WO2016032782A1 - Procédés de lubrification d'une surface revêtue de carbone de type diamant, compositions d'huile lubrifiante associées et procédés de criblage associés - Google Patents

Procédés de lubrification d'une surface revêtue de carbone de type diamant, compositions d'huile lubrifiante associées et procédés de criblage associés Download PDF

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Publication number
WO2016032782A1
WO2016032782A1 PCT/US2015/045448 US2015045448W WO2016032782A1 WO 2016032782 A1 WO2016032782 A1 WO 2016032782A1 US 2015045448 W US2015045448 W US 2015045448W WO 2016032782 A1 WO2016032782 A1 WO 2016032782A1
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WIPO (PCT)
Prior art keywords
lubricating oil
oil composition
lubricating
oil compositions
coated surface
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PCT/US2015/045448
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English (en)
Inventor
Paul Francis BASTIEN
Hong Gao
Brian Papke
Paul BOGERS
Chen ZUO
Jeffery Hsiu Hsu
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Shell Oil Company
Shell Internationale Research Maatschappij B.V.
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Publication of WO2016032782A1 publication Critical patent/WO2016032782A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N19/00—Investigating materials by mechanical methods
    • G01N19/02—Measuring coefficient of friction between materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C10M2203/1025—Aliphatic fractions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/44—Boron free or low content boron compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; viscous liquids; paints; inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2888—Lubricating oil characteristics, e.g. deterioration

Definitions

  • DLC diamond-like carbon
  • ZnDTP zinc dithiophosphate compounds
  • ZnDTC zinc dialkyl-, diaryl- and/or alkylaryl- dithiophosphates
  • organo-molybdenum compounds such as molybdenum dithiocarbamates (MoDTC), molybdenum dithiophosphates (MoDTP), molybdenum amines, molybdenum alcoholates, and molybdenum alcohol-amides
  • ashless anti-wear additives such as substituted or unsubstituted thiophosphoric acids, and salts thereof.
  • a Schwingung, Reibung, Verschleiss (SRV) high-frequency, linear-oscillation test device has been used to evaluate friction and wear properties of lubricating oil compositions for lubrication of non-DLC coated surfaces, as decribed in ASTM D7421 and D6425.
  • SSV Streibung, Verschleiss
  • lubricating oil compositions suitable for lubricating a DLC coated surface and associated methods of lubrication.
  • the lubricating oil compositions provided herein are substantially free of a boron-containing compound. Methods of screening lubricating oil compositions and evaluating friction and wear properties to determine compatibility with a DLC coated surface are also provided.
  • the present disclosure provides a method of lubricating a diamond-like carbon (DLC) coated surface, the method comprising: supplying to the DLC coated surface a lubricating oil composition that is substantially free of boron-containing additives.
  • DLC diamond-like carbon
  • the present disclosure provides methods for testing a lubricating oil composition comprising: supplying a lubricating oil composition to a SRV test device that comprises two DLC coated test specimens; and measuring a coefficient of friction for the lubricating oil composition according to the following procedure and conditions:
  • the SRV test device comprising the two DLC coated test specimens at a load of from 20 to 100 N, an oscillation frequency of from 10 to 50 Hz, and a stroke length of from 1 to 4 mm at a temperature of from 100 to 150°C for at least one hour; while maintaining a temperature of from 100 to 150°C and a stroke length of from 1 to 4 millimeters, increasing the load to from 500 to 1000 N and decreasing the oscillation frequency to from 2 to 10 Hz; and
  • FIG. 1 is a schematic illustration of a SRV test device.
  • Fig. 2 is a graph depicting the coefficient of friction results for comparative lubricating oil compositions and lubricating oil compositions provided herein.
  • the lubricating oil compositions of the present disclosure comprise a base oil and optionally one or more additives, wherein the lubricating oil composition is substantially free of a boron-containing compound.
  • a lubricating oil composition that is "substantially free" of a boron-containing compound refers to a lubricating oil composition that contains less than 50 ppm, less than 20 ppm, or less than 10 of boron, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may also be free of a boron- containing compound.
  • a lubricating oil composition that is "free" of a boron- containing compound refers to a lubricating oil composition that contains from 0 ppm to 50 ppm of boron, based on the total weight of the lubricating oil composition.
