL works with its partners to optimize their product portfolios, develop unique solutions for complex and demanding applications, and to identify new growth markets and segment opportunities.
A Focus on Partnership and Growth AXEL’s sole focus is on defining, developing and producing high-quality lubricating grease products, and providing unique services to grow its cusztomers’ grease business and brands. This is why some of the worlds’ largest and most prestigious lubricating grease manufacturers have put their trust and good name into AXEL’s hands. For AXEL, Customized Label™ is about true partnership and alignment, and about teams of people working on a common objective. It is the modern way of making money on lubricating greases.
AXEL’s Global Presence and Reach
Axel Locations AXEL CHRISTIERNSSON AB STRANDVÄGEN 10, BOX 2100 449 41 NOL SWEDEN PHONE: +46 303 33 25 00 EMAIL: INFO@AXELCH.COM
AXEL AMERICAS LLC 150 RUSSEL CRUTCHER ROAD, ROSEDALE, MS. 38769 USA PHONE: +1 662 759 6808 EMAIL: INFO@AXELCH.COM
AXEL CHRISTIERNSSON B.V. 1 FEBRUARIWEG 13 4794 SM HEIJNINGEN NETHERLANDS PHONE: +31 167 522 980 EMAIL: INFO@AXELCH.COM
AXEL AMERICAS LLC 1440 ERIE ST. NORTH KANSAS CITY, MO. 64116 USA PHONE: +1 816 471 4590 EMAIL: INFO@AXELCH.COM
AXEL FRANCE SAS 30 RUE DE PIED DE FOND ZI ST LIGUAIRE - CS 98821 79028 NIORT CEDEX FRANCE PHONE: +33 5 49 77 13 71 EMAIL: INFO.FRANCE@AXELCH.COM
AXEL CHRISTIERNSSON INTERNATIONAL AB STRANDVÄGEN, BOX 2100 449 41 NOL SWEDEN PHONE: +46 303 33 25 00 EMAIL: INFO@AXELCH.COM CONTACT: TOM SCHROEDER PRESIDENT AXEL AMERICAS
AXEL products are produced under the strictest quality standards including ISO 9001, 14001, 21469 and TS 16949.
NLGI is proud to announce the introduction of the ‘NLGI Member Spotlight’, a new feature of the 2016 all-digital Spokesman magazine. All NLGI members may take advantage of this opportunity to highlight your company’s history, global reach, vision, employees or whatever you’d like our readership to know about your company. You may talk about products & services, however, no competitor trade names may be used, nor mention of product pricing. There is no limit on words and we welcome many photos
of your headquarters, offices, plant & employee photos. We will accept articles for publication on a first received, first published basis. Contact Marilyn Brohm Marilyn@nlgi.org at NLGI if you would like to submit an article for possible publication in an upcoming issue. There is absolutely no charge to have your article appear in the NLGI Member Spotlight
the Expert Q:
Can you tell me what is the best solvent for dissolving hardened calcium sulfonate grease?
A:
Most hydrocarbon solvents will dissolve greases, including calcium sulfonate grease. Solvents such as heptane, kerosene, Stoddard Solvent, etc. should provide the desired effect. Toluene may also prove useful to dissolve the hardened grease.
Q:
Please guide me if lithium hydroxide is not available, what is the alternate chemicals for manufacturing lithium base grease?
A:
Lithium hydroxide monohydrate (LiOH•H2O) is the commonly used material for the manufacture of lithium soap thickened greases. Other compounds of lithium are not sufficiently reactive to react with the carboxylic acids (weak acids) used in grease manufacture.
Q:
At Servotronics Inc. we manufacture aerospace servovalves to ISO requirements. The extreme pressure lube we use to lubricate detail parts, which are press
fit together, has been inconsistent. We press a 440A stainless steel pin into a titanium hole with a .0008/.0012 inch interference fit. Grease fresh out of the can causes galling and seizing during the press while grease, which has been sitting out in a paper cup for weeks (months?) and has stiffened up works very well. The difference in performance took us by surprise. We are looking for a more consistent product or advice about our use of grease in this manner. Ideally we want a product that works right out of the can. Can you offer a recommendation?
A:
Press fit applications are often best served by incorporating lubricants with high concentrations of solid lubricants to overcome boundary friction. While NLGI cannot recommend a specific product or brand, it may be worthwhile exploring the use lubricating pastes for your press fit application.
Q:
Can a blend of fumed silica and bright stock be called a silicon grease?
A:
In general, greases that are claimed to be “silicone” (not silicon) are those based on a silicone fluid (some form of siloxane fluid). Some of those products are thickened
- 26 VOLUME 80, NUMBER 2
with fumed silica, but other thickeners are also possible in greases based on silicone fluids. In the case of the composition described, it would be proper to call the product “silica-thickened grease,” but not simply “silicon grease,” since the majority of the composition would be mineral oil (bright stock), which contains no silicon.
Q:
I am looking for a grease compatibility chart. Also, I am looking for information on the effects of combining Lithium based and Polyurea based greases.
A:
There is a grease compatibility chart found in NLGI’s “Lubricating Grease Guide”, available for purchase on the NLGI website. There are also plenty of charts found on the Internet that, for the most part, contain the same information.
The effects of combining lithium and polyurea based greases may vary in that the thickening systems can react to form either very soft thickening matrix that is unable to hold the base oil, or become chunky and lose it’s smooth homogeneity. Also, keep in mind that base fluids and additive incompatibilities can also change the combined grease properties. The term “polyurea” encompasses quite a variety of thickeners. Some polyurea thickeners are well known to be compatible with lithium and lithium complex greases, while other polyurea thickeners are well not to be incompatible with lithium and lithium complex thickeners. It is always best to perform a compatibility test using the specific products that could be mixed in service.
Generally, these compatibility charts are ok to get an idea of compatibility, however to be sure compatibility testing should be completed using a standard test method like, ASTM D6185, “Standard Practice for Evaluating Compatibility of Binary Mixtures of Lubricating Greases”.
Is inadequate product testing putting your company at risk? Don’t wait to find out . . . Our experience with over 600 standard, industry, and customized test methods enables us to offer the best assurance of product quality. We work closely with you to target product end use conditions with a selection of the most appropriate tests.
Petro-Lubricant Testing Laboratories, Inc.
A uniquely independent analytical tribology testing company… …with hundreds of clients around the world and a staff of scientists experienced with an extensive range of product types and applications.
