DUSTGSUURURL ETSI IITRTITITTIIITIIFITIIALE #0313 Preformed Soap as Thickener and EP-Additive for Grease Production By DIPL. ING. OTTO ROHR Chief Executive Officer Miracema-Nuodex Industria Quimica Ltda. Campinas, State of S40 Paulo, Brazil and ROBERTO HISSA Technical Grease Consultant Miracema-Nuodex Industria Quimica Ltda. Campinas, State of S40 Paulo, Brazil Preprint of Paper for NLGI's 70" Annual Meeting The Westin Resort, Hilton Head Island South Carolina / U.S.A. October 26 - 29, 2003URLS TLRU ULL LO RUST TRU RR URS TUT RTT UTTEL PREFORMED SOAP AS THICKENER AND EP-ADDITIVE FOR GREASE PRODUCTION By Otto Rohr and Roberto Hissa ‘The work to be presented in this paper deals with the feasibility to prepare a grease made with a blend of a concentrated oily preformed soaps of Bismuth-and Lithiuim-12-hydroxy-stearates used as thickeners + EP-additive, and trying to reach the same characteristics ( or better ) than those ‘greases made only with Lithium-12-hydroxy-stearate as thickener, Lithium-42-hydroxy-stearate formed by neutralization of 12-hydroxy-stearic acid, in mineral oll with lithium hydroxide, is the world-wide used thickener for multipurpose lithium greases. oH LO Pa gta r The basic idea of our experimental work was to create a concentrated and mixed oily preformed soap of 12-hydroxy-stearic acid with these two metals in the composition to have a thickener that is extreme pressure additive at the same time, too: + Lithium being responsible for thickening the mineral oil and forming grease, and Bismuth giving the exireme pressure characteristics and contributing to the formation of the grease, OH fe owl | Bi yor i ie So, this new developed compound is THICKENER and ADDITIVE at the same time with some important technical benefits, as:OUUUSTTRTSRATIIRAVLL LAAT ITIAIIVIIIITIIIIIIIIIIIE + Itis not necessary to add to the grease any extreme pressure additive in the final stage of the process. The negative effects this procedure normally causes, as lowering the dropping point and modifying penetration, are well-known. Using this ADDITIVE-THICKENER or THICKENER-ADDITIVE ( you may call it as you prefer...) none of these problems will happen The extreme-pressure-metal Bismuth is chemically bounded to the 12-hydroxy-stearic acid (as the thickener-metal Lithium ), and in this way no other chemical radical or other synthetic carboxylic acid are introduced into the grease. ‘©The grade of dispersion of the additives in the grease influences highly Its performance and extreme pressure characteristic. ‘+ Being the thickener-soap al the same time the exireme-pressure-additive, the dispersion within the mineral oil in the grease composition will be much better and the mineral oll in the grease is what gives lubrication ! The use of the concentrated soap, perhaps it seems to be a revolutionary modification of making greases compared with the historical philosophy of grease maker to prepare his own thickener *in situ’ But, | mean it is not, because this concentrated cily preformed soap the grease maker itself can prepare. The conventional preformed soaps known to the grease industry are solid powders, produced through the wet process, dried and powdered later. Conditions, the grease producers have not. ‘This process is cost-effective and thus this type of preformed soaps are too expensive. This concentrated oily preformed mixed-soap could be called a “concentrated grease" and the production cost is much lower than of the conventional grease production. Il has to be mixed up with mineral oil of grease makers choice, and after homogenizing the grease is ready. Technical "Puzzle" - Possil ‘¢ The ratio between Lithium and Bismuth content of this "additive-thickener" will pre-establish the EP-performance of the grease and can be allemnated in accordance with the grease type wanted. * According to the type of fibers required, the concentrated oily preformed soap can be adjusted during its manufacture in order to obtain higher stability against oil bleeding, ‘+ Bismuth in the thickener, in the form of 12shydroxy-stearate, gives good anticorrosion and antirust properties ~ well-known from his formerly used "twin brother’ lead. All this is nothing but new, technology well-known and how to prepare fine greases you know. However, our intention was to create a concentrated oily preformed soap that acts simultaneously * as thickener, and + as EP-additive replacing the conventional extreme pressure additives and the traditional thickener formed “in situ’. 