EP3155080A1 - Nano-tribology compositions and related methods including hard particles - Google Patents
Nano-tribology compositions and related methods including hard particlesInfo
- Publication number
- EP3155080A1 EP3155080A1 EP15805890.9A EP15805890A EP3155080A1 EP 3155080 A1 EP3155080 A1 EP 3155080A1 EP 15805890 A EP15805890 A EP 15805890A EP 3155080 A1 EP3155080 A1 EP 3155080A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- oil
- nanoparticles
- metal
- hard particles
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 183
- 239000000203 mixture Substances 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 163
- 239000002105 nanoparticle Substances 0.000 claims abstract description 146
- 239000000463 material Substances 0.000 claims description 98
- 229910052751 metal Inorganic materials 0.000 claims description 93
- 239000002184 metal Substances 0.000 claims description 91
- -1 tungsten carbides Chemical class 0.000 claims description 73
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 60
- 239000003921 oil Substances 0.000 claims description 58
- 235000019198 oils Nutrition 0.000 claims description 58
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 48
- 239000005662 Paraffin oil Substances 0.000 claims description 44
- 239000003995 emulsifying agent Substances 0.000 claims description 39
- 239000004519 grease Substances 0.000 claims description 30
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 26
- 235000019519 canola oil Nutrition 0.000 claims description 26
- 239000000828 canola oil Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 21
- 239000000194 fatty acid Substances 0.000 claims description 21
- 229930195729 fatty acid Natural products 0.000 claims description 21
- 150000004665 fatty acids Chemical class 0.000 claims description 21
- 229910052582 BN Inorganic materials 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 19
- 150000004767 nitrides Chemical class 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 150000003904 phospholipids Chemical class 0.000 claims description 14
- 229910021332 silicide Inorganic materials 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 239000000787 lecithin Substances 0.000 claims description 13
- 235000010445 lecithin Nutrition 0.000 claims description 13
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 13
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 13
- 239000008158 vegetable oil Substances 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 239000002480 mineral oil Substances 0.000 claims description 12
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 235000005687 corn oil Nutrition 0.000 claims description 11
- 239000002285 corn oil Substances 0.000 claims description 11
- 229910003460 diamond Inorganic materials 0.000 claims description 11
- 239000010432 diamond Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 235000010446 mineral oil Nutrition 0.000 claims description 11
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003549 soybean oil Substances 0.000 claims description 11
- 235000012424 soybean oil Nutrition 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 150000002989 phenols Chemical class 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 230000036961 partial effect Effects 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 230000003115 biocidal effect Effects 0.000 claims description 7
- 150000002168 ethanoic acid esters Chemical class 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 229920000223 polyglycerol Chemical class 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical class C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 claims description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical class CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000004250 tert-Butylhydroquinone Chemical class 0.000 claims description 5
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 5
- 150000007970 thio esters Chemical class 0.000 claims description 5
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical class CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 claims description 5
- QTSAVJBGNOWQRI-UHFFFAOYSA-N 1,3-benzothiazole;hydroxylamine Chemical compound ON.C1=CC=C2SC=NC2=C1 QTSAVJBGNOWQRI-UHFFFAOYSA-N 0.000 claims description 4
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229940067606 lecithin Drugs 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 239000006011 Zinc phosphide Substances 0.000 claims description 3
- 239000005083 Zinc sulfide Substances 0.000 claims description 3
- XWROSHJVVFETLV-UHFFFAOYSA-N [B+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [B+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWROSHJVVFETLV-UHFFFAOYSA-N 0.000 claims description 3
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 229940075417 cadmium iodide Drugs 0.000 claims description 3
