EP1462508B1 - Use of an organomolybdenum compound containing composition for the lubrication of diamond-like carbon coated surfaces - Google Patents
Use of an organomolybdenum compound containing composition for the lubrication of diamond-like carbon coated surfaces Download PDFInfo
- Publication number
- EP1462508B1 EP1462508B1 EP20040251370 EP04251370A EP1462508B1 EP 1462508 B1 EP1462508 B1 EP 1462508B1 EP 20040251370 EP20040251370 EP 20040251370 EP 04251370 A EP04251370 A EP 04251370A EP 1462508 B1 EP1462508 B1 EP 1462508B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- molybdenum
- oil
- lubricating
- lubricating oil
- oil composition
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 37
- 229910052799 carbon Inorganic materials 0.000 title claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 title description 18
- 238000005461 lubrication Methods 0.000 title description 6
- 239000003921 oil Substances 0.000 claims description 30
- 239000005078 molybdenum compound Substances 0.000 claims description 27
- 239000010687 lubricating oil Substances 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 18
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 230000001050 lubricating effect Effects 0.000 claims description 11
- 239000003599 detergent Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- -1 e.g. Chemical class 0.000 description 30
- 235000019198 oils Nutrition 0.000 description 28
- 239000003446 ligand Substances 0.000 description 23
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 description 16
- 239000002199 base oil Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 125000000962 organic group Chemical group 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010689 synthetic lubricating oil Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000007737 ion beam deposition Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 150000003003 phosphines Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
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- 239000010802 sludge Substances 0.000 description 2
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- 150000003871 sulfonates Chemical class 0.000 description 2
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- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
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- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
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- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
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- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical group [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 1
- XWKKZTDYIZDRQS-UHFFFAOYSA-J [Mo+4].[S-][PH2]=S.[S-][PH2]=S.[S-][PH2]=S.[S-][PH2]=S Chemical compound [Mo+4].[S-][PH2]=S.[S-][PH2]=S.[S-][PH2]=S.[S-][PH2]=S XWKKZTDYIZDRQS-UHFFFAOYSA-J 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- WLLCYXDFVBWGBU-UHFFFAOYSA-N bis(8-methylnonyl) nonanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC(C)C WLLCYXDFVBWGBU-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OSMZVRQRVPLKTN-UHFFFAOYSA-N calcium;1-nonyl-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical compound [Ca].C1=CC=CC2(CCCCCCCCC)C1(O)S2 OSMZVRQRVPLKTN-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- DZQISOJKASMITI-UHFFFAOYSA-N decyl-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound CCCCCCCCCCP(O)(O)=O DZQISOJKASMITI-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- SFPKXFFNQYDGAH-UHFFFAOYSA-N oxomolybdenum;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.[Mo]=O SFPKXFFNQYDGAH-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PQRRMYYPKMKSNF-UHFFFAOYSA-N tris(4-methylpentan-2-yl) tris(4-methylpentan-2-yloxy)silyl silicate Chemical compound CC(C)CC(C)O[Si](OC(C)CC(C)C)(OC(C)CC(C)C)O[Si](OC(C)CC(C)C)(OC(C)CC(C)C)OC(C)CC(C)C PQRRMYYPKMKSNF-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- 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
Definitions
- This invention relates to lubricating oil compositions (also known as lubricants) particularly useful for lubricating surfaces coated with diamond-like carbon (DLC) films or coatings.
- lubricating oil compositions also known as lubricants
- DLC diamond-like carbon
- Diamond-like carbon hereinafter is a known amorphous carbon material usually provided in the form of a film or coating, and so-named because its properties resemble, but do not duplicate, those of diamond. Some of these properties are high hardness (about 3 to about 22 GPa), a low friction coefficient (approximately 0.1) and transparency across a major part of the electromagnetic spectrum. At least some of the carbon atoms in DLC are bonded in chemical structures similar to those of diamond, but without long-range crystal order.
- the term DLC embraces not only pure carbon material, but also extends to amorphous, hard carbon materials containing up to 50 atomic percent of hydrogen.
- Such hydrogen-containing DLC materials are also referred to variously as “amorphous hydrogenated carbon", “hydrogenated diamond-like carbon” and “diamond-like hydrocarbon”.
- amorphous hydrogenated carbon hydrogenated diamond-like carbon
- diamond-like hydrocarbon diamond-like hydrocarbon
- the structure of these hydrogen-containing hard carbon materials may be described as a random covalent network of graphitic-type structures interconnected by sp 3 linkages, although such a structure has yet to be universally accepted.
- DLC may be doped with other elements or combinations of elements. The addition of such elements, e.g. silicon and germanium, can provide or enhance useful material properties such as wear resistance, adhesion, hardness, stress, and oxidation resistance.
- the term "DLC” as used in this specification includes amorphous non-hydrogenated hard carbon materials, amorphous hydrogenated hard carbon materials and doped modifications thereof.
- DLC films or coatings are known in the art, including (i) direct ion beam deposition, dual ion beam deposition, glow discharge, radio frequency (RF) plasms, direct current (DC) plasma or microwave plasma deposition from a carbon-containing gas or vapour which can also be mixed with hydrogen and/or inert gas and/or other gases containing doping elements, (ii) electron beam evaporation, ion-assisted evaporation, magnetron sputtering, ion beam sputtering, or ion-assisted sputter deposition from a solid carbon or doped carbon target material, or (iii) combinations of (i) and (ii).
- RF radio frequency
- DC direct current
- microwave plasma deposition from a carbon-containing gas or vapour which can also be mixed with hydrogen and/or inert gas and/or other gases containing doping elements
- DLC films used in coating the components of internal combustion engines is described, for example, in U.S. Patent 5,771,873 .
- the present invention is based on the discovery that surfaces, such as those of engine components, coated with DLC films or coatings can be effectively lubricated.