2DEGRA R RIAA TITIIAALL LRTI TITITTIIITITIIIIIIIIIIIE EXTREME PRESSURE ADDITIVES In the history of EP-greases, sulphur and lead ~ as sulphurized whale oil and lead naphthenate — were the basic additives to provide extreme pressure properties, ‘As well-known, lead was banned because of its toxicity and whale oll was eliminated as international agreements were signed stopping hunting of whales. Synthetic phosphorus — sulphur compounds were developed as EP-additives meeting under ‘extreme conditions only on "border line” the very severe specifications for the application of greases in high speed bearings and other industrial equipments. ‘Other reasons to use the studied material are: + Reducing time of the grease production, because the saponification process is avoided by using the concentrated oily preformed soap mentioned above; + Pressurized kettles are not necessary when the grease is being made by this procedure; + Of course, energy is saved — a must today ! ‘+ Producing grease by the conventional process, and depending on the falty material, water has to be added for ionizing the alkali o make possible the chemical reaction to start up. Later, this water has to be eliminated by drying the soap — a costly process that can be risky, is slow and eats up precious production time. ‘© Less items of raw materials have to be Kept in stock. This means reduction of financial costs, Ten years ago, we developed our BISMUTH-TECHNOLOGY replacing the toxic lead by its "win brother" Bismuth, another heavy metal, but non-toxic and with extremely similar cheracteristics tolead. Allow me to spend some words about BISMUTH ~ THE GREEN HEAVY METAL: Bismuth is considered non-toxic or the least toxic of all of today's known metals, with the atomic umber 83 (lead has the number 82 ) in the 5b Group, having the atomic weight of 208 while lead has 207. Itis the unique metal that shows volume expansion on solidification ( about 3 percent), with a large range between melting point and bolling point: melting point of 271°C and boiling point of 1560°C | Ithas the lowest thermal and heat conductivity ofall metals, (Table 1) Bismuth can be considered non-toxic and harmless to intact-human skin, The largest single use for Bismuth is up-to-date by the pharmaceutical industry in the production of ‘antacid preparations for stomach based on bismuth salts, Next in importance is its application in cosmetics, where Bismuth provides the pearlescent sheen in lipsticks, nail polish and eye shadow.STVLANCUAGS fi 7 sivian-Non sasvo ava [7 | Fd! WL le — | 1] oner] pa | wpe] axe] ag = we] gee te] Spo mye! ag] ape] sox pom] 3v| par| apg] man] oy az) ng st] Ins) o>¢¢| 939%] upyse | =] uel ase] oe] | » By) ent! ae] i} z mE YOIA VHA VIA YA VAL Yill € = @ Ug, — giN iA GA GAL am Yo WE Table 1 LULCRELEEEELE KALE LKR ELLELAULLEELEL EEREDODVSTTTTRVAR LTRS TIIITATIAITIIIIIIIIIITE Another application — we think litle known ~ is its use in the fusible alloys for sprinkler systems, where the addition of Bismuth makes possible melting points of only a little above room temperature. (Figure 1) Antocid ps leased or besrath sey Fire sprinkler systoms dopond fon bismuth alloys with low medting te to tolecrse thet fire quenching sprery when neckedWULELEREISISISSIAAVE RTS IATAT IAT II IIT ITIIIIIIIIGE Bismuth also has mild antiseptic properties and is being used in wound-powders to help cauterizing. A Bismuth-salt-based compound WAS ONE OF THE FIRST anti-syphilis medicines. This is to document the non-toxicity of Bismuth, ‘Allow us to show you other applications ~ not related to our lubricating greases — but just 10 emphasize the non-toxicity and harmlessness of Bismuth and its compounds, where absolutely ‘nor-toxicity is required and proved: (Table 2) $0, we mean that nothing can be risen against the use of Bismuth in industrial lubricants and lubricating greases, replacing the toxic element lead. EXPERIMENTAL WORK With the same equipment and manufacture process and using the same mineral oil, two greases were prepared without any additivation: (One batch has used the Lithium-12-hydroxy-stearate as thickener. ‘Another batch has utilized the Lithium and Bismuth 12-hydroxy-stearates as thickeners. Both products were adjusted to NLGI grade 2 in consistency, and evaluated in common laboratory inspection and bench tests.PESPPFPPPEELISSITEEEIEPESIErrrrer rer r ret iy Table 2 To illustrate the non-toxicity of Bismuth, allow me to mention some applications - not related to our field of lubrication - in the pharmaceutical area, cosmetics and food. BISMUTH SUBNITRATE BSN - is used to reduce the toxic-side-effect of the antitumor activity of Adriamycin (Kitasato University, Tokyo, 1988) and the side effects of anticancer drugs, BISMUTH SUB-GALLATE is approved by Food and Drug Administration of USA in the composition of pharmaceutical deodorants for intemal use. (Federal Register Vol. 65, no. 92, May 11, 1990) BISMUTH BROMIDE is used in different plastics to make them detectable by X-rays. So plastics - as prosthetic devices or medical implants - can be detected by X-rays and spotted inside the human