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Use of Moly Dithiocarbamate As an Antiwear Additive for Ceramic/Metal Interface

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Use of Moly Dithiocarbamate As an Antiwear Additive for Ceramic/Metal Interface iiililiili^ @ EuroPean Patent Office ^-S Office europeen des brevets (fi) Publication number: 0 610 045 A1 @ EUROPEAN PATENT APPLICATION (2j) Application number: 94300691.6 © int. ci.5 : C10M 135/18, //C1 ON 10/00, C1 ON 10/1 2, C10N30/06, (22) Date of filing : 31.01.94 C10N40/25 (§) Priority: 01.02.93 US 12076 @ Inventor : Hong, Hyun-Soo 3800 Wiltshire Road Moreland Hills, Ohio 44022 (US) (43) Date of publication of application 10.08.94 Bulletin 94/32 @) Representative : Mallalieu, Catherine Louise et al @ Designated Contracting States : D. Young & Co., BE DE ES FR GB IT NL SE 21 New Fetter Lane London EC4A 1DA (GB) (n) Applicant : The Lubrizol Corporation 29400 Lakeland Boulevard Wickliffe, Ohio 44092 (US) @) Use of moly dithiocarbamate as an antiwear additive for ceramic/metal interface. (57) Hybrid engines containing a metal-ceramic interface can be lubricated with composition comprising a carrier fluid and a molybdenum thiocarbamate. Friction and wear are low even when detergent and dispersant additives are present in the lubricant. O O S o Q_ LU Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 610 045 A1 The present invention relates to a method for lubricating a ceramic-metal interface, such as may be found in an internal combustion engine. The increased use of ceramic components in passenger cars, such as ceramic valve train components, requires a lubricant which can be used in hybrid ceramic engines. However, high wear losses of metals in con- 5 tact with ceramics in the presence of conventional lubricants containing zinc dithiophosphate extreme pressure agents are a concern. It has been reported in Lub. Eng., 45, 1989, p. 761, F. Rounds, that interaction among surface-active additives (detergents and dispersants) in lubricants has a negative effect on the anti-wear per- formance of zinc dithiophosphate at a low load region in the anti-wear regime. The present invention, therefore, provides an improved method for lubricating such ceramic-metal interfaces. w Tribology Transactions, 34 (1991) 41 7-425 (Preprint No. 90-TC-2C-1, October 8- 10, 1990), Gates and Hsu, "Effect of Selected Chemical Compounds on the Lubrication of Silicon Nitride," discloses lubrication of ceramic surfaces with a variety of compounds including organo molybdenum dithiocarbamate and sulfur-molybdenum compounds. Molybdenum-sulfur compounds are reported to only act as friction reducers for silicon nitride un- less they also contain phosphorus. When phosphorus is also present, low wear can be obtained in addition 15 to low friction. Tribology Transactions 32 (1989) 2, 251-257, Yamamoto and Gondo, "Friction and Wear Characteristics of Molybdenum Dithiocarbamate and Molybdenum Dithiophosphate," discloses the use of molybdenum dithio- carbamate in a hydrocarbon baseline oil for reducing friction between surfaces of high carbon chromium bear- ing steel. 20 U.S. Patent 4,832,867, Seiki etal., May 23, 1989, discloses a lubricating oil composition which comprises lubricating base oil, at least one organophosphorus compound, and at least one organomolybdenum com- pound selected from the group consisting of molybdenum oxysulf ide alkylphosphorodithioates and molybde- num oxysulf ide alkyldithiocarbamates. The lubricating composition is reportedly excellent in antiwear proper- ties, anti-seizure properties, and corrosion resistance, and is suitable for gear oils, bearing oils, internal com- 25 bustion engine oils, automatic transmission fluids, hydraulic fluid, and metal working fluids. U.S. Patent 4,846,983, Ward, Jr., July 11, 1989, discloses molybdenum or tungsten thiocarbamate addi- tives for functional fluids, e.g., lubricating oils, automatic transmission fluids, and fuel compositions. According to one aspect of the invention there is provided a method for lubricating a metal-ceramic inter- face, comprising supplying to said interface a composition comprising: 30 (a) a carrier fluid, and (b) a thiocarbamate compound. The present invention further provides an internal combustion engine containing a metal-ceramic interface lubricated by the aforementioned method. Various preferred features and embodiments of the present invention will now be described by way of non- 35 limiting example. In the present invention a lubricant composition is supplied to a metal-ceramic interface. Metals include any of the metals which can be used for structural purposes, including ferrous metals, aluminum, magnesium, nickel, titanium, tungsten, vanadium, chromium, copper, palladium, silver, cadmium, tin, platinum, gold, lead, and alloys, blends, and metallic compounds of these metals with each other and with other