- a method of lubricating a surface coated with a diamond-like carbon film or coating which comprises supplying to said surface a lubricating oil composition comprising an oil of lubricating viscosity, preferably in a major amount, and an effective friction reducing amount of an oil-soluble organo-molybdenum compound. It has been found that the organo-molybdenum additive will substantially reduce friction on the DLC surfaces to an extent not observed on steel surfaces.
- an organo-molybdenum additive is used so as to provide 25 to 1000 ppm (parts per million, by weight), preferably 200 to 750 ppm, of elemental molybdenum in the lubricating oil compositions (as determined by ASTM D5185).
- a further aspect of the invention relates to the use of a lubricating oil composition
- a lubricating oil composition comprising an oil of lubricating viscosity and an effective friction-reducing amount of an oil-soluble organo-molybdenum compound to lubricate a surface coated with a diamond-like carbon film or coating.
- the method of this invention is especially applicable to the lubrication of spark-ignited or compression-ignited two-stroke or four-stroke internal combustion engines which have parts or components with DLC films or coatings.
- Such components include the carn shaft, especially the cam lobes; pistons, especially the piston skirt; cylinder liners; and valves.
- oil-soluble organo-molybdenum compounds there may be mentioned dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates and sulfides of molybdenum and mixtures thereof.
- the molybdenum compounds may be acidic molybdenum compounds. These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl 4 , MoO 2 Br 2 , Mo 2 O 3 Cl 6 , molybdenum trioxide or similar acidic molybdenum compounds.
- molybdenum compounds useful in the compositions of this invention are organo-molybdenum compounds of the formulae Mo(ROCS 2 ) 4 and Mo(RSCS 2 ) 4 wherein R is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms.
- dialkyldithiocarbamates of molybdenum are especially preferred.
- a further class of organo-molybdenum compounds is represented by the formula: where R 1 to R 4 independently denote a straight chain, branched chain or aromatic hydrocarbyl group having 1 to 24 carbon atoms; and X 1 to X 4 independently denote an oxygen atom or a sulfur atom.
- the four hydrocarbyl groups, R 1 to R 4 may be identical or different from one another.
- organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula MO 3 S k L n Q z and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values.
- n 3 or 1
- appropriately charged ionic species is required to confer electrical neutrality to the trinuclear molybdenum compound.
- the ionic species may be of any valence, for example, monovalent or divalent. Further the ionic species may be negatively charged, i.e. an anionic species, or may be positively charged, i.e. a cationic species or a combination of an anion and a cation. Such terms are known to a skilled person in the art.
- the ionic species may be present in the compound through covalent bonding, i.e.
- anionic species include disulfide, hydroxide, an alkoxide, an amide and a thiocyanate or derivate thereof; preferably the anionic species is disulfide ion.
- cationic species include an ammonium ion and a metal ion, such as an alkali metal, alkaline earth metal or transition metal, ion, preferably an ammonium ion, such as [NR 4 ] + where R is independently H or alkyl group, more preferably R is H, i.e. [NH 4 ] + . At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
- the ligands are independently selected from the group of ⁇ X ⁇ R 1, and and mixtures thereof, wherein X, X 1 , X 2 , and Y are independently selected from the group of oxygen and sulfur, and wherein R 1 , R 2 , and R are independently selected from hydrogen and organo groups that may be the same or different.
- the organo groups are hydrocarbyl groups such as alkyl (e.g., in which the carbon atom attached to the remainder of the ligand is primary or secondary), aryl, substituted aryl and ether groups. More preferably, each ligand has the same hydrocarbyl group.
- hydrocarbyl denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention.
- substituents include the following:
- the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil.
- the number of carbon atoms in each group will generally range between 1 to 100, preferably from 1 to 30, and more preferably between 4 to 20.
- Preferred ligands include dialkyldithiophosphate, alkylxanthate, and dialkyldithiocarbamate, and of these dialkyldithiocarbamate is more preferred.
- Organic ligands containing two or more of the above functionalities are also capable of serving as ligands and binding to one or more of the cores. Those skilled in the art will realize that formation of the compounds of the present invention requires selection of ligands having the appropriate charge to balance the core's charge.
- Oil-soluble or oil-dispersible trinuclear molybdenum compounds can be prepared by reacting in the appropriate liquid(s) and/or solvent(s) a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide.
- a molybdenum source such as (NH 4 ) 2 Mo 3 S 13 .n(H 2 O), where n varies between 0 and 2 and includes non-stoichiometric values
- oil-soluble or oil-dispersible trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as of (NH 4 ) 2 Mo 3 S) 13 ⁇ n(H 2 O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur-abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
- a molybdenum source such as of (NH 4 ) 2 Mo 3 S) 13 ⁇ n(H 2 O)
- a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate
- sulfur-abstracting agent such cyanide ions, sulfite ions, or substituted phosphines.
- a trinuclear molybdenum-sulfur halide salt such as [M'] 2 [Mo 3 S 7 A 6 ], where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s) and/or solvent(s) to form an oil-soluble or oil-dispersible trinuclear molybdenum compound.
- the appropriate liquid and/or solvent may be, for example, aqueous or organic.
- a compound's oil solubility or dispersibility may be influenced by the number of carbon atoms in the ligand's organo groups. In the compounds employed in the present invention, at least 21 total carbon atoms should be present among all the ligand's organo groups. Preferably, the ligand source chosen has a sufficient number of carbon atoms in its organo groups to render the compound soluble or dispersible in the lubricating composition.
- the molybdenum compound is preferably an organo-molybdenum compound. Moreover, the molybdenum compound is preferably selected from the group consisting of a molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate, molybdenum dithiophosphinate, molybdenum xanthate, molybdenum thioxanthate and mixtures thereof. Most preferably, the molybdenum compound is present as molybdenum dithiocarbamate. The molybdenum compound is preferably a trinuclear molybdenum compound, such as a trinuclear molybdenum dithiocarbamate.