ISO 9001 and ISO/IEC 17025 certifications info@petrolube.com
www.petrolube.com
Lafayette, NJ 07848 973-579-3448
Calcium Sulfonate Complex Greases Using Calcium Hydroxyapatite as a Hydroxide-Containing Basic Reactant J. Andrew Waynick
ABSTRACT Calcium sulfonate-based grease has been documented as far back as at least 1948, although more typically used simple calcium sulfonate grease technology was first disclosed in 1966. Calcium sulfonate complex greases were first disclosed in 1985 and differed from the previous simple calcium sulfonate greases by their use of complementary acids reacted with either calcium hydroxide or its anhydride equivalent, calcium oxide. All subsequent advances in calcium sulfonate complex grease technology have involved these calcium-containing bases - almost always the hydroxide - for reaction with the additionally added acids. A new technology for making calcium sulfonate complex greases has been developed that uses the hydroxide-containing material calcium hydroxyapatite as a complete or partial substitute for calcium hydroxide or calcium oxide. The greases resulting from this new technology solve a problem sometimes observed when some previously established calcium sulfonate complex technologies are employed. These new calcium sulfonate complex greases using calcium hydroxyapatite have been shown to be significantly superior to those of equivalent final reacted composition wherein earlier known technology is used. This paper describes aspects of this new composition and process technology. INTRODUCTION Lubricating greases thickened by salts of alkylbenzene sulfonic acids have been documented as early as 19481. However, highly overbased calcium sulfonate greases were first disclosed in 19662 with additional aspects of this technology described in 1968 and 19703,4,5,6. This technology involved using previously developed highly overbased calcium alkylbenzene sulfonate wherein the overbasing was primarily due to calcium carbonate. These highly overbased calcium sulfonates were typically prepared in a sealed pressurized vessel
by reacting an alkylbenzene sulfonic acid with a large stoichiometric excess of calcium oxide/hydroxide in the presence of water, a complementary promoting agent, and carbon dioxide. The calcium carbonate in the final overbased calcium sulfonate was shown to be devoid of any crystallinity by X-Ray diffraction and was therefore referred to as amorphous. The overbased calcium sulfonates were clear and bright with Newtonian rheology. When such overbased sulfonates were heated with converting agents, the amorphous calcium carbonate converted to a very small dispersed phase of crystalline calcium carbonate, desirably calcite. This dispersed phase was believed to be stabilized by the now neutral calcium alkylbenzene sulfonate that surrounded it in some sort of a micelle structure. Since the particle size of the dispersed calcite phase was largely in the nano range (as small as 4 - 5 nm), the extremely high surface area affected a stable gel structure sufficiently strong to provide a grease-like consistency. In 1972, additional work was described wherein the same calcium sulfonate greases could be made from alkylbenzene sulfonic acid, excess calcium oxide or hydroxide, water, carbon dioxide and a system of agents that acted both as a promoter and a converter, thereby forming the highly overbased sulfonate in situ and converting it to a grease structure in one smooth step without ever isolating the overbased calcium sulfonate7. Such a process was named a one-step process, whereas the previous methodology was named a two-step process. These overbased calcium sulfonate greases had excellent rust protection properties due to being nominally 50% of the original overbased calcium sulfonate. However, their poor pumpability, especially at lower temperatures, limited their use in other grease applications. A major advance in calcium sulfonate chemistry occurred in 1985 when these calcium sulfonate greases were modified by post-conversion addition of calcium
- 28 VOLUME 80, NUMBER 2
oxide or (usually) hydroxide followed by reaction with boric acid and 12-hydroxystearic acid8. Acetic acid was also typically used, although usually added preconversion. The additional thickening provided by the formed calcium 12-hydroxystearate and “calcium borate� resulted in significant reduction in the amount of the original overbased calcium sulfonate in the final grease. The rheology was also less tacky. This resulted in improved low temperature performance while maintaining the excellent corrosion protection properties. Shear stability and extreme pressure/antiwear properties (EP/AW) were also reported as being improved. These greases became known as calcium sulfonate complex greases wherein the complementary acids added post-conversion were called the complexing acids. By comparison, the earlier overbased calcium sulfonate greases became known as simple calcium sulfonate greases. It should be pointed out that in this original work and all subsequent work by the same group of researchers, the reaction product of boric acid and calcium hydroxide was referred to as simply calcium borate. Technically speaking, calcium borate has the formula Ca3(BO3)2, although the term is sometimes loosely used as a catch-all to cover any of the many complex borates that are well known to form. However, Ca3(BO3)2 is not the actual borate that is formed by reaction of calcium hydroxide and boric acid under the conditions used in making calcium sulfonate complex greases. An examination within any of the well-known advanced inorganic chemistry texts will show that boric acid is not a Bronsted acid, but is only a weak, mono-basic Lewis acid9. The protons attached to the oxygen atoms in boric acid are not normally removed by reaction with hydroxide-containing bases. Instead, the boron atom in boric acid accepts an electron pair from any available electron pair donor to form a tetravalent boron species. In the case of boric acid and water, the boron tetrahydroxide anion is formed, also forming a hydronium cation. Additional reactions are well documented where within the same molecule some boron atoms are trivalent while others are tetravalent, often with bridgehead structures connecting different points of ring systems (i.e. the tetraborate anion). The actual borate or borates formed under conditions used in making calcium sulfonate complex greases will reflect this boron chemistry A definitive analytical study showing which borate or borates are present in these calcium
sulfonate complex greases has not been found by this author. By 1995, several additional modifications of calcium sulfonate complex greases had been reported. In one case, boric acid was replaced with phosphoric acid, and the converting agents were required to be limited to only water and isopropyl alcohol10. In two other cases, the original calcium sulfonate complex grease was modified by adding a portion of the complexing acids pre-conversion so as to provide further improvements in thickener yield (lower levels of the original overbased calcium sulfonate in the final grease)11,12. In 2002, work was reported on the chemical structure of overbased calcium sulfonate complex greases wherein boric and 12-hydroxystearic acids were used as the complexing acids13. This paper claimed that no previous published work had explored this area. The most important information provided in this paper was: 1. Calcium sulfonate complex grease structure is based on extremely small dispersed calcite wherein the dispersion is provided by the neutral calcium alkylbenzene sulfonate in a micelle structure, as had previously been expected. 2. 12-hydroxystearic acid (presumably in its neutralized calcium salt) is incorporated into the shell of neutral calcium alkylbenzene sulfonate surrounding the calcite nucleus of the micelle. 3. The reaction product formed by boric acid is claimed to be calcium tetraborate, although no experimental data or referenced work is provided to support that assertion. 4. Calcium tetraborate actually enters into the calcite-occupied center of the micelle around which is the dispersing shell of neutral calcium alkylbenzene sulfonate and calcium 12-hydroxystearate. 5. No mention is made of acetic acid or calcium acetate. Apparently acetic acid was not used in making most of the greases for this study. However, one commercially available calcium sulfonate complex grease was used, and that grease is known to use a small amount of acetic acid in its production. No mention of the disposition of the calcium acetate in this grease
- 29 NLGI SPOKESMAN, MAY/JUNE 2016
was made. In 2008, a further refinement of the manufacturing process of calcium sulfonate-based greases was reported wherein a converting agent was incorporated within the highly overbased calcium sulfonate14. This allowed a calcium sulfonate-based grease to be made by adding only water and also eliminated the use of isopropyl alcohol as previously required in some prior work. During the development of calcium sulfonate based greases, there have been at least two published reviews covering this area of grease chemistry15,16. Finally, one important detail concerning the manufacture of calcium sulfonate greases needs to be described. During the development of the technology for producing highly overbased Newtonian calcium alkylbenzene sulfonates, it was determined that not all of the excess calcium oxide or hydroxide should be promoted to amorphous calcium carbonate. Originally it was determined that in order to achieve a stable clear and bright Newtonian product, about 5% of the excess calcium base needs to remain as calcium hydroxide in the final product17. (Since water is always one of the promoting agents used, any calcium oxide not promoted to calcium carbonate will be changed to calcium hydroxide in the final product.) While this relative amount of non-promoted calcium hydroxide in the final clear and bright overbased calcium sulfonate may have changed as the overbasing technology advanced, a certain portion of the nominally 400 mg KOH/g total base number (TBN) in today’s overbased calcium sulfonates will be present as amorphous calcium hydroxide, not calcium carbonate This amount of internal calcium hydroxide can be easily determined by the strong base number (SBN) procedure of ASTM D4739 or any other equivalent method. SBN values for today’s commercially available 400 TBN overbased calcium sulfonates are most often between 50 and 60 mg KOH/g, although some have been found to have values as low as 35 mg KOH/g. This author could find no reported work on whether or not the SBN of an overbased calcium alkylbenzene sulfonate has any effect on the properties of calcium sulfonate-based greases. This latter point became important a few years ago when it was noticed that some calcium sulfonate complex
greases in the U.S. and Europe had dropping points that were intermittently lower than what was expected. Calcium sulfonate complex greases with typical ASTM D2265 dropping points higher than 315 C (600 F) were sometimes as low as 254 C (490 F). A study was initiated with the following objective:
1. Determine whether the SBN of the overbased calcium sulfonate has any effect on the greases made from them. As the study progressed, it quickly became apparent that two additional objectives would be needed. They were:
2. Develop a more detailed understanding of the reaction of complexing acids with the calcium hydroxide when preparing calcium sulfonate complex greases from simple calcium sulfonate greases.