body. Studies concerning the biocompatibility of bismuth-containing plastics indicate that they are neither toxic nor carcinogenic. ‘TRIPHENYL-BISMUTH is a new radiopaque additive for dental-resins showing the lowest cytotoxicity among the different curing-agents and acrylic sealants, BISMUTH-CHLORIDE replaces LEAD SUBACETATE as a non-toxic clarifying agent for polarimetry in sugar analysis. BISMUTH OXYCHLORIDE pearlescent white pigment largely used in cosmetics - was tested by oral administration of high doses to rats in the feed, at concentrations from 1%, 2% and 5%, during up to two years by the GERMAN CANCER RESEARCH CENTER, INSTITUTE FOR TOXICOLOGY AND CHEMOTHERAPY in HEIDELBERG and was found as NON- CARCINOGENIC. BISMUTH's skin and mucous membrane tolerance did not show any toxic effects according to communications of FARBSTOFF-KOMISSION DER DEUTSCHEN FORSCHUNGSGEMEINSCHAFT (Dyestuff Commission). BISMUTH-SALTS are widely used in the pharmaceutical industry as antacid preparations for stomach, in the form of colloidal bismuth subcitrate for the treatment of peptic ulcer disease. ORGANO-BISMUTH COMPOUNDS catalyst in two component polyurethane elastomeric system, BISMUTH METAL trace element in carbon steel and aluminum. Constituent in thermoelectric compounds, neutron windows in nuclear reactors and shield against gamma and xray radiationDUTT UU Taka aaa aa aa aaa TTI TITEL LABORATORY TESTS The laboratory test data on the experimental grease are showed in Table 3, The experimental grease showed good results in the shear stability test when submitted to mechanical working for 60, and 10.000 strokes. Also good shear stabilily was obtained in the Roll Stability test In other tasts such as Dropping Point ( D-2256 ), Bomb Oxidation ( D-942 ), Corrosion Copper Strip, 50 hours at 160°F (71°C), water washout ( D-1264 ), and level of soap content, the product revealed normal when compared with the commercial type of lithium greases made with ‘a-hydroxy-stearic acid. Regarding to the 4-Ball EP Test ( D-2266 }, the sludied grease exhibited a Weld Point of 200 and pass on 160, while this class of product, without additvation usually present a Weld Point of 160. Making comparison between the two greases on observation, the grease based on bismuth soap revealed EP-characteristics, according to 4-Ball test results, of approximately 7% higher and wear was reduced by 11%. FIELD TEST AA field test evaluation in several regular applications will be made comparing with a grease NLGI Grade 2 CONCLUSIONS AND DISCUSSION Based on the data obtained in this study, the following conclusions may be drawn: 1. It is feasible to prepare greases using concentrated oily preformed soaps of lithium- and bismuth-12-hydroxy-stearates, where the final product revealed characteristics considered normal for this grade of greases prepared by using Lithium-12-hydroxy-stearate + EP-additive; 2. Being the soap the additive too, the dispersion is almost perfect and guarantees higher performance than the added additives can give; 3. The negative influence on the dropping point and penetration is excluded; 4. The well-known formation of the so-called “intermetallic compound" shown when in the past ead was used between iron of the surface of the balls in the bearings and lead of the (grease, happens between iron and bismuth too, thus protecting the surfaces during rolling; 5. As Bismuth is considered non-toxic and consequently Bismuth 12-hydroxy-stearate is Ron-toxic, too, this “additive-soap" is an appropriate tool to produce food-grade greases when the mineral oil is replaced by vegetable oils, as for example genetically modified soybean oll of "high oleic” type to guarantee oxidation stability; 6. Generally all the other well-known properties of preformed soaps and the advantages in cost-saving when compared to the traditional soap production remain, when using this new concentrated oily preformed "additive-soap", ‘September 2003DISAAAVELETIIAIIIIIIIITITIIITIITZIIIVGL Table 3 Grease Characterization Tests ‘Soap Content, wt. % Li 12-Hydroxy-stearate Bi 12-Hydroxy-stearate Pen al 77°F (25°C) — ASTM D-217 Unworked, Worked 60 st Worked 10,000 st Roll Stability Test, 2 h, 25°C ‘Change in penetration Bomb Oxidation, psi drop - ASTM D-942 40h EMCOR Test ASTM D-1743 Dropping Point, °C - ASTM D-2266 Corrosion, 50 h, 160°F (74°C) Copper Strip Water Washout % Loss at 100%F (37,7°C) % Loss at 175°F (79,4°C) Four Ball EP Test, kg Weld Point 7% 5,5 % (Bi metal content 1%) 29 aan 246° * variation 2,07 % 3% Softening pass 190 ta 7 13 pass 160 200 In combination with a sulphur carrier (+), containing 10% inactive sulphur (copper corrosion t Four Ball EP Test, kg ‘Weld Point ‘1b), the Four Ball results are increased to: pass 250 with 2% (+) pass 400 with 4% (+) 315 with 29% (+) 500 with 4% (+)