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WO1998008921A1 - Utilisation de composes bismuth dans des refrigerants lubrifiants - Google Patents

Utilisation de composes bismuth dans des refrigerants lubrifiants Download PDF

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Publication number
WO1998008921A1
WO1998008921A1 PCT/EP1997/004515 EP9704515W WO9808921A1 WO 1998008921 A1 WO1998008921 A1 WO 1998008921A1 EP 9704515 W EP9704515 W EP 9704515W WO 9808921 A1 WO9808921 A1 WO 9808921A1
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WIPO (PCT)
Prior art keywords
water
additive
miscible
weight
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1997/004515
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German (de)
English (en)
Inventor
Jürgen Geke
Wiltrud Klose
Matthias Kampmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU42056/97A priority Critical patent/AU4205697A/en
Publication of WO1998008921A1 publication Critical patent/WO1998008921A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/022Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/241Manufacturing joint-less pipes
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    • C10N2040/242Hot working
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    • C10N2040/243Cold working
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    • C10N2040/244Metal working of specific metals
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10N2040/244Metal working of specific metals
    • C10N2040/245Soft metals, e.g. aluminum
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10N2040/244Metal working of specific metals
    • C10N2040/246Iron or steel
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10N2040/244Metal working of specific metals
    • C10N2040/247Stainless steel
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    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01Emulsions, colloids, or micelles
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    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