- MoDTC molybdenum dithiocarbamate
- the molybdenum compound is preferably a trinuclear molybdenum compound, such as a trinuclear molybdenum dithiocarbamate.
- Natural oils useful as the oil of lubricating viscosity (also known as basestocks) in this invention include animal oils and vegetable oils (e.g. castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
- Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification or etherification constitute a class of known synthetic lubricating oils useful as basestocks in this invention. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g.
- methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3 -C 8 fatty acid esters and C 13 Oxo acid diester of tetraethylene glycol.
- Another suitable class of synthetic lubricating oils useful in this invention comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (i-butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
- dicarboxylic acids e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic
- esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
- Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
- Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tertbutylphenyl) silicate, hexa-(4-methyl-2-pentoxy) disiloxane, poly(methyl) siloxanes and poly(methylphenyl) siloxanes.
- Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
- liquid esters of phosphorus-containing acids e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid
- polymeric tetrahydrofurans e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid
- Unrefined, refined and rerefined oils can be used in the lubricating oil compositions of the present invention.
- Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
- a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improved one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
- Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
- Molybdenum-containing lubricating oil compositions for use in the present invention may also contain any of the conventional additives listed below (including any additional friction modifiers) which are typically used in a minor amount, e.g. such an amount so as to provide their normal attendant functions. Typical amounts for individual components are also set forth below. All the values listed are stated as mass percent active ingredient in the total lubricating oil composition.
- each of the components may be added directly to the basestock by dispersing or dissolving it in the basestock at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
- all the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate (or additive package) that is subsequently blended into basestock to make a finished lubricating oil composition.
- a concentrate or additive package
- the concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final lubricating oil composition when the concentrate is combined with a predetermined amount of base oil.
- the concentrate is conveniently made in accordance with the method described in U.S. 4,938,880 .
- That patent describes making a pre-mix of ashless dispersant and metal detergents that is pre-blended at a temperature of at least about 200°C. Thereafter, the pre-mix is cooled to at least 85°C and the additional components are added.
- the final crankcase lubricating oil composition may employ from 2 to 20 mass % and preferably 4 to 15 mass % of the concentrate (or additive package), the remainder being base oil.
- Ashless dispersants maintain in suspension oil-insoluble matter resulting from oxidation of the oil during wear or combustion. They are particularly advantageous for preventing precipitation of sludge and formation of varnish, particularly in gasoline engines.
- Ashless dispersants comprise an oil-soluble polymeric hydrocarbon backbone bearing one or more functional groups that are capable of associating with particles to be dispersed.
- the polymer backbone is functionalized by amine, alcohol, amide, or ester polar moieties, often via a bridging group.
- the ashless dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
- the oil-soluble polymeric hydrocarbon backbone of these dispersants is typically derived from an olefin polymer or polyene, especially polymers comprising a major molar amount (i.e. greater than 50 mole %) of a C 2 to C 18 olefin (e.g. ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene), and typically a C 2 to C 5 olefin.
- the oil-soluble polymeric hydrocarbon backbone may be a homopolymer (e.g. polypropylene or polyisobutylene) or a copolymer of two or more of such olefins (e.g.
- Other copolymers include those in which a minor molar amount of the copolymer monomers, for example, 1 to 10 mole %, is an ⁇ , ⁇ -diene, such as a C 3 to C 22 non-conjugated diolefin (for example, a copolymer of isobutylene and butadiene, or a copolymer of ethylene, propylene and 1,4-hexadiene or 5-ethylidene-2-norbornene).
- Preferred are polyisobutenyl (Mn 400-2500, preferably 950-2200) succinimide dispersants.
- the viscosity modifier functions to impart high and low temperature operability to a lubricating oil composition.
- the VM used may have that sole function, or may be multifunctional.
- Multifunctional viscosity modifiers that also function as dispersants are also known.
- Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic ester, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
- Metal-containing or ash-forming detergents may be present and these function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
- Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acid organic compound.
- the salts may contain a substantially stoichiometric amount of the metal in which they are usually described as normal or neutral salts, and would typically have a total base number (TBN), as may be measured by ASTM D-2896 of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as carbon dioxide.
- the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle.
- a metal base e.g. carbonate
- Such overbased detergents may have a TBN of 150 or greater, and typically from 250 to 450 or more.
- Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali, e.g. sodium, potassium, lithium and magnesium.
- Preferred are neutral or overbased calcium and magnesium phenates and sulfonates, especially calcium.
- friction modifiers include oil-soluble amines, amides, imidazolines, amine oxides, amidoamines, nitriles, alkanolamides, alkoxylated amines and ether amines; polyol esters; and esters of polycarboxylic acids.
- Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents.
- the metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. They may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P 2 S 5 and then neutralizing the formed DDPA with a zinc compound.
- DDPA dihydrocarbyl dithiophosphoric acid
- a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols.
- multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character.
- any basic or neutral zinc compound may be used but oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
- the lubricating oil compositions of the invention preferably contain no more than 0.8 wt %, such as from 50 ppm to 0.06 wt %, of phosphorus.
- the lubricating oil composition preferably has no more than 0.5 wt %, preferably from 50 ppm to 0.3 wt %, of sulfur, the amounts of sulfur and of phosphorus being measured in accordance with ASTM D5185.
- Oxidation inhibitors or antioxidants reduce the tendency of basestocks to deteriorate in service, which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.
- oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C 5 to C 12 alkyl side chains, calcium nonylphenol sulfide, ashless oil-soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil-soluble copper compound as described in U.S. 4,867,890 , and molybdenum-containing compounds.
- Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
- Copper- and lead-bearing corrosion inhibitors may be used, but are typically not required in the lubricating oil compositions of the present invention.
- such compounds are thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
- Derivatives of 1,3,4-thiadiazoles such as those described in U.S. Patent Nos. 2,719,125 ; 2,719,126 ; and 3,087,932 , are typical.