  • the base oil may comprise one or more mineral oils, one or more synthetic oils, or a mixture of one or more mineral oils and one or more synthetic oils; thus, as used herein, the term "base oil” may refer to a mixture containing more than one base oil.
  • base oil there are no particular limitations regarding the base oil, and various conventional mineral oils, synthetic oils, as well Group I-III mineral base oils, Group IV poly-alpha olefins (PAOs), Group II-III Fischer-Tropsch derived base oils, Group V base oils, and mixtures thereof may be used.
  • Group ⁇ By “Group ⁇ , “Group ⁇ ” “Group III” and “Group IV” and “Group V” base oils, it is meant base oils according to the definitions of American Petroleum Institute (API) for categories I, II, III, IV and V. These API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002.
  • API American Petroleum Institute
  • Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing.
  • Naphthenic base oils have low viscosity index ("VI”) (generally 40-80) and a low pour point.
  • VI viscosity index
  • Such base oils are produced from feedstocks rich in naphthenes and low in wax content and are used mainly for lubricants in which color and color stability are important, and VI and oxidation stability are of secondary importance.
  • Paraffinic base oils have higher VI (generally >95) and a high pour point. Such base oils are produced from feedstocks rich in paraffins, and are used for lubricants in which VI and oxidation stability are important.
  • Synthetic oils include hydrocarbon oils and halosubstituted hydrocarbon oils, such as olefin oligomers (including polyalphaolefin base oils; PAOs), dibasic acid esters, polyol esters, polyalkylene glycols (PAGs), Fischer-Tropsch derived base oils, alkyl naphthalenes and dewaxed waxy isomerates.
  • olefin oligomers including polyalphaolefin base oils; PAOs
  • PAGs polyalkylene glycols
  • Fischer-Tropsch derived base oils alkyl naphthalenes and dewaxed waxy isomerates.
  • Fischer-Tropsch derived base oils may be used as the base oil.
  • Fischer-Tropsch derived is meant that a base oil is, or is derived from, a synthesis product of a Fischer-Tropsch process.
  • a Fischer-Tropsch derived base oil may also be referred to as a GTL (Gas-To-Liquids) base oil.
  • Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166.
  • Poly-alpha olefin base oils PAOs
  • Suitable poly-alpha olefin base oils include those derived from linear C 2 to C32, preferably C 6 to C 1 ⁇ 2 , alpha olefins.
  • Particularly preferred feedstocks for said poly-alpha olefins are 1-octene, 1-decene, 1-dodecene and 1-tetradecene.
  • the base oil comprises mineral oils and/or synthetic oils which contain more than 80% wt of saturates, preferably more than 90 % wt, as measured according to ASTM D2007.
  • the base oil contains less than 1.0 wt. %, preferably less than 0.03 wt. % of sulfur, calculated as elemental sulfur and measured according to ASTM D2622, ASTM D4294, ASTM D4927 or ASTM D3120.
  • the base oil has a kinematic viscosity at 100°C (as measured by ASTM D445) in the range of from 1 to 35 mm 2 /s (cSt), from 2 to 25 mm 2 /s (cSt), from 5 mm 2 /s to 20 mm 2 /s, or from 5 mm 2 /s to 17 mm 2 /s.
  • the base oil has a kinematic viscosity at 100°C (as measured by ASTM D445) of at least 2.5 mm 2 /s, more preferably at least 3.0 mm 2 /s.
  • the base oil preferably has a kinematic viscosity at 40°C (as measured by ASTM D445) of from 10 to 180 mm 2 /s (cSt), from 15 to 170 mm 2 /s, or from 20 to 100 mm 2 /s.
  • the base oil preferably has a viscosity index (according to ASTM D 2270) in the range of from 80 to 300.
  • the base oil has a viscosity index of at least 120, at least 130, or at least 150.
  • the base oil preferably has a pour point (as measured according to ASTM D97) of -10°C or below,-30°C or below, or -40°C or below.
  • the flash point (as measured by ASTM D92) of the base oil is preferably greater than 120°C, greater than 140°C, greater than 160°C, greater than 180°C, greater than 200°C, or greater than 220°C.