3. Investigate a new method to improve the dropping points of calcium sulfonate complex greases under certain circumstances while maintaining excellent dropping point in all other circumstances.
The remainder of this paper discusses work done to achieve these objectives. EXPERIMENTAL General Approach An experimental program was initiated to achieve the three previously listed objectives. First, a series of calcium sulfonate complex greases were made according to the same formula. The only differences in the greases were the overbased calcium sulfonate that was used and the SBN of the overbased calcium sulfonate. Dropping points and penetrations were measured for each of the greases. Next, several series of calcium sulfonate-based greases were made so as to provide a more detailed examination of the post-conversion reaction of complexing acids with the calcium hydroxide. Simple calcium sulfonate greases were made first as a baseline for comparison, followed by calcium sulfonate complex greases. Particular emphasis was placed on considering which calcium hydroxide was reacting - either the calcium hydroxide that derived from the overbased calcium sulfonate or the separately added powdered calcium hydroxide. The complexing acids first
- 30 VOLUME 80, NUMBER 2
examined were acetic acid and 12-hydroxystearic acid. The reaction of boric acid was examined separately since boric acid is, as already stated, a Lewis acid instead of a Bronsted acid. The resulting data were used to develop a series of propositions. These propositions then suggested a potential new solution to the dropping point issue. Finally, the potential new solution was evaluated by making and testing additional calcium sulfonate complex greases. Equipment, Test Methods, and Raw Materials The first series of greases were made in a closed reactor. Heating was provided by an electric heating mantle and stirring was achieved by a rotary stirrer. All other greases were made using a Kitchen Aid-style mixer with a planetary stirrer and heating mantle. All weights were measured using an open pan analytical balance capable of measuring to the nearest 0.01 gram. Each grease was given three passes through a three-roll mill with both gaps set at 0.001 inches. Test methods used to evaluate the greases were dropping point by ASTM D2265 and penetration by ASTM D217 or D1403. Concerning ASTM D2265, it should be noted that this test was used to detect changes in grease structure. Regardless of the real world significance of specific dropping point values, if two greases of similar bulk composition and consistency have significantly different dropping points, clearly there is a significant
difference in the structure of those greases. The suppliers of the various overbased calcium sulfonates provided the values for TBN, SBN, and other compositional data from which the %(wt) of calcium hydroxide, calcium carbonate, and neutral calcium alkylbenzene sulfonate were calculated. This allowed precise compositional information to be determined for the final reacted greases. All TBN values were determined by ASTM D4739. SBN values were determined by a proprietary method that provides the same results as ASTM D4739, but with greater precision. The units of mg KOH/gram for TBN and SBN will be understood to apply throughout this paper without actually using them within the text. All raw materials were essentially 100% pure unless otherwise indicated. Calcium hydroxide, calcium carbonate, and calcium hydroxyapatite were all food grade purity with a mean particle size below 5 microns. RESULTS AND DISCUSSION Initial Evaluation of Overbased Calcium Sulfonate SBN A series of six calcium sulfonate complex greases were made according to the technology as described in U.S. Patent 5,126,062. The process profile and composition of all six greases are provided in Figure 1 and Table 1, respectively.
Water and isopropyl alcohol (IPA) were used as the converting agents. Also, a small amount of dodecylbenzene sulfonic acid (DDBSA) was added before conversion began. All previous calcium sulfonate complex grease technologies teach using a small amount of DDBSA, claiming it is a detergent to help disperse the calcite that forms during conversion. The complexing acids used in these six greases were acetic, 12- hydroxystearic, and phosphoric acids. These complexing acids were added after calcium hydroxide was added to the converted simple calcium sulfonate grease. Since each of the overbased calcium sulfonates used in these greases already contained between 2.3% and 3.4% calcium hydroxide, the added calcium hydroxide further increased the total level that was available for reaction with complexing acids. It should be pointed out that none of the previous calcium sulfonate literature attempts to distinguish between the calcium hydroxide that was part of the overbased calcium sulfonate (internal) and that which was added separately (external) to insure a total amount sufficient for reaction with complexing acids. However, distinguishing between the two sources may be useful. The calcium hydroxide originally part of the overbased calcium sulfonate is very likely still buried within the micelle arrangement of the initial simple calcium sulfonate grease. The added calcium hydroxide will be outside that micelle structure. The issue of which source of calcium hydroxide reacts first will be explored throughout this paper. Grease 1 used an overbased calcium sulfonate (Sulfonate A) that had a TBN of 387 and a SBN of 50. Grease 2 used a different lot of the same overbased calcium sulfonate that had a TBN of 413 and a SBN of 41. Greases 3 - 6 used a different overbased calcium sulfonate (Sulfonate B). Greases 3 and 4 used sulfonates with SBN’s of 35 and 37, respectively. Grease 5 used the same sulfonate as Grease 4, but had additional calcium hydroxide added postconversion so as to bring the total calcium hydroxide level to what it would have been if the sulfonate had a SBN of 50. Finally, Grease 6 was made from a lot of the same sulfonate with a SBN of 50. Results are provided in Table 2. - 32 VOLUME 80, NUMBER 2
As can be seen, when the SBN of Sulfonate A varied from 41 to 50, no real effect on dropping point was observed. However, for greases made with Sulfonate B, there was a very significant effect of SBN on dropping point. For Greases 3 and 4 where SBN values were around 35, the dropping point was much lower than either of the two Sulfonate A greases. When extra calcium hydroxide was added post-conversion to Grease 5 so as to simulate a SBN of 50, the dropping point significantly improved, but not nearly to the level of Greases 1 and 2 where Sulfonate A was used. Likewise, using a Sulfonate B lot with a SBN of 50 improved the Grease 6 dropping point to about the same level as the simulated SBN 50 Grease 5. Also, Sulfonate A provided much better thickener yield than Sulfonate B. The data in Table 2 also shows that all greases had a significant excess of total calcium hydroxide relative to what was needed to react with all the complexing acids. At most, about 73% of the calcium hydroxide in Grease 3 was consumed, leaving about 27% unreacted. However, more information is obtained if one distinguishes between the calcium hydroxide that was part of the overbased calcium sulfonate and the part that was added separately after conversion. The calcium hydroxide from the overbased sulfonate may be less accessible for reaction as it is protected by the surrounding shell of neutral calcium alkylbenzene
sulfonate. However, it will have the higher surface area to volume ratio which tends to increase its reactivity. The added calcium sulfonate, as already stated, can be expected to be outside the micelle structure of the simple calcium sulfonate grease, but its surface area to volume ratio will be much less than the calcium sulfonate associated with the micelle structure. Table 2 provides an analysis of how the calcium sulfonate could have reacted with complexing acids depending on whether internal or external calcium hydroxide first reacted. As can be seen, regardless of which scenario is chosen, the first portion of calcium hydroxide fully reacts. However, if the added (external) calcium hydroxide reacts first, then much less of the sulfonate (internal) calcium hydroxide will react compared to how much added calcium hydroxide will react if the sulfonate calcium hydroxide reacts first. Although this is interesting, it is not sufficient to provide clear understanding of why Sulfonate B shows a very clear effect of SBN on grease dropping point. More systematic and detailed work is required if an understanding of the relationship between overbased sulfonate SBN and grease dropping point is to be obtained. Even so, two propositions can be made based on this initial data: Proposition 1: The SBN of overbased calcium sulfonates can affect the dropping point of calcium sulfonate-based greases, with sufficiently low SBN values being linked to