- Other similar material are described in U.S. Patent Nos. 3,821,236 ; 3,904,537 ; 4,097,387 ; 4,107,059 ; 4,136,043 ; 4,188,299 ; and 4,193,882 .
- additives are thio and polythio sulfenamides of thiadiazoles such as those described in GB-A-1,560,830 .
- Benzotriazoles derivatives also fall within this class of additive. When these compounds are included in the lubricating oil compositions, they are preferably present in an amount not exceeding 0.2 wt.% active ingredient.
- a small amount of a demulsifying component may be used.
- a preferred demulsifying component is described in EP-A-330 522 . It is obtained by reacting an alkylene oxide with an adduct obtained by reacting a bis-epoxide with a polyhydric alcohol.
- the demulsifier should be used at a level not exceeding 0.1 mass % active ingredient. A treat rate of 0.001 to 0.05 mass % active ingredient is convenient.
- Pour point depressants otherwise known as lube oil improvers, lower the minimum temperature at which the fluid will flow or can be poured.
- Such additives are well-known. Typical of those additives, which improve the low temperature fluidity of the fluid, are C 8 and C 18 dialkyl fumarate/vinyl acetate copolymers and polyalkylmethacrylates.
- Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
- the term “comprising” means the presence of stated features, integers, steps or components, but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. If the term “comprising” (or cognates) is used herein, the term “consisting essentially of” (and its cognates) is within its scope and is a preferred embodiment; consequently the term “consisting of” (and its cognates) is within the scope of “consisting essentially of” and is a preferred embodiment thereof.
- oil-soluble or “oil-dispersible” do not mean that the compounds are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. They do mean, however, that the compounds are, for instance, soluble or stably dispersible in the oil to an extent sufficient to exert their intended effect in the environment in which the composition is employed. Moreover, the additional incorporation of other additives such as those described above may affect the solubility or dispersibility of the compounds.
- major amount means in excess of 50 mass % of the composition.
- minor amount means less than 50 mass % of the composition.
- the coefficients of friction for the lubrication of steel on steel surfaces were measured and compared with the coefficients of friction for DLC coated steel surfaces using the same lubricants.
- the DLC coating is sold as "Dymon-iC" the trademark for a hydrogenated carbon coating supplied by Teer Coatings Ltd. Both types of surfaces were lubricated with:
- Table 2 indicates that, in the lubrication of contacting DLC surfaces, the molybdenum-containing lubricating oil composition is substantially better at increasing fnction reduction than the composition containing a conventional friction reducing agent, glycerol mono-oleate.
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Description
- This invention relates to lubricating oil compositions (also known as lubricants) particularly useful for lubricating surfaces coated with diamond-like carbon (DLC) films or coatings.
- Diamond-like carbon hereinafter (DLC), is a known amorphous carbon material usually provided in the form of a film or coating, and so-named because its properties resemble, but do not duplicate, those of diamond. Some of these properties are high hardness (about 3 to about 22 GPa), a low friction coefficient (approximately 0.1) and transparency across a major part of the electromagnetic spectrum. At least some of the carbon atoms in DLC are bonded in chemical structures similar to those of diamond, but without long-range crystal order. The term DLC embraces not only pure carbon material, but also extends to amorphous, hard carbon materials containing up to 50 atomic percent of hydrogen. Such hydrogen-containing DLC materials are also referred to variously as "amorphous hydrogenated carbon", "hydrogenated diamond-like carbon" and "diamond-like hydrocarbon". Without wishing to be bound by any theory, the structure of these hydrogen-containing hard carbon materials may be described as a random covalent network of graphitic-type structures interconnected by sp3 linkages, although such a structure has yet to be universally accepted. In addition DLC may be doped with other elements or combinations of elements. The addition of such elements, e.g. silicon and germanium, can provide or enhance useful material properties such as wear resistance, adhesion, hardness, stress, and oxidation resistance. The term "DLC" as used in this specification, includes amorphous non-hydrogenated hard carbon materials, amorphous hydrogenated hard carbon materials and doped modifications thereof.
- Many methods for directly depositing DLC films or coatings are known in the art, including (i) direct ion beam deposition, dual ion beam deposition, glow discharge, radio frequency (RF) plasms, direct current (DC) plasma or microwave plasma deposition from a carbon-containing gas or vapour which can also be mixed with hydrogen and/or inert gas and/or other gases containing doping elements, (ii) electron beam evaporation, ion-assisted evaporation, magnetron sputtering, ion beam sputtering, or ion-assisted sputter deposition from a solid carbon or doped carbon target material, or (iii) combinations of (i) and (ii).
- The use of such DLC films in coating the components of internal combustion engines is described, for example, in
U.S. Patent 5,771,873 . The present invention is based on the discovery that surfaces, such as those of engine components, coated with DLC films or coatings can be effectively lubricated. - In accordance with the present invention there has been discovered a method of lubricating a surface coated with a diamond-like carbon film or coating which comprises supplying to said surface a lubricating oil composition comprising an oil of lubricating viscosity, preferably in a major amount, and an effective friction reducing amount of an oil-soluble organo-molybdenum compound. It has been found that the organo-molybdenum additive will substantially reduce friction on the DLC surfaces to an extent not observed on steel surfaces.
- Typically an organo-molybdenum additive is used so as to provide 25 to 1000 ppm (parts per million, by weight), preferably 200 to 750 ppm, of elemental molybdenum in the lubricating oil compositions (as determined by ASTM D5185).
- A further aspect of the invention relates to the use of a lubricating oil composition comprising an oil of lubricating viscosity and an effective friction-reducing amount of an oil-soluble organo-molybdenum compound to lubricate a surface coated with a diamond-like carbon film or coating.