  • the amount of base oil present in a fully formulated lubricating oil composition will typically be the amount remaining to equal 100% after the remaining additives are accounted for.
  • the base oil may be present in an amount in the range of from 60 to 99.99 wt. %, in an amount in the range of from 65 to 95 wt. %, in an amount in the range of from 70 to 90 wt. %, or in an amount in the range of from 75 to 88 wt. %, with respect to the total weight of the lubricating oil composition.
  • the lubricating oil compositions may further comprise one or more additional additives to impart or enhance the desired properties of the fully formulated composition.
  • Any lubricating oil additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein, provided that the lubricating oil composition remains substantially free of a boron-containing compound.
  • suitable additives include, but are not necessarily limited to, anti-oxidants, anti-wear additives, detergents, dispersants, friction modifiers, viscosity index improvers, pour point depressants, corrosion inhibitors, seal fix/seal compatibility agents, defoamers/foam inhibitors, and combinations thereof.
  • the concentration of each of the additives in the lubricating oil composition when used, may range from about 0.001 wt. % to about 20 wt. %, from about 0.01 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 5 wt. %, based on the total weight of the lubricating oil composition.
  • the total amount of the additives in the lubricating oil composition may range from about 0.001 wt. % to about 25 wt. %, from about 0.01 wt. % to about 20 wt. %, or from about 0.1 wt. % to about 10 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise an antioxidant to reduce or prevent the oxidation of the base oil.
  • Any antioxidant known to a person of ordinary skill in the art may be used in the lubricating oil compositions.
  • Suitable anti-oxidants include, but are not limited to, aminic antioxidants, phenolic antioxidants, and mixtures thereof.
  • aminic antioxidants which may be conveniently used include alkylated diphenylamines, phenyl- a-naphthylamines, phenyl- -naphthylamines and alkylated a-naphthylamines.
  • Preferred aminic antioxidants include dialkyldiphenylamines such as p,p'-dioctyl- diphenylamine, p,p'-di-a-methylbenzyl-diphenylamine and N-p-butylphenyl-N-p'- octylphenylamine, monoalkyldiphenylamines such as mono-t-butyldiphenylamine and mono- octyldiphenylamine, bis(dialkylphenyl)amines such as di-(2,4-diethylphenyl)amine and di(2- ethyl-4-nonylphenyl)amine, alkylphenyl-l-naphthylamines such as octylphenyl-l-naphthylamine and n-t-dodecylphenyl-l-naphthylamine, 1-naphthyl
  • Preferred aminic antioxidants include those available under the following trade designations: "Sonoflex OD-3" (ex. Seiko Kagaku Co.), “Irganox L-57” (ex. Ciba Specialty Chemicals Co.) and phenothiazine (ex. Hodogaya Kagaku Co.).
  • phenolic antioxidants which may be conveniently used include C 7 - C9 branched alkyl esters of 3,5-bis(l,l-dimethyl-ethyl)-4-hydroxy-benzenepropanoic acid, 2-t- butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2,4-di-t-butylphenol, 2,4- dimethyl-6-t-butylphenol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2,5-di-t- butylhydroquinone, 2,6-di-t-butyl-4-alkylphenols such as 2,6-di-t-butylphenol, 2,6-di-t-butyl-4- methylphenol and 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-alkoxyphenols such as 2,6-d
  • Suitable phenolic antioxidants include those which are commercially available under the following trade designations: "Irganox L-135" (ex. Ciba Specialty Chemicals Co.), “Yoshinox SS” (ex. Yoshitomi Seiyaku Co.), “Antage W-400” (ex. Kawaguchi Kagaku Co.), “Antage W-500” (ex. Kawaguchi Kagaku Co.), “Antage W-300” (ex. Kawaguchi Kagaku Co.), “Irganox L109” (ex. Ciba Speciality Chemicals Co.), “Tominox 917” (ex. Yoshitomi Seiyaku Co.), “Irganox LI 15" (ex.
  • Ciba Speciality Chemicals Co. Ciba Speciality Chemicals Co.
  • Sudilizer GA80 Ex. Sumitomo Kagaku
  • Antage RC ex. Kawaguchi Kagaku Co.
  • Irganox L101 ex. Ciba Speciality Chemicals Co.