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lower dropping points. Proposition 2; Not all overbased calcium sulfonates show the SBN dropping point effect to the same extent if at all. Some are SBN-sensitive; some are not. Simple Calcium Sulfonate Grease To further evaluate the effect of overbased calcium sulfonate SBN on grease dropping point, new samples of Sulfonates A and B were obtained. Both sulfonates had TBN values of about 400. Sulfonate A had a SBN of 50; Sulfonate B had a SBN of 35. Before further examination of calcium sulfonate complex greases, both sulfonates were used to make simple calcium sulfonate greases. The base oil was a commonly used 600 solvent neutral paraffinic Group I base oil. The converting agents were water and a glycol. Figure 2 provides the process profile for these two greases. Table 3 provides the final compositions in %(wt). Note that the water is given as the actual grams used for the specific batch size that was made. This is done to separate
water from the other components since water is not part of the final grease but is lost during the heating process. The batch size in grams is also provided so that the actual gram amounts of each component can be readily calculated if desired. This format for grease batch compositions will be used for other greases in this paper. As can be seen, both greases had very high dropping points, on the same level as the highest dropping points of any of the previous six greases. Taking into account the concentrations of the original overbased sulfonate and the worked penetration, Sulfonate A continues to show superior thickener yield. The percent of calcium hydroxide consumed is due to the facilitating acid DDBSA, since that is the only acid used. A higher percentage of calcium hydroxide is consumed for Grease 8 because Sulfonate B has less initial calcium hydroxide. Since no added calcium hydroxide is used, the DDBSA must react with the most basic component available, which is the amorphous calcium hydroxide present in the overbased sulfonate. This information provides another proposition, which is an extremely critical one:
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Proposition 3: The lower dropping point observed in calcium sulfonate complex greases using low SBN Sulfonate B must be linked to something that happens when complexing acids react with calcium hydroxide to form the co-thickener components. Calcium Sulfonate Complex Grease Without Added Calcium Hydroxide Armed with this important proposition, a series of calcium sulfonate complex greases were made using increasing levels of only acetic and 12-hydroxystearic acids. The ratio of acetic to 12-HSA was similar for these
greases. The total level of complexing acids was not allowed to exceed the stoichiometric equivalent level of calcium hydroxide provided by the overbased calcium sulfonate. Thus the internally provided calcium hydroxide was never exhausted. No added calcium hydroxide was used. Accordingly, this series of greases provided information on what happens to the simple calcium sulfonate grease structure when the internal calcium hydroxide is neutralized. Figure 3 provides the process profile for these greases. Table 4 provides the composition and data.
As can be seen from this data, the calcium sulfonate complex greases made from 50 SBN Sulfonate A continue to have very high dropping points, unaffected even when about 95% of the internal calcium hydroxide is neutralized by the complexing acids. However, when the 35 SBN Sulfonate B is used, the resulting calcium sulfonate complex grease with 95% of the calcium hydroxide neutralized suffers a very large decrease in dropping point. It was also observed that when the acetic acid was added to the Sulfonate B greases, immediate white solid particulates formed in the grease. As the 12-HSA was then added and the grease was fully reacted and heated, the visible white particulates disappeared. When acetic acid was added to the Sulfonate A greases, very little if any white particulates could be seen. Comparing the worked penetrations of these four calcium sulfonate complex greases to their simple grease counterparts in Table 3, the thickener yield improvement for both overbased sulfonates is apparent. Also, Sulfonate A greases continue to have superior thickener yield to Sulfonate B greases. This data provides two more propositions:
Proposition 4: When most of the internal calcium hydroxide in the low SBN Sulfonate B is neutralized by complexing acids, the dropping point of the resulting calcium sulfonate complex grease is significantly reduced. This does not occur in the case of the higher SBN Sulfonate A. Proposition 5: When no added calcium hydroxide is present, adding acetic acid to simple calcium sulfonate grease made with low SBN Sulfonate B causes the resulting calcium acetate to move outside the grease micelle structure in such a way as to initially be largely non-dispersed relative to the rest of the thickener structure. This does not occur in the case of the higher SBN Sulfonate A. These two propositions suggest the possibility that when no added calcium hydroxide is present, the reactivity of the internal calcium hydroxide in Sulfonates A and B may not be the same with regard to one or more of the following: 1. Reactivity towards Bronsted acids 2. Location of neutralized products relative to the thickener micelle structure 3. Disruptive/destabilizing effects on
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thickener micelle structure Calcium Sulfonate Complex Greases With Added Calcium Hydroxide The next series of five calcium sulfonate complex greases extended the previous series by adding calcium hydroxide to the formed simple calcium sulfonate grease before adding acetic acid and 12-HSA. The manufacturing process for the first four greases (Greases 13 - 16) is the same as provided in Figure 3 except for an additional 30 minutes just after conversion wherein the calcium hydroxide is added and allowed to mix into the simple calcium sulfonate grease matrix. Grease 17 was made using the previously described simple calcium sulfonate Grease 8 as the starting material. The process for making Grease 17 began at the point in Figure 3 just after conversion. At that point, a very large excess of calcium hydroxide was added relative to the stoichiometric amount required to neutralize the added acetic and 12-hydroxystearic acids. The two acids were then added at about 88 C and allowed to react for 30 minutes. Then
the grease was heated, cooled, and milled like the other greases. Final compositions and data are provided in Table 5. All of these five calcium sulfonate complex greases have higher levels of complexing acids than the previous series of calcium sulfonate complex greases. This is a reflection of the added calcium hydroxide present in these five greases relative to the previous series where only the internal calcium hydroxide was available for reaction. As can be seen, Grease 13, the one grease using the 50 SBN Sulfonate A, had a very high dropping point, equivalent to the previous Sulfonate A Grease 7 (simple calcium sulfonate) and Greases 9 and 10 (calcium sulfonate complex without added calcium hydroxide). Note that 95% of the total calcium hydroxide was neutralized by the complexing acids in Grease 13. Furthermore, regardless of which source of calcium hydroxide is neutralized first, no less than 95% of the internal calcium hydroxide must have been neutralized. Thus, for the greases made with
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50 SBN Sulfonate A, no significant reduction in dropping point is observed regardless of how much calcium hydroxide is neutralized.
excess of added calcium hydroxide provided only slight improvement, possibly indicating an adverse effect due to the high excess base during the process heating step.