elements. Partic- 40 ularly preferred are ferrous metals including iron, cast iron, steel, and stainless steel. Most preferred is cast iron, and in particular grades of cast iron which are suitable for use as components in internal combustion en- gines. Ceramics can be generally described as inorganic solids prepared by the well-known process of sintering of inorganic powders. Inorganic powders in general can be metallic or non-metallic powders, but as used in 45 the present invention they are normally non-metallic powders. Such powders may also be oxides or non-oxides of metallic or non-metallic elements. The inorganic powders may comprise inorganic compounds of one or more of the following metals or semi-metals: calcium, magnesium, barium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, niobium, molybdenum, ruthenium, rhodium, silver, cad- mium, lanthanum, actinium, gold, rare earth elements including the lanthanide elements having atomic num- 50 bers from 57 to 71, inclusive, the element yttrium, atomic number 39, and silicon. The inorganic compounds include ferrites, titanates, nitrides, carbides, borides, fluorides, sulfides, hydroxides and oxides of the above elements. Specific examples of the oxide powders include, in addition to the oxides of the above-identified metals, compounds such as beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, lanthanum oxide, gallium oxide, indium oxide, selenium oxide, etc. Specific examples of oxides containing 55 more than one metal, generally called double oxides, include perovskite-type oxides such as NaNb03, SrZr03, PbZr03 , SrTi03, BaZr03, BaTi03; spinel-type oxides such as MgAI204, ZnAI204, CoAI204, NiAI204, NiCr204, FeCr204, MgFe204, ZnFe204, etc.; illmenite-types oxides such as MgTi03, MnTi03, FeTi03, CoTi03, ZnTi03, LiTa03, etc.; and garnet-type oxides such as Gd3Ga5012 and rare earth-iron garnet represented by Y3Fe5012. 2 EP 0 610 045 A1 An example of non-oxide powders include carbides, nitrides, borides and sulfides of the elements descri- bed above. Specific examples of the carbides include SiC, TiC, WC, TaC, HfC, ZrC, AIC; examples of nitrides include Si3N4, AIN, BN and Ti3N4; and borides include TiB2, ZrB2 and LaB6. The inorganic powders may also be a clay. Examples of clays include kaolinite, nacrite, dickite, montmor- 5 illonite, nontronite, spaponite, hectorite, etc. In one embodiment, the inorganic powder is silicon nitride, silicon carbide, zirconia, alumina, aluminum nitride, barium ferrite, barium-strontium ferrite or copper oxide. In another embodiment, the inorganic powder is alumina or clay. Preferably the ceramic is prepared from alumina, aluminum nitride, silicon carbide, barium ferrite copper oxide, or most preferably silicon nitride (Si3N4). 10 Organic binders may be included in the compositions of inorganic powder to facilitate the production of so-called "green bodies" as an intermediate step to preparation of the final ceramic material. Such green bodies can be produced by extrusion or injection molding, press molding or slip casting or other methods. The amount of binder included in the compositions is an amount which provides the desired properties for the green and sintered shapes. Generally, the compositions will contain about 5% by weight of the binder based on the weight 15 of the inorganic powder although larger amounts, such as to about 30% by weight, can be utilized in some applications. The binder may be present in amounts greater than 0.5% by weight of the inorganic powder. A variety of binders have been suggested and utilized in the prior art and can be utilized in preparing cer- amics. Examples of these binders include starch, cellulose derivatives, polyvinyl alcohols, polyvinylbutyral, etc. Examples of synthetic resin binders include thermoplastic materials such as polystyrene, polyethylene, poly- 20 propylene and mixtures thereof. Other binders include vegetable oils, petroleum jelly and various wax-type binders which may be hydrocarbon waxes or oxygen-containing hydrocarbon waxes. Sintering aids may also be used to facilitate formation of ceramic materials. Sintering aids can be organic or inorganic materials which improve properties of the final sintered product. Examples of inorganic materials include the hydroxides, oxides or carbonates of alkali metals, alkaline earth metals, and the transition metals 25 including, in particular, the rare earth elements. Specific examples of inorganic sintering aids include calcium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc oxide, zinc carbonate, yttrium oxide, yttrium carbonate, zirconium oxide, zirconium carbonate, lanthanum oxide, neodymium oxide, samarium oxide, etc. Other traditional additives and components for formation of ceramics can also be used. The formation of ceramics generally includes as a first step the dispersion of the
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