  • Yoshinox 930 ex. Yoshitomi Seiyaku Co.
  • antioxidants may be present in an amount in the range of from 0.01 to 10 wt. %, in an amount in the range of from 0.3 to 3.0 wt. %, or in an amount in the range of from 0.5 to 1.5 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise an anti-wear additive.
  • Any anti-wear additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron-containing compound.
  • suitable anti-wear additives include, but are not limited to, zinc- containing compounds, such as zinc dithiophosphate compounds selected from zinc dialkyl-, diaryl- and/or alkylaryl- dithiophosphates, molybdenum-containing compounds, and ashless anti- wear additives such as substituted or unsubstituted thiophosphoric acids, and salts thereof.
  • zinc- containing compounds such as zinc dithiophosphate compounds selected from zinc dialkyl-, diaryl- and/or alkylaryl- dithiophosphates, molybdenum-containing compounds
  • ashless anti- wear additives such as substituted or unsubstituted thiophosphoric acids, and salts thereof.
  • Zinc dithiophosphate is a well known additive in the art and may be conveniently represented by general formula I: wherein R 2 to R 5 may be the same or different and are each a primary alkyl group containing from 1 to 20 carbon atoms preferably from 3 to 12 carbon atoms, a secondary alkyl group containing from 3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, an aryl group or an aryl group substituted with an alkyl group, said alkyl substituent containing from 1 to 20 carbon atoms preferably 3 to 18 carbon atoms.
  • Zinc dithiophosphate compounds in which R 2 to R 5 are all different from each other can be used alone or in admixture with zinc dithiophosphate compounds in which R 2 to R 5 are all the same.
  • suitable zinc dithiophosphates include those which are commercially available under the following trade designations: “Lz 1097”, “Lz 1395”, “Lz 677 A”, “Lz 1095”, “Lz 1370”, “Lz 1371”, and “Lz 1373” (ex. Lubrizol Corporation); “OLOA 267”, “OLOA 269R”, “OLOA 260” and “OLOA 262” (ex. Chevron Oronite); and “HITEC 7197” and "HITEC 7169” (ex. Afton Chemical).
  • Examples of molybdenum-containing compounds may conveniently include molybdenum dithiocarbamates, trinuclear molybdenum compounds, for example as described in WO 98/26030, sulphides of molybdenum and molybdenum dithiophosphate.
  • Examples of ashless anti-wear additives may also conveniently include phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, and reaction products of dicyclopentadiene and thiophosphoric acids.
  • the lubricating oil compositions may comprise in the range of from 0.4 to 5 wt. % of an anti-wear additive, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise a detergent. Any detergent known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron- containing compound.
  • suitable detergents include, but are not limited to, a neutral or overbased metal detergent, such as salicylate, phenate, phosphonate and sulphonate detergents.
  • the metal can be any metal suitable for making such detergents detergents, including alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li, etc.
  • a detergent may be present in an amount in the range of from 0.001 to 20 wt. %, in an amount in the range of from 0.05 to 10 wt. %, or in an amount in the range of from 1 to 5 wt. %, based on the total weight of the lubricating oil composition.
  • the detergents independently, have a TBN (total base number) value in the range of from 10 to 500 mg.KOH/g, more preferably in the range of from 30 to 350 mg.KOH/g and most preferably in the range of from 50 to 300 mg.KOH/g, as measured by ISO 3771.
  • TBN total base number
  • the lubricating oil compositions may comprise a dispersant. Any dispersant known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron- containing compound.
  • Suitable dispersants include, but are not limited to, polyalkenyl succinimides and polyalkenyl succininic acid esters disclosed in Japanese Patent Nos. 1367796, 1667140, 1302811 and 1743435.
  • a dispersant may be present in an amont in the range of from .01 to 15 wt. %, in an amount in the range of from 0.05 to 10 wt. %, or in an amount in the range of from 0.1 to 5 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise a friction modifier. Any friction modifier known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron-containing compound.
  • Suitable friction modifiers include, but are not limited to, fatty carboxylic acids; derivatives (e.g., alcohol, estersamides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives (e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di- alkyl substituted amides, etc.