- The method of this invention is especially applicable to the lubrication of spark-ignited or compression-ignited two-stroke or four-stroke internal combustion engines which have parts or components with DLC films or coatings. Examples of such components include the carn shaft, especially the cam lobes; pistons, especially the piston skirt; cylinder liners; and valves.
- As examples of such oil-soluble organo-molybdenum compounds, there may be mentioned dithiocarbamates, dithiophosphates, dithiophosphinates, xanthates, thioxanthates and sulfides of molybdenum and mixtures thereof.
- Additionally, the molybdenum compounds may be acidic molybdenum compounds. These compounds will react with a basic nitrogen compound as measured by ASTM test D-664 or D-2896 titration procedure and are typically hexavalent. Included are molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate, and other alkaline metal molybdates and other molybdenum salts, e.g., hydrogen sodium molybdate, MoOCl4, MoO2Br2, Mo2O3Cl6, molybdenum trioxide or similar acidic molybdenum compounds.
- Among the molybdenum compounds useful in the compositions of this invention are organo-molybdenum compounds of the formulae
Mo(ROCS2)4
and
Mo(RSCS2)4
wherein R is an organo group selected from the group consisting of alkyl, aryl, aralkyl and alkoxyalkyl, generally of from 1 to 30 carbon atoms, and preferably 2 to 12 carbon atoms and most preferably alkyl of 2 to 12 carbon atoms. Especially preferred are dialkyldithiocarbamates of molybdenum. - A further class of organo-molybdenum compounds is represented by the formula:
- Another group of organo-molybdenum compounds useful in the lubricating compositions of this invention are trinuclear molybdenum compounds, especially those of the formula MO3SkLnQz and mixtures thereof wherein the L are independently selected ligands having organo groups with a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil, n is from 1 to 4, k varies from 4 through 7, Q is selected from the group of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z ranges from 0 to 5 and includes non-stoichiometric values. In the instance n is 3, 2 or 1, appropriately charged ionic species is required to confer electrical neutrality to the trinuclear molybdenum compound. The ionic species may be of any valence, for example, monovalent or divalent. Further the ionic species may be negatively charged, i.e. an anionic species, or may be positively charged, i.e. a cationic species or a combination of an anion and a cation. Such terms are known to a skilled person in the art. The ionic species may be present in the compound through covalent bonding, i.e. coordinated to one or more molybdenum atoms in the core, or through electrostatic bonding or interaction as in the case of a counter-ion or through a form of bonding intermediate between covalent and electrostatic bonding. Examples of anionic species include disulfide, hydroxide, an alkoxide, an amide and a thiocyanate or derivate thereof; preferably the anionic species is disulfide ion. Examples of cationic species include an ammonium ion and a metal ion, such as an alkali metal, alkaline earth metal or transition metal, ion, preferably an ammonium ion, such as [NR4]+ where R is independently H or alkyl group, more preferably R is H, i.e. [NH4]+. At least 21 total carbon atoms should be present among all the ligands' organo groups, such as at least 25, at least 30, or at least 35 carbon atoms.
- The ligands are independently selected from the group of
――X――R 1,
- The term "hydrocarbyl" denotes a substituent having carbon atoms directly attached to the remainder of the ligand and is predominantly hydrocarbyl in character within the context of this invention. Such substituents include the following:
- 1. Hydrocarbon substituents, that is, aliphatic (for example alkyl or alkenyl), alicyclic (for example cycloalkyl or cycloalkenyl) substituents, aromatic-, aliphatic- and alicyclic-substituted aromatic nuclei and the like, as well as cyclic substituents wherein the ring is completed through another portion of the ligand (that is, any two indicated substituents may together form an alicyclic group).
- 2. Substituted hydrocarbon substituents, that is, those containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbyl character of the substituent. Those skilled in the art will be aware of suitable groups (e.g., halo, especially chloro and fluoro, amino, alkoxyl, mercapto, alkylmercapto, nitro, nitroso and sulfoxy).
- 3. Hetero substituents, that is substituents which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
- Importantly, the organo groups of the ligands have a sufficient number of carbon atoms to render the compound soluble or dispersible in the oil. For example, the number of carbon atoms in each group will generally range between 1 to 100, preferably from 1 to 30, and more preferably between 4 to 20. Preferred ligands include dialkyldithiophosphate, alkylxanthate, and dialkyldithiocarbamate, and of these dialkyldithiocarbamate is more preferred. Organic ligands containing two or more of the above functionalities are also capable of serving as ligands and binding to one or more of the cores. Those skilled in the art will realize that formation of the compounds of the present invention requires selection of ligands having the appropriate charge to balance the core's charge.
- Compounds having the formula Mo3SkLnQz have cationic cores surrounded by anionic ligands and are represented by structures such as
- Oil-soluble or oil-dispersible trinuclear molybdenum compounds can be prepared by reacting in the appropriate liquid(s) and/or solvent(s) a molybdenum source such as (NH4)2Mo3S13.n(H2O), where n varies between 0 and 2 and includes non-stoichiometric values, with a suitable ligand source such as a tetralkylthiuram disulfide. Other oil-soluble or oil-dispersible trinuclear molybdenum compounds can be formed during a reaction in the appropriate solvent(s) of a molybdenum source such as of (NH4)2Mo3S)13·n(H2O), a ligand source such as tetralkylthiuram disulfide, dialkyldithiocarbamate, or dialkyldithiophosphate, and a sulfur-abstracting agent such cyanide ions, sulfite ions, or substituted phosphines. Alternatively, a trinuclear molybdenum-sulfur halide salt such as [M']2[Mo3S7A6], where M' is a counter ion, and A is a halogen such as Cl, Br, or I, may be reacted with a ligand source such as a dialkyldithiocarbamate or dialkyldithiophosphate in the appropriate liquid(s) and/or solvent(s) to form an oil-soluble or oil-dispersible trinuclear molybdenum compound. The appropriate liquid and/or solvent may be, for example, aqueous or organic.