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- HOKBIQDJCNTWST-UHFFFAOYSA-N phosphanylidenezinc;zinc Chemical compound [Zn].[Zn]=P.[Zn]=P HOKBIQDJCNTWST-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- 229940048462 zinc phosphide Drugs 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- 229910033181 TiB2 Inorganic materials 0.000 claims description 2
- 229910007948 ZrB2 Inorganic materials 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 239000011881 graphite nanoparticle Substances 0.000 claims description 2
- MELCCCHYSRGEEL-UHFFFAOYSA-N hafnium diboride Chemical compound [Hf]1B=B1 MELCCCHYSRGEEL-UHFFFAOYSA-N 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 claims 1
- ZLANVVMKMCTKMT-UHFFFAOYSA-N methanidylidynevanadium(1+) Chemical class [V+]#[C-] ZLANVVMKMCTKMT-UHFFFAOYSA-N 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 description 52
- 238000000498 ball milling Methods 0.000 description 39
- 238000005260 corrosion Methods 0.000 description 32
- 230000007797 corrosion Effects 0.000 description 30
- 239000000654 additive Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 24
- 238000003801 milling Methods 0.000 description 24
- 230000000996 additive effect Effects 0.000 description 19
- 238000005461 lubrication Methods 0.000 description 19
- 239000013078 crystal Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000001238 wet grinding Methods 0.000 description 16
- 239000000956 alloy Substances 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000011164 primary particle Substances 0.000 description 13
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 230000000670 limiting effect Effects 0.000 description 11
- 231100000241 scar Toxicity 0.000 description 11
- 229910052961 molybdenite Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000009837 dry grinding Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000003139 biocide Substances 0.000 description 6
- CXRFFSKFQFGBOT-UHFFFAOYSA-N bis(selanylidene)niobium Chemical compound [Se]=[Nb]=[Se] CXRFFSKFQFGBOT-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 239000002052 molecular layer Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 125000004434 sulfur atom Chemical group 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003701 mechanical milling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
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- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/08—Metal carbides or hydrides
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- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M171/06—Particles of special shape or size
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- C10M2201/041—Carbon; Graphite; Carbon black
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- C10M2201/066—Molybdenum sulfide
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- C10M2201/081—Inorganic acids or salts thereof containing halogen
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- C10M2201/085—Phosphorus oxides, acids or salts
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- C10M2201/087—Boron oxides, acids or salts
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- C10M2201/10—Compounds containing silicon
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- C10M2201/103—Clays; Mica; Zeolites
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2207/283—Esters of polyhydroxy compounds
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Definitions
- This specification also relates to compositions and methods in the sub-field of nano-tribology and associated solid surface nano-engineering, nano-lubrication, and nano-wear.
- Tribology refers to the science and engineering of solid surfaces. Tribology includes the study and application of surface chemistry and structure, friction, lubrication, corrosion, and wear. The tribological interactions of a solid surface with interfacing materials and the surrounding environment may result in the loss of material from the surface in processes generally referred to as "wear.” Major types of wear include abrasion, friction (adhesion and cohesion), erosion, and corrosion. Wear may be reduced by the use of lubricants and/or other anti-wear agents. Wear may also be reduced by modifying the surface properties of solids using one or more "surface engineering" processes (i.e., modifying the chemical and/or structural properties of solid surfaces).
- a composition comprises a plurality of hard particles and a plurality of lubricant nanoparticles.
- the lubricant nanoparticles have an average primary particle size of less than or equal to about 500 nm and an open architecture.
- An organic medium is intercalated in the lubricant nanoparticles.
- a composition comprises a plurality of hard particles and a plurality of molybdenum disulfide nanoparticles.
- the molybdenum disulfide nanoparticles have an average primary particle size of less than or equal to about 100 nm and an open architecture.
- An oil medium is intercalated in and encapsulates the molybdenum disulfide nanoparticles.