For Greases 14-17 where 35 SBN Sulfonate B is used, a much different picture is seen. All four of these greases had extremely low dropping points compared to any of the Sulfonate A greases of this study. Greases 14 - 16 provide a progressively increasing level of excess added calcium hydroxide. This was done intentionally so as to determine if a sufficient excess of added calcium hydroxide might protect the internal calcium hydroxide from being neutralized. Grease 16 did show a significant dropping point improvement compared to Greases 14 and 15. However, it was still far lower than the dropping point of any of the 50 SBN Sulfonate A greases. Grease 17 was made from the simple calcium sulfonate Grease 8, and was formulated so as to compositionally duplicate Grease 15 except for the much larger stoichiometric excess of calcium hydroxide. For Grease 17, the even higher
The most important information in Table 5 is the calculated amount of calcium hydroxide consumed. Since it has already been shown that neutralizing most of the internal Sulfonate B calcium hydroxide is linked to lower dropping points, it is useful to look at the two different possibilities for how complexing acids react with calcium hydroxide when added to calcium sulfonate-based greases. Figure 4 provides a direct comparison of the two ways that the internal calcium hydroxide from 35 DBN Sulfonate B can be consumed in all the greases thus far evaluated for which such data applies.
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Knowing that a depletion of internal calcium hydroxide from the 35 SBN Sulfonate B results in lower dropping points, which of the two sets of points in Figure 4 makes the most sense? Clearly, the preferential consumption of internal calcium hydroxide is most consistent with what has been shown to be true for greases made with this specific overbased calcium sulfonate. This data provides four more propositions: Proposition 6: When using the low SBN Sulfonate B, complexing acids added post-conversion preferentially react with the internal calcium hydroxide, even when additional calcium hydroxide has been previously allowed to mix into the matrix. Proposition 7: When using the low SBN Sulfonate B, adding stoichiometric excess calcium hydroxide post-conversion provides only minor protection for the internal calcium hydroxide. Proposition 8: The disruption and destabilization of the simple calcium sulfonate grease structure caused by neutralization of internal calcium hydroxide which is observed when Sulfonate B is used does not occur when Sulfonate A is used. This is true even when Sulfonate A has a SBN as low as 41.
Proposition 9: There is some yet unidentified structural difference between overbased Sulfonates A and B that renders Sulfonate B greases sensitive to destabilization when SBN is sufficiently low, but that renders Sulfonate A greases comparatively insensitive to the same destabilization. Calcium Sulfonate Complex Greases With Boric Acid A series of three greases, Greases 18 - 20, were made where boric acid was also used as a complexing acid, according to the scope of the original calcium sulfonate complex grease technology8. Only the 35 SBN Sulfonate B was used. Since Sulfonate A has been shown to provide very high dropping points in all the greases thus far described, no further work with this overbased calcium sulfonate was done. The process profile for making Greases 18 -20 is provided in Figure 5.
As with the previous series of calcium sulfonate complex greases, additional calcium hydroxide was added immediately after conversion and allowed to mix in. Then, a boric acid/water mixture was added and allowed to react for 15 minutes. The water/boric acid wt/wt ratio was about 13.5, and the water used was heated to near boiling before mixing with the boric acid. The acetic and 12-hydroxystearic acids were then added as the other complexing acids and allowed to react before heating, cooling, and milling like the previous greases. Grease 18 was formulated to be similar to Grease 15 except for the boric acid and the corresponding additional calcium hydroxide. Grease 19 was similar to Grease 18 except that the concentration of boric acid was reduced by almost half with a similar reduction in the calcium hydroxide. Grease 20 was made using Grease 15 as the starting material. This was done to determine the effect
of boric acid on a finished calcium sulfonate complex grease with a very low dropping point. The process for making Grease 20 began according to Figure 5 just after conversion. First, just enough acetic acid was added to completely neutralize the last minor amount of calcium hydroxide. This insured that no free calcium hydroxide from Grease 15 remained. Calcium hydroxide was then added followed by the boric acid/water mixture. The concentration of all three complexing acids was the same as in Grease 18. The added calcium hydroxide was only 1% more than the stoichiometric equivalent of the boric acid, assuming boric acid to be a Lewis acid that accepts one electron pair from either water or hydroxide. The composition and test data for Greases 18 - 20 are provided in Table 6. Grease 15 is also provided for easy comparison.
The ability of boric acid to dramatically increase the dropping point of calcium sulfonate complex greases is readily seen by comparing Greases 18 to Grease 15. Also, this effect is fully retained even when the boric acid concentration is significantly reduced, as indicated by Grease 19. However, it is the Grease 20 dropping point that provides the most important information. Although Grease 15 had a dropping point of 206 C (403F), Grease 20 had a dropping point greater than 343 C (650 F). The addition of a boric acid and water mixture was able to recover the dropping point of a previously made calcium sulfonate complex grease. Furthermore, before the boric acid was added to Grease 15, all the remaining free calcium hydroxide, including any internal calcium hydroxide still present, was neutralized. Only the added calcium hydroxide was available for any reactions. Also, as previously mentioned, boric acid is not a Bronsted acid. The added calcium hydroxide and boric acid would not form Ca3(BO3)2. The fact that boric acid is a Lewis acid is key in understanding how the dropping point is so dramatically increased. Boric acid will react with water under basic conditions to first form the boron tetrahydroxide anion, B(OH)4 -. This anion can react with other boric acid molecules and water to form one or more of the many polyborates. Since tetraborate has been cited as being present in boroncontaining calcium sulfonate complex greases13, its structure is provided below in Figure 6 as an example of polyborates in general.
a formal negative charge. This could allow tetraborate to form strong ionic associations with different calcium cations. Also, each trivalent boron atom in the tetraborate anion and other polyborate structures will possess some Lewis acidity that could allow for the formation of borate esters by reaction with organic oxygen. These features could allow such polyborates to form connections between different parts of a calcium sulfonate-based thickener system including calcium within the core of a calcium sulfonate micelle, calcium that may be external to it (such as the calcium in calcium 12-hydroxystearate or calcium acetate), hydroxy groups in calcium 12- hydroxystearate, and sulfonate groups. Any such linkage that provides a more intimate association of different thickener components may provide additional improvements in the grease structural stability. In fact, if the calcite/calcium sulfonate micelle structure is destabilized by neutralization of internal calcium hydroxide as previously proposed, any linkages provided by the borates may explain how the dropping point of Grease 15 was dramatically improved when it was reacted with boric acid to form Grease 20. While the data in Table 6 in no way constitutes proof of this mechanism, it certainly suggests it as a viable explanation. Thus, this data provides two final propositions: Proposition 10: When using low SBN Sulfonate B, boric acid can greatly increase calcium sulfonate complex grease dropping point when added either as the first or last complexing acid. Internal calcium hydroxide is not required to achieve this effect. Proposition 11: The Lewis acid properties of boric acid suggest that one or several complex borates provide linkages that more intimately associate various thickener components, thereby enhancing the structural integrity of the entire thickener.