- A compound's oil solubility or dispersibility may be influenced by the number of carbon atoms in the ligand's organo groups. In the compounds employed in the present invention, at least 21 total carbon atoms should be present among all the ligand's organo groups. Preferably, the ligand source chosen has a sufficient number of carbon atoms in its organo groups to render the compound soluble or dispersible in the lubricating composition.
- The molybdenum compound is preferably an organo-molybdenum compound. Moreover, the molybdenum compound is preferably selected from the group consisting of a molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate, molybdenum dithiophosphinate, molybdenum xanthate, molybdenum thioxanthate and mixtures thereof. Most preferably, the molybdenum compound is present as molybdenum dithiocarbamate. The molybdenum compound is preferably a trinuclear molybdenum compound, such as a trinuclear molybdenum dithiocarbamate.
- Natural oils useful as the oil of lubricating viscosity (also known as basestocks) in this invention include animal oils and vegetable oils (e.g. castor, lard oil) liquid petroleum oils and hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
- Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification or etherification constitute a class of known synthetic lubricating oils useful as basestocks in this invention. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of poly-ethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-1500); and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C8 fatty acid esters and C13 Oxo acid diester of tetraethylene glycol.
- Another suitable class of synthetic lubricating oils useful in this invention comprises the esters of dicarboxylic acids (e.g. phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (i-butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
- Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
- Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tertbutylphenyl) silicate, hexa-(4-methyl-2-pentoxy) disiloxane, poly(methyl) siloxanes and poly(methylphenyl) siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g. tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.
- Unrefined, refined and rerefined oils can be used in the lubricating oil compositions of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improved one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for removal of spent additives and oil breakdown products.
- Molybdenum-containing lubricating oil compositions for use in the present invention may also contain any of the conventional additives listed below (including any additional friction modifiers) which are typically used in a minor amount, e.g. such an amount so as to provide their normal attendant functions. Typical amounts for individual components are also set forth below. All the values listed are stated as mass percent active ingredient in the total lubricating oil composition.
ADDITIVE MASS %
(Broad)MASS %
(Preferred)Ashless Dispersant 0.1 - 20 1 - 8 Metal Detergents 0.1 - 15 0.2 - 9 Corrosion Inhibitors 0 - 5 0 - 1.5 Metal Dihydrocarbyl Dithiophosphate 0.1 - 6 0.1 - 4 Anti-oxidant 0 - 5 0.01 - 3 Pour Point Depressant 0.01 - 5 0.01 - 1.5 Anti-foaming Agent 0 - 5 0.001 - 0.15 Supplemental Anti-wear Agents 0 - 5 0 - 2 Additional Friction Modifier 0 - 5 0 - 1.5 Viscosity Modifier 0 - 6 0.01 - 4 - The individual additives may be incorporated into a basestock in any convenient way. Thus, each of the components can be added directly to the basestock by dispersing or dissolving it in the basestock at the desired level of concentration. Such blending may occur at ambient temperature or at an elevated temperature.
- Preferably, all the additives except for the viscosity modifier and the pour point depressant are blended into a concentrate (or additive package) that is subsequently blended into basestock to make a finished lubricating oil composition. Use of such concentrates is conventional. The concentrate will typically be formulated to contain the additive(s) in proper amounts to provide the desired concentration in the final lubricating oil composition when the concentrate is combined with a predetermined amount of base oil.
- The concentrate is conveniently made in accordance with the method described in
U.S. 4,938,880 . That patent describes making a pre-mix of ashless dispersant and metal detergents that is pre-blended at a temperature of at least about 200°C. Thereafter, the pre-mix is cooled to at least 85°C and the additional components are added. - The final crankcase lubricating oil composition may employ from 2 to 20 mass % and preferably 4 to 15 mass % of the concentrate (or additive package), the remainder being base oil.
- Ashless dispersants maintain in suspension oil-insoluble matter resulting from oxidation of the oil during wear or combustion. They are particularly advantageous for preventing precipitation of sludge and formation of varnish, particularly in gasoline engines.
- Ashless dispersants comprise an oil-soluble polymeric hydrocarbon backbone bearing one or more functional groups that are capable of associating with particles to be dispersed. Typically, the polymer backbone is functionalized by amine, alcohol, amide, or ester polar moieties, often via a bridging group. The ashless dispersant may be, for example, selected from oil-soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons; long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
- The oil-soluble polymeric hydrocarbon backbone of these dispersants is typically derived from an olefin polymer or polyene, especially polymers comprising a major molar amount (i.e. greater than 50 mole %) of a C2 to C18 olefin (e.g. ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene), and typically a C2 to C5 olefin. The oil-soluble polymeric hydrocarbon backbone may be a homopolymer (e.g. polypropylene or polyisobutylene) or a copolymer of two or more of such olefins (e.g. copolymers of ethylene and an alpha-olefin such as propylene or butylene, or copolymers of two different alpha-olefins). Other copolymers include those in which a minor molar amount of the copolymer monomers, for example, 1 to 10 mole %, is an α,ω-diene, such as a C3 to C22 non-conjugated diolefin (for example, a copolymer of isobutylene and butadiene, or a copolymer of ethylene, propylene and 1,4-hexadiene or 5-ethylidene-2-norbornene). Preferred are polyisobutenyl (Mn 400-2500, preferably 950-2200) succinimide dispersants.
- The viscosity modifier (VM) functions to impart high and low temperature operability to a lubricating oil composition. The VM used may have that sole function, or may be multifunctional.
- Multifunctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers are polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkylmethacrylates, methacrylate copolymers, copolymers of an unsaturated dicarboxylic acid and a vinyl compound, inter polymers of styrene and acrylic ester, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, as well as the partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene.