- Figure 1 is a diagram illustrating a method of producing lubricant nanoparticles
- Figure 2 is a diagram illustrating one method of preparing nanoparticle based lubricants
- Figure 3 shows transmission electron microscopy (TEM) micrographs of molybdenum disulfide particles;
- Figure 3(A) shows molybdenum disulfide as it is available, typically from about a few microns to submicron size;
- Figure 3(B) shows molybdenum disulfide that has been ball milled in air for 48 hours;
- Figure 3(C) is a high resolution electron microscopy image that shows molybdenum disulfide that has been ball milled in air for 48 hours;
- Figure 3(D) is a high-resolution transmission electron microscopy (HRTEM) image that shows molybdenum disulfide that has been ball milled in air for 48 hours followed by ball milling in oil for 48 hours;
- HRTEM transmission electron microscopy
- Figure 4 is a graph showing XRD spectra of molybdenum disulfide particles;
- Figure 4(A) is the XRD spectra for molybdenum disulfide that has been ball milled in air for 48 hours followed by ball milling in oil for 48 hours;
- Figure 4(B) is the XRD spectra for molybdenum disulfide that has been ball milled in air for 48 hours;
- Figure 4(C) is the XRD spectra for molybdenum disulfide that has not been ball milled;
- Figure 5 is a graph showing XPS spectra of molybdenum disulfide particles in which the carbon peak for molybdenum disulfide that has not been ball milled is shown, as well as the carbon peak for molybdenum disulfide that has been ball milled in air for 48 hours, followed by ball milling in oil for 48 hours;
- Figures 6(A)-6(D) show graphs and bar charts depicting tribological test data for different additives in paraffin oil;
- Figure 6(A) shows the average wear scar diameter for a base oil (paraffin oil), paraffin oil with micron sized M0S 2 , paraffin oil with M0S 2 that was milled in air for 48 hours, and paraffin oil with M0S 2 that was milled in air for 48 hours followed by milling in canola oil for 48 hours;
- Figure 6(B) shows the load wear index for paraffin oil without a nanoparticle additive, paraffin oil with micron sized M0S 2 , paraffin oil with M0S 2 that was milled in air for 48 hours, and paraffin oil with M0S 2 that was milled in air for 48 hours followed by milling in canola oil for 48 hours;
- Figure 6(C) shows the coefficient of friction for paraffin oil without a nanoparticle additive, paraffin oil with micron sized M0S 2 (C-M0S 2
- Figure 7 is a TEM image showing the architecture of molybdenum disulfide nanoparticles (15-70 nm average size);
- Figure 7(A) shows the close caged dense oval shaped architecture of molybdenum disulfide nanoparticles that have been ball milled in air for 48 hours;
- Figure 7(B) shows the open ended oval shaped architecture of molybdenum disulfide nanoparticles that have been ball milled in air for 48 hours followed by ball milling in canola oil for 48 hours;
- Figure 8 is a graph depicting a comparison of wear scar diameters for different additives in paraffin oil; one additive is crystalline molybdenum disulfide (c- M0S 2 ); another is molybdenum disulfide nanoparticles that were ball milled in air (n- M0S 2 ); another additive is molybdenum disulfide nanoparticles that were ball milled in air followed by ball milling in canola oil and to which a phospholipid emulsifier was added (n-MoS 2 +Emulsifier);
- c- M0S 2 crystalline molybdenum disulfide
- n- M0S 2 molybdenum disulfide nanoparticles that were ball milled in air
- n-MoS 2 +Emulsifier molybdenum disulfide nanoparticles that were ball milled in air followed by ball milling in canola oil and to which a phospholipid emulsifier was added
- Figure 9 shows photographs and graphs produced using energy dispersive x-ray analysis (EDS) depicting the chemical analysis of wear scar diameters in four-ball tribological testing for nanoparticle based lubricants;
- EDS energy dispersive x-ray analysis
- Figure 9(A) shows paraffin oil without any nanoparticle composition additive;
- Figure 9(B) shows paraffin oil with molybdenum disulfide nanoparticles that have been ball milled in air for 48 hours followed by ball milling in oil for 48 hours and treated with a phospholipid emulsifier;
- Figures 10(A) and 10(B) show schematic diagrams of the crystal structure of molybdenum disulfide.
- Figure 1 1 shows a schematic diagram of the crystal structure of hexagonal boron nitride.
- any numerical range recited in this specification is intended to include all sub-ranges of the same numerical precision subsumed within the recited range.
- a range of "1 .0 to 10.0" is intended to include all sub-ranges between (and including) the recited minimum value of 1 .0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1 .0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6.
- Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein.
- corrosion generally refers to the undesired chemical reaction of material surfaces with components in the surrounding environment.
- corrosion is a type of chemical degradation and the term is usually used in connection with the electrochemical oxidation of metal and alloy surfaces.
- the rusting of iron and steel alloys i.e., the electrochemical oxidation of elemental iron atoms to iron oxide compounds
- Corrosion is a diffusion-controlled process; therefore, corrosion occurs on material surfaces exposed to an oxidative external environment. Corrosion can develop more or less uniformly over exposed material surfaces.
- Pitting corrosion is a form of localized corrosion that results in the formation of small holes or "pits" in the metal or alloy forming the surface of an article.