  • a friction modifier may be present in an amount in the range of from 0.01 to 10 wt. %, in an amount in the range of from 0.05 to 5 wt. %, or in an amount in the range of from 0.1 to 2 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise a viscosity index improver. Any viscosity index improver known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron-containing compound.
  • suitable viscosity index improvers include, but are not limited to, polymers and copolymers of methacrylate, butadiene, olefins or alkylated styrenes, styrene- butadiene copolymers, styrene-isoprene stellate copolymers, polymethacrylate, polyisobutylene and ethylene-propylene copolymers.
  • Such viscosity index improvers may be conveniently employed in an amount in the range of from 1 to 20 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise a pour point depressant. Any pour point depressant known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron-containing compound.
  • pour point depressants include, but are not limited to, polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, alkyl fumarate polymers, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates of a chlorinated paraffin with naphthalene, alkylated naphthalenes, styrene esters, oligomerized alkyl phenols, phthalic acid esters, ethylene-vinyl acetate copolymers, etc.
  • a pour point depressant may be present in an amount in the range of from 0.01 to 10 wt. %, in an amount in the range of from 0.05 to 5 wt. %, or in an amount in the range of from 0.1 to 1 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise a corrosion inhibitor. Any corrosion inhibitor known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron-containing compound.
  • corrosion inhibitors include, but are not limited to, alkenyl succinic acid or ester moieties thereof, benzotriazole-based compounds and thiodiazole-based compounds, etc.
  • a corrosion inihibitor may be present in an amount in the range of from .01 to 10 wt. %, in an amount in the range of from 0.05 to 5 wt. %, or in an amount in the range of from 0.01 to 1 wt. %, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may comprise a seal fix additive.
  • Any seal fix additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron-containing compound.
  • suitable seal fix additives include, but are not limited to, commercially available aromatic esters, etc. 10.
  • the lubricating oil compositions may comprise a defoamer. Any defoamer known to a person of ordinary skill in the art may be used in the lubricating oil compositions, provided that the lubricating oil composition remains substantially free of a boron- containing compound.
  • suitable defoamers include, but are not limited to, silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines, etc.
  • the defoamer comprises glycerol monostearate, polyglycol palmitate, a trialkyl monothiophosphate, an ester of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or glycerol dioleate.
  • suitable defoamers may comprise a solvent, such as a paraffinic mineral oil, naphthenic mineral oil, petroleum naphtha, aromatics, toluene, xylene, benzene, hexane, heptane, octane, dodecane, kerosene, etc. and combinations thereof.
  • a solvent such as a paraffinic mineral oil, naphthenic mineral oil, petroleum naphtha, aromatics, toluene, xylene, benzene, hexane, heptane, octane, dodecane, kerosene, etc. and combinations thereof.
  • the silicone oil may be dispersed or dissolved in the solvent.
  • the defoaming agent may be dispersed or dissolved in the solvent.
  • a defoamer may be present in an amount in the range of from 0.1 to 1000 ppm, in an amount in the range of from 1 to 500 ppm, in an amount in the range of from 1 to 100 ppm, in an amount in the range of from 5 to 50 ppm, or in an amount in the range of from 10 to 30 ppm, based on the total weight of the lubricating oil composition.
  • the lubricating oil compositions may be conveniently prepared in any manner, including using conventional formulation techniques.
  • the lubricating oil compositions may be prepared by admixing a base oil with one or more optional additives. Any mixing equipment known to a person of ordinary skill in the art may be used herein.
  • the lubricating oil compositions may generally be used to lubricate any DLC coated surface that is in relative movement to another surface.
  • the lubricating oil compositions may be used to lubricate a DLC coated surface of a rotating or sliding member in a vehicle or industrial machine.
  • the lubricating oil compositions may be used to lubricate a DLC coated surface that is in relative movement to another DLC coated surface.
  • the lubricating oil compositions may also be useful to lubricate a DLC coated surface in an engine (e.g., an internal combustion engine), a gear mechanism, a speed-change gearbox, a bearing, a hydraulic apparatus, compression machinery, etc.
  • the lubricating oil compositions provided herein may be particularly suitable for use in a high output engine comprising one or more component having a DLC coated surface, for example those found in racing cars and sports cars.
  • the lubricating oil compositions provide improved wear protection and decreased energy loss under severe operating conditions.