Definitions

  • the invention relates to non-water-miscible or water-miscible cooling lubricants or their concentrates for metal cutting.
  • the invention relates to an additive for such cooling lubricants, consisting of a mixture of organic bismuth compounds and organic sulfur compounds.
  • Cooling lubricants are preparations / mixtures that are used in metal cutting and metal forming to cool and lubricate the tools.
  • the most important machining processes which differ in the type of movements that the machined part and tool perform and in the geometry of the parts to be manufactured, are referred to as milling, turning, drilling and grinding as machining operations, as well as rolling, deep drawing and cold extrusion as non-cutting Deformations.
  • the common principle of metal-cutting processes is that the cutting edge engages in the material and lifts a chip off the surface, so that a new surface is created. Very high pressures are required to break up the material. The deformation of the chip and the friction that occurs under pressure generate heat that heats up the workpiece, the tool and, above all, the chips.
  • the desired effect of using cooling lubricants is therefore the lowering of the temperature that would otherwise occur in the chips.
  • B. can rise to 1000 ° C, and which has an influence on the dimensional accuracy of the manufactured parts.
  • Another main task of cooling lubricants is to improve the service life of tools that wear out quickly under the influence of high temperatures.
  • the use of a cooling lubricant reduces the roughness of the surfaces, since the lubricant welds the tool and the workpiece surface prevents surface and prevents particles from sticking.
  • the cooling lubricant takes on the task of removing the chips that have formed.
  • Water-mixed cooling lubricants are produced by the user by mixing a concentrate of the water-miscible cooling lubricant with process water. As a rule, approximately 5% aqueous emulsions are produced.
  • the advantage of this type of cooling lubricant is the good cooling effect, which is based on the thermal properties of the water. Due to the good cooling effect, it is possible to achieve very high working speeds and thus increase the productivity of machines.
  • the lubricating effect of the water-mixed cooling lubricants is sufficient for most machining processes in machining. Another advantage is the low cost that can be achieved by mixing the concentrate with water.
  • the disadvantage of water-mixed cooling lubricants is that they are sensitive to attack by microorganisms and therefore require more control and care.
  • Non-water-miscible and water-miscible cooling lubricants are often based on mineral oil.
  • the mineral oil qualities used are predominantly combinations of paraffinic, naphthenic and aromatic hydrocarbon compounds.
  • so-called synthetic lubricants such as polyalphaolefins, polyalkylene glycols and glycol ethers, dialkyl ethers, natural ester oils and synthetic esters and their derivatives are also important.
  • cooling lubricants In order to meet practical requirements, cooling lubricants must contain various components in addition to the base oil.
  • the most important substance groups are the emulsifiers, corrosion protection additives, biocides, EP additives, polar additives.
  • Emulsifiers e.g. surfactants, petroleum sulfonates, alkali soaps, alkanolamine soaps
  • Emulsifiers stabilize the fine distribution of oil droplets in the aqueous working fluid, which is an oil-in-water emulsion.
  • the emulsifiers represent an important group of additives for water-miscible cooling lubricants.
  • Usual corrosion protection additives e.g.
  • alkanolamines and their salts, sulfonates, organic boron compounds, fatty acid amides, aminodicarboxylic acids, phosphoric acid esters, thiophosphonic acid esters, dialkyldithiophosphates, mono- and dialkylarylsulfonates, benzotriazoles, polyisobutene succinic acid surfaces) are intended to prevent rusting of metal surfaces.
  • Some corrosion protection additives also have emulsifying properties and are therefore also used as emulsifiers.
  • Biocides e.g. phenol derivatives, formaldehyde derivatives, Kathon MW
  • EP additives e.g.
  • sulfurized fats and oils, compounds containing phosphorus, organochlorine compounds are intended to prevent micro-welding between metal surfaces at high pressures and temperatures.
  • Polar additives e.g. natural fats and oils, synthetic esters
  • Anti-aging agents e.g. organic sulfides, zinc dithiophosphates, aromatic amines ensure a long service life of the cooling lubricants.
  • the second important function of the cooling lubricants lies in the lubricating effect (see the article by W. Klose: "Cooling lubricants on metal surfaces", messages from the Association of German Email Specialists, 41, Issue 11, pages 138-142 (1993))
  • the effect of the lubricating components on the formation of surface layers which have a lower shear strength compared to the base material and thus reduce friction and wear.
  • the spectrum of the surface conditions ranges from adsorptively bound layers through chemical sorption to chemical reaction layers that create a firm bond to the metal surface .
  • lubricant coating on a surface is adsorptive lubricant layers. They are produced, for example, by mineral oils without special additives. The formation of the adsorption layers can be increased by adding polar active ingredients such as fatty alcohols or fatty esters. In addition to the purely physical adsorption, there is an interaction between the metal surface and the lubricant molecules, which leads to a partial chemisorptive binding of the fatty alcohols or fatty esters. Typical representatives of chemisorptive lubricant film formers are fatty acids. The hydrophilic carboxyl group is chemically bound to the metal surface by reaction with the metal atoms and the hydrophobic hydrocarbon residue is aligned perpendicular to the surface.
  • the increased adhesive strength of the chemisorptive layer improves the pressure absorption capacity compared to purely adsorptive lubricant layers, but is still not sufficient for many cases of metal forming to reduce friction and wear. It is only when EP or AW additives (extreme pressure or anti wear additives) are added that the lubricating performance is sufficiently improved so that even difficult forming processes are possible. These are usually chlorine, phosphorus or sulfur-containing active ingredients. Their effect is based on the formation of chemical reaction layers in the form of metal chlorides, metal phosphates or metal sulfides. For reasons of disposal, there is an attempt today to avoid using chlorine-containing EP additives wherever possible.
  • the reaction layers formed on the metal surface act on the one hand as solid lubricant layers, which are constantly removed and renewed during the shaping process. On the other hand, they form monomolecular surface films that can attach additional lubricant components.
  • bismuth alkyl carboxylates having 6 to 10 carbon atoms in the alkyl radical and especially bismuth octoate are particularly preferred. These bismuth compounds are intended in particular to replace the lead compounds which have the same effect but are toxicologically unsafe.
  • the object of the invention is to provide non-water-miscible or water-mixed cooling lubricants or their water-miscible concentrates with an improved lubricating effect.
  • an additive which improves the lubricating effect must be designed in such a way that it is compatible with the other components of the cooling lubricants or their concentrates.
  • the invention relates to a friction-reducing additive for water-miscible or non-water-miscible cooling lubricants, comprising