- Metal-containing or ash-forming detergents may be present and these function both as detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life. Detergents generally comprise a polar head with a long hydrophobic tail, the polar head comprising a metal salt of an acid organic compound. The salts may contain a substantially stoichiometric amount of the metal in which they are usually described as normal or neutral salts, and would typically have a total base number (TBN), as may be measured by ASTM D-2896 of from 0 to 80. It is possible to include large amounts of a metal base by reacting an excess of a metal compound such as an oxide or hydroxide with an acid gas such as carbon dioxide. The resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g. carbonate) micelle. Such overbased detergents may have a TBN of 150 or greater, and typically from 250 to 450 or more. Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil-soluble carboxylates of a metal, particularly the alkali, e.g. sodium, potassium, lithium and magnesium. Preferred are neutral or overbased calcium and magnesium phenates and sulfonates, especially calcium.
- Other friction modifiers include oil-soluble amines, amides, imidazolines, amine oxides, amidoamines, nitriles, alkanolamides, alkoxylated amines and ether amines; polyol esters; and esters of polycarboxylic acids.
- Dihydrocarbyl dithiophosphate metal salts are frequently used as anti-wear and antioxidant agents. The metal may be an alkali or alkaline earth metal, or aluminum, lead, tin, molybdenum, manganese, nickel or copper. They may be prepared in accordance with known techniques by first forming a dihydrocarbyl dithiophosphoric acid (DDPA), usually by reaction of one or more alcohol or a phenol with P2S5 and then neutralizing the formed DDPA with a zinc compound. For example, a dithiophosphoric acid may be made by reacting mixtures of primary and secondary alcohols. Alternatively, multiple dithiophosphoric acids can be prepared where the hydrocarbyl groups on one are entirely secondary in character and the hydrocarbyl groups on the others are entirely primary in character. To make the zinc salt, any basic or neutral zinc compound may be used but oxides, hydroxides and carbonates are most generally employed. Commercial additives frequently contain an excess of zinc due to use of an excess of the basic zinc compound in the neutralization reaction.
- ZDDP provides excellent wear protection at a comparatively low cost and also functions as an antioxidant. However, there is some evidence that phosphorus in lubricant can shorten the effective life of automotive emission catalysts. Accordingly, the lubricating oil compositions of the invention preferably contain no more than 0.8 wt %, such as from 50 ppm to 0.06 wt %, of phosphorus. Independently of the amount of phosphorus, the lubricating oil composition preferably has no more than 0.5 wt %, preferably from 50 ppm to 0.3 wt %, of sulfur, the amounts of sulfur and of phosphorus being measured in accordance with ASTM D5185.
- Oxidation inhibitors or antioxidants reduce the tendency of basestocks to deteriorate in service, which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth. Such oxidation inhibitors include hindered phenols, alkaline earth metal salts of alkylphenolthioesters having preferably C5 to C12 alkyl side chains, calcium nonylphenol sulfide, ashless oil-soluble phenates and sulfurized phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorous esters, metal thiocarbamates, oil-soluble copper compound as described in
U.S. 4,867,890 , and molybdenum-containing compounds. - Rust inhibitors selected from the group consisting of nonionic polyoxyalkylene polyols and esters thereof, polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be used.
- Copper- and lead-bearing corrosion inhibitors may be used, but are typically not required in the lubricating oil compositions of the present invention. Typically such compounds are thiadiazole polysulfides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof. Derivatives of 1,3,4-thiadiazoles, such as those described in
U.S. Patent Nos. 2,719,125 ;2,719,126 ; and3,087,932 , are typical. Other similar material are described inU.S. Patent Nos. 3,821,236 ;3,904,537 ;4,097,387 ;4,107,059 ;4,136,043 ;4,188,299 ; and4,193,882 . Other additives are thio and polythio sulfenamides of thiadiazoles such as those described inGB-A-1,560,830 - A small amount of a demulsifying component may be used. A preferred demulsifying component is described in
EP-A-330 522 - Pour point depressants, otherwise known as lube oil improvers, lower the minimum temperature at which the fluid will flow or can be poured. Such additives are well-known. Typical of those additives, which improve the low temperature fluidity of the fluid, are C8 and C18 dialkyl fumarate/vinyl acetate copolymers and polyalkylmethacrylates.
- Foam control can be provided by many compounds including an antifoamant of the polysiloxane type, for example, silicone oil or polydimethyl siloxane.
- In this specification, the term "comprising" (or cognates such as "comprises") means the presence of stated features, integers, steps or components, but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof. If the term "comprising" (or cognates) is used herein, the term "consisting essentially of" (and its cognates) is within its scope and is a preferred embodiment; consequently the term "consisting of" (and its cognates) is within the scope of "consisting essentially of" and is a preferred embodiment thereof.
- The terms "oil-soluble" or "oil-dispersible" do not mean that the compounds are soluble, dissolvable, miscible or capable of being suspended in the oil in all proportions. They do mean, however, that the compounds are, for instance, soluble or stably dispersible in the oil to an extent sufficient to exert their intended effect in the environment in which the composition is employed. Moreover, the additional incorporation of other additives such as those described above may affect the solubility or dispersibility of the compounds.
- The term "major amount" means in excess of 50 mass % of the composition.
- The term "minor amount" means less than 50 mass % of the composition.
- The invention is further illustrated by the following examples which are not to be considered as limitative of its scope. All percentages are by weight active ingredient content of an additive without regard for carrier or diluent oil.
- The coefficients of friction for the lubrication of steel on steel surfaces were measured and compared with the coefficients of friction for DLC coated steel surfaces using the same lubricants. The DLC coating is sold as "Dymon-iC" the trademark for a hydrogenated carbon coating supplied by Teer Coatings Ltd. Both types of surfaces were lubricated with:
- 1. a base oil having a viscosity of 4 mm2s-1 at 100°C;
- 2. a composition containing the base oil of (1) and 550 ppm of molybdenum as trinuclear molybdenum dithiocarbamate; and
- 3. a composition containing the base oil of (1) and 0.3 wt.% of glycerol mono-oleate (GMO), a conventional friction reducing agent used in engine crankcase lubricants.