  • the disclosure herein further provides methods for evaluating the friction and/or wear properties of a lubricating oil composition when used to lubricate a DLC coated surface in relative movement to another DLC coated surface. Additionally, the present disclosure provides screening methods to identify lubricating oil compositions that are suitable for lubricating a DLC coated surface that is in relative movement to another DLC coated surface.
  • the methods generally comprise supplying a lubricating oil composition to a SRV test device that comprises two DLC coated test specimens and measuring the coefficient of friction of the lubricating oil composition according to the following procedure and conditions:
  • the SRV test device 100 comprises an oscillation drive 110, an upper specimen holder 120 and a lower specimen holder 130.
  • an upper DLC coated test specimen 125 such as a DLC coated cylinder, ring or ball, is placed into the upper specimen holder 120 and a lower DLC coated test specimen 135, such as a DLC coated disk, is placed into the lower specimen holder 130.
  • the lubricating oil composition to be tested is interposed between the two DLC coated specimens and a load is applied.
  • the upper DLC coated test specimen is oscillated against the lower DLC coared test specimen at the conditions specified above.
  • the SRV test device may measure other properties, such as wear scar depth.
  • a suitable SRV test device is an Optimol SRV-4 (available from Optimol Instruments Priiftechnik GmbH Kunststoff, Germany(Optimol)) .
  • Test Method The SRV test device used was an Optimol SRV-4 (available from
  • the lower test specimen was a 6.9 x 22mm DLC coated disk and the upper test specimen was a 11 x 16 mm (diameter x length) DLC coated cylinder, both purchased from Optimol.
  • a custom sample pan holder was manufactured to fit the 6.9 x 22 mm DLC coated disk.
  • the sample pan holds approximately 2 ml of a lubricating oil composition, and allows fully flooded extended duration lubricant testing to be conducted in the SRV-4.
  • the upper and lower test specimens (e.g. cylinder and disk) were installed in the SRV test device and testing was performed on Lubricating Compositions A-C in accordance with the methods described herein.
  • Lubricating oil compositions comprising a base oil, a calcium-containing detergent, a zinc -containing anti-wear additive, and a molybdenum-containing anti-wear additive were formulated and had the composition indicated in Table 1.
  • Lubricating Oil A additionally contained a boron-containing dispersant. All formulations were manufactured by blending together the base oil and the additives using conventional mixing techniques. TABLE 1
  • Figure 2 shows the measured coefficient of friction for each of the Lubricating Oils A-C.
  • Lubricating Oil A which was comparative, contained boron, while Lubricating Oils B and C contained 0 ppm boron.
  • the boron-containing oil, Oil A showed high and sticky friction while the boron-free oils, Oils B and C showed low and smooth friciton.
  • the high friction could cause DLC coating failures such as overheating, wear, flaking or delamination under stress.
  • the low and smooth friction improves the fuel efficiency and prevent DLC coatings from wear and flaking.

Abstract

La présente invention concerne des compositions d'huile lubrifiante appropriées pour lubrifier une surface revêtue de carbone sous forme de diamant amorphe et des procédés de lubrification associés. Les compositions d'huile lubrifiante selon l'invention sont pratiquement exemptes d'un composé contenant du bore. L'invention concerne également des procédés de criblage de compositions d'huile lubrifiante et d'évaluation des propriétés de frottement et d'usure pour déterminer la compatibilité avec une surface à revêtement en carbone sous forme de diamant amorphe.
PCT/US2015/045448 2014-08-27 2015-08-17 Procédés de lubrification d'une surface revêtue de carbone de type diamant, compositions d'huile lubrifiante associées et procédés de criblage associés WO2016032782A1 (fr)

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Publication number Priority date Publication date Assignee Title
CZ307068B6 (cs) * 2016-06-23 2017-12-27 Technická univerzita v Liberci Způsob vyhodnocení modifikace olejů užívaných do převodových systémů nebo olejů pro obrábění kovových materiálů

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CZ307068B6 (cs) * 2016-06-23 2017-12-27 Technická univerzita v Liberci Způsob vyhodnocení modifikace olejů užívaných do převodových systémů nebo olejů pro obrábění kovových materiálů

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