- Pitting corrosion is typically encountered in passivating metals and alloys, i.e. , alloys such as stainless steels, aluminum and aluminum-base alloys, titanium and titanium-base alloys, and nickel-base alloys, for example, that oxidize in air to form a stable, adherent, and inert metal oxide layer that provides a surface barrier to corrosive attack of the underlying metallic atoms.
- Pitting corrosion may also be encountered in other metal and alloy materials such as non-stainless steels that have been passivated by special treatments such as chromate conversion, phosphate conversion, and galvanization.
- a carbon steel article may corrode uniformly in sea water, while a stainless steel article may develop localized pitting corrosion in the same environment.
- the chemical driving force for pitting corrosion is the depassivation of a small localized area of a metal or alloy article surface where the passivating layer is breached or otherwise compromised.
- the depassivated area becomes anodic (i.e., electrochemically oxidative) while an adjacent area becomes cathodic (i.e., electrochemically reductive), leading to localized galvanic corrosion at the depassivated area.
- the localized galvanic corrosion penetrates through the passivating layer and into the sub-surface region of the metal or alloy article, thereby forming the small holes or "pits" characteristic of pitting corrosion.
- Pitting corrosion may be particularly problematic because the localization of the pitting results in a relatively small wear effect on material surfaces, but produces significant material wear deep into the sub-surface regions of the material.
- Pitting corrosion may be initiated by a small surface defect such as damage to a passivating surface layer (e.g., a surface scratch), a local change in surface material composition, or other non-uniformities in a material surface such as high levels of surface roughness. Accordingly, polished metal and alloy surfaces may exhibit higher resistance to pitting corrosion.
- a passivating surface layer e.g., a surface scratch
- a local change in surface material composition e.g., a local change in surface material composition
- polished metal and alloy surfaces may exhibit higher resistance to pitting corrosion.
- pitting corrosion is a concern in many mechanical systems comprising mechanically engaging components (e.g. , gears) that are made of metals or alloys such as stainless steels, aluminum, or titanium, for example.
- mechanically engaging components e.g. , gears
- the mechanical contact between the engaging components may cause localized frictional wearing, abrasion, and/or erosion of the metallic surfaces, thereby forming localized surface non-uniformities and/or damaging passivating surface layers, thereby providing localized areas for the development of pitting corrosion.
- Lubrication processes and compositions are intended to reduce frictional wearing of the surfaces of mechanically engaging components.
- conventional lubrication processes and compositions do not address the removal of surface non- uniformities and nascent pitting corrosion.
- compositions and methods that simultaneously provide synergistic lubrication and polishing of mechanically-engaging components, such as, for example, gears and other mechanical components commonly fabricated from metals and alloys.
- the compositions may comprise hard particles and lubricant nanoparticles.
- the hard particles comprise micron-scale or nano-scale particles that provide micro-polishing or nano-polishing action to the surfaces of mechanically- engaging components, thereby removing surface non-uniformities and nascent pitting corrosion that may form on the components.
- the lubricant nanoparticles provide enhanced lubrication to the surfaces of mechanically-engaging components, thereby reducing the coefficient of friction and attendant wear.
- the combination of hard particles and lubricant nanoparticles provides the synergistic combination of simultaneous surface polishing and surface lubrication that reduces, minimizes, or eliminates pitting corrosion in mechanical systems, in situ, under operating conditions.
- a composition may comprise a plurality of hard particles and a plurality of lubricant nanoparticles.
- the hard particles may have an average primary particle size of 10 micrometers or less.
- the lubricant nanoparticles may have an average primary particle size of less than or equal to 1000 nanometers, and in some embodiments, less than or equal to 500 nanometers, less than or equal to 400 nanometers, less than or equal to 300 nanometers, less than or equal to 200 nanometers, less than or equal to 100 nanometers, less than or equal to 75 nanometers, less than or equal to 50 nanometers, or less than or equal to 25 nanometers.
- the term "average primary particle size” refers to a particle size as determined by visually examining a microscopy image of a sample of particles, measuring the largest length dimension of the individual particles in the image (i.e., the diameters of the smallest spheres that completely surround the individual particles in the image), and calculating the average of the length dimensions (diameters) based on the magnification of the image.