  • the sulfur content of the additive is in the range from 2 to 30% by weight and the bismuth content is in the range from 1 to 25% by weight.
  • the mixing ratio is preferably chosen such that the sulfur content of the mixture is in the range from about 5 to about 25% by weight and the bismuth content is in the range from about 4 to about 20% by weight.
  • Additives in which the ratio of sulfur content to bismuth content are in the range from 1: 0.1 to 1: 2, preferably in the range from 1: 0.15 to 1: 1, are particularly preferred.
  • the bismuth compounds are preferably selected from naphthenates and / or from carboxylates of the general formula (R-CO 2 ) Bi, in which R is a linear, branched or cyclic alkyl radical with 1 to 30 C. -Atoms or an aryl, alkylaryl or arylalkyl radical having 5 to 20 carbon atoms.
  • the bismuth compounds are preferably selected from Naphthenates and / or from alkyl carboxylates with 6 to 10 carbon atoms in the alkyl radical. Bismutoctoate is particularly preferred. For better compatibility with water-mixed cooling lubricants, these bismuth compounds can be reacted with ethylene oxide and / or propylene oxide.
  • Organic sulfur compounds are generally known in the lubricant field as so-called extreme pressure additives (EP additives). Examples of these are organic sulfides and disulfides, sulfurized paraffins, sulfurized fatty oils, sulfurized polyisobutene, sulfurized polypropylene or sulfurized polystyrene. These can be used together with phosphorus-containing organic compounds to further increase the activity. Sulfurized fatty oils and sulfurized paraffins are particularly preferred for the purposes of the present connection.
  • the additive according to the invention can furthermore contain up to 5% by weight, based on the total mass of the additive, of compounds selected from the group of the esters and / or the polyglycols.
  • esters are di- and triglycerides such as turnip oil.
  • polymer esters such as butanol esters of ⁇ -olefin-dicarboxylic acid copolymers.
  • Polymer esters of this type which can have a molecular weight of around 1,800, for example, are sold by Akzo under the name Ketjenlube 135.
  • An example of a usable polyalkylene glycol is the Emkarox VG 180 from Erbslöh.
  • the invention relates to the use of the additive described above as a friction-reducing additive in water-mixed or non-water-miscible cooling lubricants.
  • the additive is preferably used in a concentration range such that the ready-to-use water-mixed cooling lubricants, which are usually in the form of an oil-in-water emulsion, are prepared by adding a concentrate to water , the bismuth content is in the range from 0.01 to 0.2% by weight, preferably in the range from 0.02 to 0.15% by weight.
  • the additive is used in a concentration range such that the bismuth content is in the range from 0.2 to 4% by weight, preferably in the range from 0.4 to 3% by weight.
  • the invention further relates to the use of cooling lubricants which contain the additive according to the invention for the so-called minimal lubrication technology.
  • This is sometimes, albeit misleadingly, referred to as low-quantity lubrication.
  • it is explained in the article by A. Walter: ..Minimal lubrication technology and dry machining; possible fields of application ", German Industry Forum for Technology 10/95 (DIF 17/21 / WA).
  • minimal lubrication technology compared to the conventional use of cooling lubricants, cooling lubricant quantities are significantly reduced. This leads to a greatly reduced cooling of the tool and workpiece Increased importance is attached to the lubrication to reduce the frictional heat in the process.
  • the lubrication can only be carried out by using a suitable cooling lubricant when using minimal quantity lubrication.
  • the cooling lubricant is sprayed onto the tool and workpiece.
  • the additive mixture according to the invention can be used as such, ie without mixing with other components, but it is also possible to use the additive in a mixture with mineral oils, vegetable oils or synthetic polar compounds, the proportion of the additive in the total mixture being at least 10 Ge % w.
  • the invention relates to a water-miscible concentrate for preparing a water-mixed cooling lubricant which contains the additive described above, preferably in an amount of about 2 to about 20% by weight, based on the total concentrate.
  • the concentrate contains at least one base oil, an emulsifier and a selection from the additives listed above.
  • the concentrate is usually mixed with about 50 to about 10, for example with about 20, parts by weight of water.
  • a suitable concentrate emulsifies spontaneously and forms a stable oil-in-water emulsion.
  • the invention further comprises a water-immiscible cooling lubricant which contains about 2 to about 20% by weight, for example about 10% by weight, of the additive described above.
  • the method according to this standard is used to determine the good and weld strength of liquid lubricants with active ingredients that should allow high surface pressures in the mixed friction area between surfaces that move relative to each other (EP behavior).
  • the lubricant is tested in a four-ball system, which consists of a rotating ball (running ball) that slides on three balls of the same size (standing balls) under selectable test forces. The test force is gradually increased until the four-ball system is welded.
  • test balls and the ball cup are cleaned with mineral spirits in order to obtain reproducible and thus meaningful results.
  • Three test balls are firmly clamped in the cleaned ball cup.
  • the ball cup is then filled with the lubricant to be tested so that the test balls are completely covered.
  • test ball is carefully pressed into the ball holder and inserted into the test spindle. After inserting the ball cup, the test force is applied. The test force is set by moving a barrel weight on the balance beam. This pressure generated in this way corresponds to the test ball load. The duration of the test run is one minute, unless it is interrupted by welding the test balls.
  • the lubricant is tested in a four-ball system, which consists of a rotating ball (running ball), which is applied to three of it under a specified test force same balls (standing balls), exists.
  • a test load of 300 N is set as the test force.
  • the test time is one hour.
  • the calotte diameters of the three standing balls are then measured and averaged.
  • the wear diameter is measured with a Brinell magnifying glass or with a measuring microscope.
  • the value determined in this way is regarded as a measure of the strength of the wear and is referred to as the average wear diameter (“AW wear”).
  • a test roller is adapted to a rotating slip ring by means of a lever system, the lower third of which is immersed in the lubricant to be tested.
  • the test roll which has been cleaned in white spirit, is installed in the swiveling holder.
  • the holder is swung in and clamped.
  • the slip ring remains clamped in the device for several test runs, where it is also cleaned with white spirit after each test run.
  • the test roller is placed on the slip ring by slowly applying the load weight (1.5 kg).
  • the counter on the Reichertwaage is set to 0.
  • Example 3 90% beet oil 5% bi-naphthenate 1.65 0.85 9000 0.8
  • Concentrate 1 (composition in% by weight) 36% paraffinic mineral oil
  • Comp. 1 concentrate 1 sulfurized hydrocarbon 18 and polymer ester (3% S)
  • Example 1 concentrate 1 sulfurized fat oil, bi-octoate 1.3 (1.3% S, l, 2% Bi)
  • Example 2 concentrate 2 sulfurized fat oil, Bi-Octoat 25 (1.3% S, 1.2% Bi)
  • Comp. 5 concentrate 3 polyalkylene glycol, bi-octoate 1 1 (2.4% Bi)
  • Example 3 concentrate 3 sulfurized fat oil, bi-octoate 2.0 (1.3% S, 1.2% Bi)
  • Example 4 concentrate 3 sulfurized fat oil, bi-octoate, 1,3