Each of the four boron atoms is trivalent, and two oxygen atoms on either end of the three-ring system bear
A New Solution is Proposed Clearly, boric acid provides a solution to low dropping points associated with the use of overbased calcium sulfonates similar to the 35 SBN Sulfonate B. However, the test data thus far provided in this paper and the resulting eleven propositions suggest a more general solution that may have other specific solutions. If the boric acid does improve calcium sulfonate-based grease dropping point
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by providing chemical bonding or linkages between different parts of the thickener system, then other chemicals that have the potential to do the same thing might also work. It should be noted that in all the previously documented calcium sulfonate grease technology, the calciumcontaining base cited, taught, and claimed has been exclusively calcium oxide and calcium hydroxide. When calcium oxide or hydroxide is reacted with a complexing acid such as 12-hydroxystearic acid, once the calcium salt is formed, the calcium portion is no longer capable to form other strong linkages. However, if another hydroxide-providing calcium-containing base had additional functionality already bonded to the basic calcium capable of forming additional linkages after neutralization by complexing acids, and if that calciumcontaining base was used with a low SBN overbased sulfonate similar to the 35 SBN Sulfonate B, a final grease structure with enhanced stability might be obtained. One such potential calcium-containing base is calcium hydroxyapatite, Ca5(PO4)3OH. Calcium hydroxyapatite is a crystalline solid, and as the formula indicates, it contains a hydroxide ion. It also contains phosphate anions. By using simple algebraic manipulation, calcium hydroxyapatite’s formula can be rewritten as 2[Ca5(PO4)3OH] = 3Ca3(PO4)2 .Ca(OH)2. This has had the unfortunate effect of causing some to consider calcium hydroxyapatite to be nothing more than a blend of tricalcium phosphate, Ca3(PO4)2, and calcium hydroxide, Ca(OH)2. However, this is easily shown to not be correct. Calcium hydroxyapatite has a melting point of 1,100 C18 whereas tricalcium phosphate has a melting point of 1670 C19. Furthermore, calcium hydroxide does not have a melting point, but at 580 C it dehydrates to form calcium oxide20. Since calcium hydroxyapatite shows no such dehydration at 580 C, but melts at 1,100 C, this demonstrates that calcium hydroxyapatite contains no actual calcium hydroxide. Thus, not only is calcium hydroxyapatite not the same compound as tricalcium phosphate, it is also not a blend of tricalcium phosphate and calcium hydroxide. The solid state ionic bond between calcium cations and phosphate anions is very strong, as evidenced by the nearly water-insoluble nature of both calcium
hydroxyapatite and tricalcium phosphate. If calcium hydroxyapatite was efficiently dispersed within an overbased calcium sulfonate before adding complexing acids, the complexing acid salts formed (still in a dispersed solid state) would have phosphate anions bound to the calcium. If the phosphate was able to form similar bonds with other calcium cations, including those in the center of the calcite-calcium sulfonate micelle, this might improve thickener stability. It should be noted that the in-situ formed tricalcium phosphate of the initial evaluation calcium sulfonate complex greases using low SBN Sulfonate B (Table 2) would not be expected to provide as much structural improvement since the calcium cations originated from calcium hydroxide and would not in any way be bound to complexing acids or any other thickener component. An examination of the dropping points of Greases 3 and 4 (Table 2) show this to be so. Even Grease 6, which used a 50 SBN sample of Sulfonate B, did not provide a dropping point close to what was achieved when using Sulfonate A. A New Solution is Evaluated In order to determine the functionality of calcium hydroxyapatite as a calcium-containing base for reaction with complexing acids, two calcium sulfonate complex greases were made using another sample of the same Sulfonate B with SBN between 35 and 40. The process steps used to make these two greases are summarized side by side in Table 7. As can be seen, Grease 21 and 22 are nearly identical. In step 5, Grease 21 had 151.6 grams calcium hydroxyapatite added. This provided sufficient hydroxide for reaction with all complexing acids that would be added after conversion. Note that 151.6 grams of calcium hydroxyapatite has the same composition as if it contained 140.4 grams of tricalcium phosphate and 11.2 grams of calcium hydroxide. In the same step 5 for Grease 22, 11.2 grams calcium hydroxide were added instead. Thus, during and just after conversion, Greases 21 and 22 have the same molar amount of hydroxide present. In order that Greases 21 and 22 have the same final composition of all thickener-related components, Grease 22 must also have 140.4 grams of tricalcium phosphate added after conversion and reaction with complexing acids. This was accomplished in steps 10 and 13. In step 10, the stoichiometric amount of calcium hydroxide needed to form 140.4 grams of tricalcium
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phosphate was added. In step 13, after the complexing acids had reacted with their stoichiometric portion of the calcium hydroxide, the required stoichiometric amount of phosphoric acid was added and allowed to react under open conditions. Through step 18, both greases are identical in final reacted composition. The only difference between Greases 21 and 22 at this point was the source of hydroxide that was made available before and during conversion for reaction with complexing acids. Finally, both greases were finished with enough base oil to make them as similar in W/60 penetration as possible. The calcium hydroxyapatite was added before conversion so that it mixed into the initial simple calcium sulfonate grease as it formed. This provided the most intimate mixing possible so that the calcium
hydroxyapatite had the maximum availability for reaction with complexing acids after conversion. So as to make the comparison between Greases 21 and 22 valid, the hydroxide-equivalent amount of calcium hydroxide was also added before conversion to accomplish the same level of mixing and availability. Another grease, Grease 23, was made using the same steps as Grease 21 except that the calcium hydroxyapatite was added after conversion but before the 12-hydroxystearic and acetic acids were added. Compositional information and test data for Greases 21 - 23 are provided in Table 8.
The effect of using calcium hydroxyapatite as a hydroxide-equivalent substitute for calcium hydroxide is apparent in the dropping points of Greases 21 and 22. The dropping point of Grease 21 is much higher than the Sulfonate B calcium sulfonate complex Greases 3 6, 12, and 14 - 17. However, Grease 23 shows that one does not have to add the calcium hydroxyapatite before conversion in order to obtain a very high dropping point. Also, the initial evaluation Greases 3, 4, and 6 (Table 2) were similar to Grease 22 except that the calcium hydroxide used for reaction with all three acids was added postconversion. By comparing these three initial evaluation greases with Grease 23, one can see additional evidence of improved dropping point when calcium hydroxyapatite is used as a substitute for calcium hydroxide.
The effectiveness of calcium hydroxyapatite was further evaluated by making two more greases using the same process steps used to make Grease 21. However, Sulfonate B was not used. Grease 24 used another sample of Sulfonate A; Grease 25 used Sulfonate C, another 400 TBN sulfonate. Both of these overbased calcium sulfonates are known to generally provide acceptable dropping points when using all previously documented calcium sulfonate complex grease technologies. Compositional information and test data for Greases 24 - 25 are provided in Table 8. Grease 21 information is also included for reference. As can be seen, dropping points are very high for all three greases. Thus, calcium hydroxyapatite-based calcium sulfonate complex greases will have very high
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dropping points regardless of whether the overbased calcium sulfonate would otherwise cause lower dropping points or not. The superior thickener yield of Sulfonate A that was observed with earlier greases is apparent again here. Finally, a series of four final greases were prepared to demonstrate some variations in formulation that are possible when using calcium hydroxyapatite. All four greases used the same low SBN Sulfonate B. The process steps used to make Greases 26 and 27 are summarized side by side in Table 10.
In Grease 26, the total amount of 12-hydroxystearic and acetic acid was split so that portions were added both before and after conversion. Calcium carbonate was also added pre-conversion. Phosphoric acid was added postconversion as a third complexing acid. Grease 27 also uses boric acid and splits the addition of calcium carbonate before and after conversion. Grease 28 was made by the same process as Grease 27 with the primary difference being that 50% of the calcium hydroxyapatite was replaced by a hydroxide-equivalent amount calcium hydroxide. In Grease 29, 75% of the calcium hydroxyapatite was replaced by a hydroxideequivalent amount calcium hydroxide. Compositional information and test data for Greases 26 - 29 are provided in Table 11. Dropping points for all four greases are above 315 C (600 F). Also, greases 26 - 28 have significant improvement in thickener yield compared to previous greases in this paper. Although, it has been shown that calcium hydroxyapatite can be used as an alternative to boric acid when making calcium sulfonate complex greases, Grease 27 shows that both calcium hydroxyapatite and boric acid can be used together and still have excellent dropping points. Greases 28 and 29 demonstrate that the beneficial effect of calcium hydroxyapatite is maintained when used not only as a full replacement for calcium hydroxide, but also when used as a partial replacement. As much as 75% of the calcium hydroxyapatite can be replaced by a hydroxide-equivalent amount of calcium hydroxide and still maintain the beneficial effect on dropping points when using low SBN Sulfonate B. All previous calcium hydroxyapatite greases in this paper had a total amount of hydroxide that was more than sufficient to react with all complexing acids and the facilitating acid DDBSA. However, Greases 26 - 29 were purposely formulated so as to reduce the level of calcium hydroxyapatite to the point where the total hydroxide level was much less than what was needed to neutralize all added acids. The remaining acids were neutralized by the added calcium carbonate. Despite this, dropping points were excellent.