- The results are set forth in Tables 1 and 2 below and were obtained using a Cameron Plint reciprocating pin on plate tribometer, using the following test protocol:
Test duration 8 hours Load (N) 185 Stroke length (mm) 10 Frequency (Hz) 1 Temperature (°C) 100 Table 1 - Steel on Steel Lubrication - Co-efficients of Friction Time (min) Baseoil Baseoil + 550 ppm Mo Baseoil + 0.3%GMO 0 0.154 0.130 0.134 30 0.123 0.089 0.119 60 0.130 0.091 0.118 90 0.137 0.092 0.118 120 0.146 0.095 0.119 150 0.161 0.098 0.120 180 0.149 0.099 0.122 210 0.157 0.099 0.123 240 0.159 0.101 0.124 270 0.156 0.101 0.125 300 0.164 0.099 0.126 330 0.164 0.101 0.127 360 0.172 0.101 0.128 390 0.166 0.101 0.128 420 0.164 0.099 0.129 450 0.172 0.100 0.130 480 0.175 0.102 0.131 Table 2 - DLC on DLC Lubrication - Co-efficients of Friction Time (min) Baseoil Baseoil + 550 ppm Mo Baseoil + 0.3%GMO 0 0.111 0.113 0.111 30 0.118 0.080 0.115 60 0.119 0.076 0.109 90 0.120 0.073 0.108 120 0.120 0.071 0.109 150 0.120 0.069 0.109 180 0.119 0.068 0.109 210 0.119 0.068 0.109 240 0.119 0.067 0.109 270 0.120 0.066 0.109 300 0.120 0.066 0.110 330 0.120 0.066 0.111 360 0.121 0.067 0.112 390 0.120 0.067 0.113 420 0.121 0.067 0.114 450 0.121 0.066 0.114 480 0.121 0.067 0.112 - Table 2 indicates that, in the lubrication of contacting DLC surfaces, the molybdenum-containing lubricating oil composition is substantially better at increasing fnction reduction than the composition containing a conventional friction reducing agent, glycerol mono-oleate.
Claims (7)
- A method of lubricating a surface coated with a diamond-like carbon film or coating which comprises supplying to said surface a lubricating oil composition comprising an oil of lubricating viscosity and an effective friction reducing amount of an oil-soluble organo-molybdenum compound.
- The method of claim 1 wherein the organo-molybdenum compound is present in the lubricating oil composition in an amount of 25 to 1000 ppm of elemental molybdenum, based on the mass of the lubricating oil composition.
- The method of claim 1 or claim 2 wherein the molybdenum compound is a molybdenum dithiocarbamate.
- The method of any of claims 1 to 3 wherein the molybdenum compound is a trinuclear molybdenum compound.
- The method of any of claims 1 to 4 wherein the lubricating oil composition further comprises one or more additional additives selected from the group consisting of ashless dispersants, metal detergents, corrosion inhibitors, metal dihydrocarbyl dithiophosphates, antioxidants, pour point depressants, anti-foaming agents, additional friction modifiers, antiwear agents and viscosity modifiers.
- The method of any of claims 1 to 5 wherein the coated surface is that of a component part of an internal combustion engine, and the lubricating oil composition is supplied to the engine.
- The use of a lubricating oil composition comprising an oil of lubricating viscosity and an effective friction-reducing amount of an oil-soluble organo-molybdenum compound to lubricate a surface coated with a diamond-like carbon film or coating.
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Cited By (3)
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EP2966152A1 (en) | 2014-07-11 | 2016-01-13 | Toyota Jidosha Kabushiki Kaisha | Sliding machine |
DE102015113547A1 (en) | 2014-10-24 | 2016-04-28 | Toyota Jidosha Kabushiki Kaisha | sliding system |
DE102016119815A1 (en) | 2016-02-25 | 2017-08-31 | Toyota Jidosha Kabushiki Kaisha | sliding system |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1479946B1 (en) * | 2003-05-23 | 2012-12-19 | Nissan Motor Co., Ltd. | Piston for internal combustion engine |
WO2016032782A1 (en) * | 2014-08-27 | 2016-03-03 | Shell Oil Company | Methods for lubricating a diamond-like carbon coated surface, associated lubricating oil compositions and associated screening methods |
EP3907268A1 (en) * | 2020-05-04 | 2021-11-10 | Total Marketing Services | Lubricating composition for reducing wear and tear on dlc parts used in internal combustion engines |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE69621324T2 (en) * | 1995-12-22 | 2003-01-02 | Japan Energy Corp., Tokio/Tokyo | LUBRICATING OIL FOR INTERNAL COMBUSTION ENGINES |
US6010987A (en) * | 1996-12-13 | 2000-01-04 | Exxon Research And Engineering Co. | Enhancement of frictional retention properties in a lubricating composition containing a molybdenum sulfide additive in low concentration |
US5771873A (en) | 1997-04-21 | 1998-06-30 | Ford Global Technologies, Inc. | Carbonaceous deposit-resistant coating for engine components |
GB9810581D0 (en) * | 1998-05-15 | 1998-07-15 | Exxon Chemical Patents Inc | Lubricant compositions |
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2004
- 2004-03-10 EP EP20040251370 patent/EP1462508B1/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2966152A1 (en) | 2014-07-11 | 2016-01-13 | Toyota Jidosha Kabushiki Kaisha | Sliding machine |
DE102015113547A1 (en) | 2014-10-24 | 2016-04-28 | Toyota Jidosha Kabushiki Kaisha | sliding system |
DE102016119815A1 (en) | 2016-02-25 | 2017-08-31 | Toyota Jidosha Kabushiki Kaisha | sliding system |
US10301568B2 (en) | 2016-02-25 | 2019-05-28 | Toyota Jidosha Kabushiki Kaisha | Sliding system |
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