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un additif réduisant le frottement pour réfrigérants lubrifiants miscibles ou non miscibles dans l'eau, contenant: a) des composés bismuth d'acides organiques; b) des composés organiques contenant du soufre, dans un rapport de mélange tel que la teneur en soufre de l'additif soit comprise entre 2 et 30 % en poids et la teneur en bismuth, entre 1 et 25 % en poids. L'invention concerne en outre l'utilisation de cet additif dans la technique de lubrification minimale et comme adjuvant réduisant le frottement dans des réfrigérants lubrifiants non miscibles dans l'eau, ainsi que dans des réfrigérants lubrifiants mélangés dans de l'eau et leurs concentrés.
PCT/EP1997/004515 1996-08-28 1997-08-19 Utilisation de composes bismuth dans des refrigerants lubrifiants Ceased WO1998008921A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU42056/97A AU4205697A (en) 1996-08-28 1997-08-19 Use of bismuth compounds in cooling lubricants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19634733A DE19634733A1 (de) 1996-08-28 1996-08-28 Verwendung von Wismutverbindungen in Kühlschmiermitteln
DE19634733.5 1996-08-28

Publications (1)

Publication Number Publication Date
WO1998008921A1 true WO1998008921A1 (fr) 1998-03-05

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Application Number Title Priority Date Filing Date
PCT/EP1997/004515 Ceased WO1998008921A1 (fr) 1996-08-28 1997-08-19 Utilisation de composes bismuth dans des refrigerants lubrifiants

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AU (1) AU4205697A (fr)
DE (1) DE19634733A1 (fr)
WO (1) WO1998008921A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1035192A1 (fr) * 1999-01-26 2000-09-13 Stefan Graichen Additif pur un réfrigérant lubrifiant

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2348317A (en) * 1941-05-22 1944-05-09 Tide Water Associated Oil Comp Lubricant containing metal compounds
GB721411A (en) * 1951-11-29 1955-01-05 Standard Oil Dev Co Improvements in or relating to fluid extreme-pressure lubricant
US2818386A (en) * 1953-12-16 1957-12-31 Gulf Research Development Co Soluble cutting oil comprising thickened oil and method of applying the same
US4171268A (en) * 1978-05-22 1979-10-16 Mooney Chemicals, Inc. Lubricant compositions containing zirconyl soaps
SU1384603A1 (ru) * 1986-05-26 1988-03-30 Гомельский Государственный Университет Присадка к смазочным маслам
EP0675192A1 (fr) * 1994-03-28 1995-10-04 SKF Industrial Trading & Development Co, B.V. Utilisation de composés à base de bismuth dans des compositions de graisse lubrifiante résistants aux pressions extrêmes pour des paliers à roulement présentant ainsi une longévité plus élevée

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2348317A (en) * 1941-05-22 1944-05-09 Tide Water Associated Oil Comp Lubricant containing metal compounds
GB721411A (en) * 1951-11-29 1955-01-05 Standard Oil Dev Co Improvements in or relating to fluid extreme-pressure lubricant
US2818386A (en) * 1953-12-16 1957-12-31 Gulf Research Development Co Soluble cutting oil comprising thickened oil and method of applying the same
US4171268A (en) * 1978-05-22 1979-10-16 Mooney Chemicals, Inc. Lubricant compositions containing zirconyl soaps
SU1384603A1 (ru) * 1986-05-26 1988-03-30 Гомельский Государственный Университет Присадка к смазочным маслам
EP0675192A1 (fr) * 1994-03-28 1995-10-04 SKF Industrial Trading & Development Co, B.V. Utilisation de composés à base de bismuth dans des compositions de graisse lubrifiante résistants aux pressions extrêmes pour des paliers à roulement présentant ainsi une longévité plus élevée

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8842, Derwent World Patents Index; Class E12, AN 88-298267, XP002048977 *
ROHR O: "BISMUTH A NEW METALLIC BUT NON-TOXIC REPLACEMENT FOR LEAD AS EP-ADDITIVE IN GREASES", NLGI SPOKESMAN, vol. 57, no. 2, May 1993 (1993-05-01), pages 6-50 - 13-57, XP000606048 *

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