When comparing dropping points of Greases 1 - 17 to the greases where calcium hydroxyapatite was used, it is very clear that calcium hydroxyapatite is affecting the grease structure in a way that improves dropping point when the low SBN Sulfonate B is used. Thus, when using such overbased calcium sulfonates and grease technology that does not use boric acid, the use of calcium hydroxyapatite provides a superior approach to providing consistently high dropping point greases. Comparing the calcium hydroxyapatite greases to the Greases 18 - 20 where boric acid was used, it is clear that calcium hydroxyapatite provides similar improvement to grease dropping point when using low SBN Sulfonate B. CONCLUSIONS The results presented in this paper support the following conclusions: 1. To at least the extent that the structural stability of calcium sulfonate greases are indicated by dropping point, the SBN of the overbased calcium sulfonate can affect that structural stability. 2. Not all overbased calcium sulfonates are equally affected by SBN as it relates to final grease dropping point (SBN-sensitivity). 3. When complexing acids are added to a simple calcium sulfonate grease, there appears to be a bias to react with the internal calcium hydroxide from the overbased calcium sulfonate even when added micron-sized calcium hydroxide is present. 4. When SBN-sensitive overbased Sulfonate B is used, the depletion of the internal calcium hydroxide by reaction with complexing acids is one of the factors that cause a reduction in calcium sulfonate complex grease dropping point. 5. When non-SBN-sensitive overbased Sulfonate A is used, even when nearly all the internal calcium hydroxide is depleted by reaction with complexing acids, dropping point remains unaffected. 6. The mechanism whereby boric acid imparts high dropping points in calcium sulfonate complex greases that use SBN-sensitive overbased sulfonates may be due to the formation of linkages between different
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parts of the thickener system, thereby repairing or stabilizing the instabilities otherwise caused by the internal calcium hydroxide depletion. 7. Calcium hydroxyapatite, when used as a complete or partial replacement for added calcium hydroxide in calcium sulfonate complex greases, provides similar dropping point properties to those provided by the use of boric acid. 8. Calcium hydroxyapatite as a calcium-containing base for reaction with complexing acids does not react the same as a hydroxide-equivalent amount of calcium hydroxide. Neither does it react the same as if it were a simple blend of tricalcium phosphate and calcium hydroxide. Instead, it reacts in a way that provides superior calcium sulfonate complex grease dropping points when using SBN-sensitive Sulfonate B.
9. When using SBN-sensitive Sulfonate B, calcium hydroxyapatite may achieve its effect on calcium sulfonate complex grease dropping point by the formation of linkages between different parts of the thickener system, thereby repairing or stabilizing the instabilities otherwise caused by the internal calcium hydroxide depletion. However, the exact nature of those linkages will be chemically different than those formed by boric acid. ACKNOWLEDGEMENTS The author gratefully acknowledges Joe Garza for his work in preparing and testing the greases discussed in this paper.
- 47 NLGI SPOKESMAN, MAY/JUNE 2016
REFERENCES 1 Zimmer, John C.; Duncan, Gordon W. “Sulfonate Base Lubricating Grease”; U.S. Patent 2,444,970, 1948. 2 McMillen, Richard L. “Basic Metal-Containing Thickened Oil Compositions”; U.S. Patent No. 3,242,079, 1966 3 McMillen, Richard L. “Basic Metal-Containing Thickened Oil Compositions”; U.S. Patent No. 3,372,115, 1968. 4 McMillen, Richard L. “Process For Preparing Lubricating Grease”; U.S. Patent No. 3,376,222, 1968. 5 McMillen, Richard L. “Process For Preparing Thickened
Compositions”; U.S. Patent No. 3,377,283, 1968. 6 McMillen, Richard L. “Non-Newtonian Colloidal Disperse System”; U.S. Patent No. 3,492,231, 1970. 7 Rogers, Lynn C. “Method Of Improving Resistance To Corrosion Of Metal Surfaces And Resultant Article”; U.S. Patent 3,661,622, 1972 8 Muir, Ron; Blokhuis, William “High Performance Calcium Borate Modified Overbased Calcium Sulfonate Complex Greases”; U.S. Patent No. 4,560,489, 1985. 9 Cotton, F. Albert; Wilkinson, Geoffrey Advanced Inorganic Chemistry; Fifth Edition, John Wiley & Sons, pp 167-172. 10 Barnes, John F. “Calcium Sulfonate Grease And Method Of Manufacture”; U.S. Patent No. 5,126,062, 1992. 11 Olson William D.; Muir, Ronald J.; Eliades, Theo I “Sulfonate Greases”; U.S. Patent No. 5,308,514, 1994. 12 Olson William D.; Muir, Ronald J.; Eliades, Theo I “Sulfonate Grease Improvement”; U.S. Patent No. 5,338,467, 1994. 13 Kobylyanskii, E.V.; Kravchuk, G.G.; Makedonskii, O.A.; Ishchuk, Yu L. “Structure Of Ultrabasic Sulfonate Greases”; Chemistry and Technology of Fuels and Oils, 38(2), 2002. 14 Denis, R.A.; Sivik, M.R.; “Calcium Sulfonate Grease-Making Processes”; NLGI 75th Annual Meeting, Williamsburg, VA, June, 2008. 15 Mackwood, W.; Muir, R. “Calcium Sulfonate Grease - One Decade Later”; NLGI Annual Meeting, 1998. 16 Fish, Gareth; Ward Jr., William C “Calcium Sulfonate Greases Revisited”; NLGI 78th Annual Meeting, Palm Desert, CA, June, 2011. 17 Ellis, Glyn; Rhyl, Rhuddlan; Hartley, James; Wirral, Whitby; Moseley, John Campbell “Preparation Of Basic Polyvalent Metal Salts Of Organic Acids”; U.S. Patent No. 2,865,956, 1958. 18 Weast, Robert C. CRC Handbook of Chemistry and Physics; 52nd Edition, Chemical Rubber Company, p B-78. 19 American Elements, Calcium Phosphate, Tribasic, Ca5(OH)(PO4)3, technical data sheet. 20 Weast, Robert C. CRC Handbook of Chemistry and Physics; 52nd Edition, Chemical Rubber Company, p B-77.
The North American
Industrial Lubricants Congress
September 13-14 2016 // Chicago, IL, USA
SAVE $300 by booking before June 24, 2016!*
Optimizing value in lubricant formulation, selection and development in line with evolving OEM requirements ICIS and ELGI are delighted to announce that the inaugural North American Industrial Lubricants Congress will be taking place in Chicago this September. Covering both technical and commercial topics, the event will tackle some of the biggest challenges impacting the demand, formulation and performance of the industrial lubricants sector today.
Key topics on the program:
Who should attend?
Base stock market drivers – impact on
Blenders of lubricants for use in industrial applications
lubricant supply and demand Globalization of supply – defining the characteristics of
Industrial OEMs
the additives marketplace Managing regulatory complexities – how are REACH and
Base oils producers / refiners
GHS being implemented within the industrial lubricants sector?
Base oils marketers, traders and distributors
Evaluating the use of biocides and chlorine in
Additives producers and suppliers
metalworking fluids Performance optimization through innovative formulation
Consultants
– analyzing the demand for high performance lubricants
Academics
The OEM perspective – how is design evolution influencing
Terminal operators
lubrication requirements?
Logistics providers
Applications and challenges in diverse environments – challenges for water-based and high temperature operations
Government representatives
Media partners:
* Register by Friday June 24, 2016 to save $300 on the standard delegate fee N.B. You must enter the promo code JGZ74706 to receive your discount! - 49 -
NLGI SPOKESMAN, MAY/JUNE www.icisconference.com/lubricantsusa +44 (0)20 86522016 4659
events.registration@icis.com
NLGI Industry News Please send all industry news, events, employment news and press releases to Marilyn Brohm. (Your company does not have to be an NLGI member to post items.)
US Corrosion Inhibitor Demand to Reach $2.8 Billion in 2020 US demand for corrosion inhibitors is forecast to rise 3.1 percent per year to $2.8 billion in 2020; volume will approach 1.7 billion pounds. Growth in demand will be driven by overall economic expansion, with key industries for corrosion inhibitors, such as chemicals and metals manufacturing, particularly benefiting. The oil and gas market, which remained in a severe downturn entering mid-2016, is expected to see recovery take hold by 2020, leading to greater demand for corrosion inhibitors in drilling and hydraulic fracturing applications. While healthy growth is expected overall, the presence of several relatively mature markets, such as lubricant and fuel additives and pulp and paper, will prevent stronger advances. These and other trends are presented in Corrosion Inhibitors, a new study from The Freedonia Group, a Cleveland-based industry research firm. To read the complete press release visit: https://www.nlgi.org/newsand-events/industry-news/
US Lubricant Demand to Reach 2.4 Billion Gallons in 2020 US demand for lubricants is projected to expand slightly to 2.4 billion gallons in 2020, with a market value of $23.5 billion. This will follow a period of modest growth between 2010 and 2015, during which time a number of industries associated with key lubricant markets rebounded from their recessionary lows. Going forward, a positive economic outlook will benefit lubricant demand, with rising manufacturing output and increasing commercial activity offsetting the adoption of longer lasting, higher performing products that facilitate longer drain intervals. These and other trends are presented in Lubricants, a new study from The Freedonia Group, a Cleveland-based industry research firm. To read the complete press release visit: https://www.nlgi.org/news-and-events/industry-news/
Dow Corning showcases new synthetic greases for clean, more effective automotive noise-damping at SAE 2016 World Congress MIDLAND, MICHIGAN, USA: April 7, 2016 – Dow Corning Corporation – a global leader in silicones, silicon-based technology and innovation – will showcase three new Molykote® brand synthetic greases for more effective automotive noise-damping at the SAE 2016 World Congress and Exhibition, taking place April 12 through 14 at Cobo Center in Detroit, Michigan. Offering clean handling, better low-temperature capabilities, and improved squeak-and-rattle control, the new greases will be featured in a Dow Corning exhibit at the event. . To read the complete press release visit: https://www.nlgi.org/news-and-events/industry-news/ - 50 VOLUME 80, NUMBER 2
Whitmore® Expands Aviation Product Line with Safe yet Potent Cleaners Wet and Dry Cleaning Solutions that Are Biodegradable and Get the Job Done Rockwall, Texas. April 8, 2016 – Whitmore, a CSW Industrials Company and leading provider of innovative products and services that increase reliability, performance and lifespan of industrial assets, announces the addition of three new cleaning products designed for aircraft and airport ground support vehicles. The new Aviation Cleaner & Degreaser with low VOC, and Aviation Dry and Wet Wash with no VOC are ideal for painted and unpainted aircraft surfaces. . To read the complete press release visit: https://www.nlgi.org/news-and-events/ industry-news/
Whitmore® Rolls-Out State-of-the-Art Filtration Units Advanced Filtration Units in Stationary and Portable Configurations Rockwall, Texas, April 8, 2016 – Whitmore, a CSW Industrials Company and leading provider of innovative products and services which increase the reliability, productivity and lifespan of industrial assets, is pleased to announce a line of ground-breaking filtration units that are the product of extensive market insights and design work. . To read the complete press release visit: https://www.nlgi.org/news-and-events/industry-news
FULL LINE •
FOOD GRADE LUBRICANTS
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SYNTHETIC LUBRICANTS
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BIODEGRADEABLE OILS
COMPLETE LINE OF LUBRICANTS and HD GREASES •
BIODEGRADEABLE GREASES
ROYAL 865M CSC MOLY5 heavty duty CSC moly grease
DIESEL SUPREME ULTRA CJ-4 15W40 / 10W30
ROYAL 865HD calcium sulfonate complex
HALAL KOSHER ISO 9001 AN
HAL
A L F OU
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ROYAL 876 heavy duty lithium complex
ON
GL-5 85/140 GEAR OIL heavy duty gear lube
NSF
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ROZEP AW HYDRAULIC OILS full ISO grade range
“When results are important, you can rely on Royal.”
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AMERICA’S OIL SINCE 1914
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Advertiser’s Index Afton Chemical, page 6 Biederman Enterprises Ltd., page 5 Covenant Engineering, page 53 F&L Asia, page 22 ICIS, page 49 King Industries, page 53 Lubes ‘n’ Greases, page 52 Lubrizol Corporation, back cover Patterson Industries Canada, A Division of All-Weld, Co. Ltd, page 48 Petro Lubricant Testing Lab, page 27 Royal Mfg. Co., LP, page 51 Vanderbilt Chemicals, LLC, inside front cover
NE ®
RP & AW For Severe Salt Water Conditions
SPECIALTY CHEMICALS
LITHIUM 12-OH Grease (NLGI #2) + 0.5% NA-LUBE AO-142
100% Synthetic Sea Water
Distilled Water
K-CORR
K-CORR® G-1270
W
Static Rust Test EMCOR Rust Test ASTM D 1743/5969
ASTM D 6138, IP 220
1% G-1270
Pass
0,0
1% G-1107
Pass
0,0
3% G-1270
Pass
0,0
3% G-1107
Pass
2,2
Applications Automotive Greases Industrial Greases
Properties
Rust & Corrosion Protection Excellent Compatibility Low Odor Antiwear
K-CORR G-1270 is Zinc-Based K-CORR G-1107 is Ashless
K-CORR G rust inhibitor systems are specifically designed to provide outstanding rust protection to greases exposed to severe salt water conditions. Test results are available in lithium 12-hydroxystearate, complex lithium, polyurea and calcium sulfonate greases with 5% and 100% synthetic sea water and 3% sodium chloride solution. www.kingindustries.com
Helping the World Run a Little More Efficiently In today’s complex marketplace, you need a technology partner that understands the demands of ever-changing applications, environmental concerns, LEAN manufacturing and worldwide standards and protocols. Lubrizol is at the forefront of industry advancements offering our customers superior functionality, product consistency, R&D and testing. We are improving grease performance and processes worldwide. To learn more visit www.lubrizol.com.
Š 2014 The Lubrizol Corporation. All rights reserved. 14-0132