- a microscopy image e.g., light microscopy, transmission electron microscopy, and the like
- the average primary particle size of constituent particles or a subset of the constituent particles based on like particle composition
- the term "average primary particle size” refers the size of individual particles as opposed to agglomerations of two or more individual particles.
- the hard particles may comprise at least one of ceramic particles such as hard carbon particles, boride particles, carbide particles, nitride particles, oxide particles, silicide particles, carbo-nitride particles, oxy-nitride particles, and combinations of any thereof.
- the hard particles may comprise one or more of a metal boride, a metal carbide, a metal nitride, a metal oxide, or a metal silicide.
- the hard particles may also comprise a solid state solution of any two or more metal borides, metal carbides, metal nitrides, metal oxides, or metal silicides.
- the hard particles may comprise a mixed metal oxide (e.g., an aluminum-zirconium oxide), a mixed metal nitride (e.g., an aluminum- titanium nitride or aluminum chromium nitride), a mixed metal carbide (e.g., titanium- zirconium carbide), a mixed metal boride, or a mixed metal silicide.
- the hard particles may also comprise particulate mixtures of any two or more metal borides, metal carbides, metal nitrides, metal oxides, or metal silicides (e.g., a combination of silicon carbide particles and aluminum oxide particles, or a combination of cubic boron nitride particles and cubic zirconia particles).
- the hard particles may comprise at least one of a metal boride, a metal carbide, a metal nitride, a metal oxide, a metal silicide, a solid state solution of any thereof, or a particulate mixture of any thereof, wherein the metal comprises at least one element selected from groups IIIA, IVB, VB, and VIB of the periodic table (i.e., the boron group, titanium group, vanadium group, and chromium group, respectively).
- the hard particles may comprise at least one of a metal boride, a metal carbide, a metal nitride, a metal oxide, a metal silicide, a solid state solution of any thereof, or a particulate mixture of any thereof, wherein the metal comprises at least one element selected from the group consisting of boron, aluminum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten.
- the hard particles may comprise hard carbon.
- the hard particles may comprise at least one of synthetic diamond, natural diamond, amorphous carbon, or nanocrystalline carbon.
- the hard particles may comprise single crystal diamond particles or polycrystalline diamond particles (i.e., particles comprise more than one crystal grain per particle), including single- or poly-crystalline synthetic or natural diamond particles.
- the hard particles may comprise diamond particles alone or in combination with other types of hard particles such as at least one of a metal boride, a metal carbide, a metal nitride, a metal oxide, or a metal silicide.
- the hard particles may comprise at least one metal carbide such as, for example, a tungsten carbide, molybdenum carbide, chromium carbide, tantalum carbide, niobium carbide, vanadium carbide, hafnium carbide, zirconium carbide, titanium carbide, boron carbide, silicon carbide, solid state solutions of any thereof, and particulate mixtures of any thereof. While silicon and boron are often considered metalloids and not metallic elements per se, in this specification, it is understood that silicon and boron are considered metals for purposes of metal carbides, metal nitrides, and metal oxides. Silicon is also considered a metal in connection with metal borides.
- metal carbide such as, for example, a tungsten carbide, molybdenum carbide, chromium carbide, tantalum carbide, niobium carbide, vanadium carbide, hafnium carbide, zirconium carbide, titanium carbide, boron carbide, silicon
- the hard particles may comprise at least one metal nitride such as, for example, cubic boron nitride, a silicon nitride, a titanium nitride, a zirconium nitride, a hafnium nitride, a tungsten nitride, solid state solutions of any thereof, and particulate mixtures of any thereof.
- metal nitride such as, for example, cubic boron nitride, a silicon nitride, a titanium nitride, a zirconium nitride, a hafnium nitride, a tungsten nitride, solid state solutions of any thereof, and particulate mixtures of any thereof.
- the hard particles may comprise at least one metal oxide such as, for example, an aluminum oxide (e.g., i.e., corundum), a cerium oxide, a titanium oxide, a zirconium oxide, solid state solutions of any thereof, and particulate mixtures of any thereof.
- an aluminum oxide e.g., i.e., corundum
- cerium oxide e.g., a cerium oxide
- titanium oxide e.g., i.e., corundum
- the hard particles may comprise at least one metal boride such as, for example, titanium diboride, zirconium diboride, hafnium diboride, a tantalum boride, a tungsten boride (e.g., tungsten tetraboride), a silicon boride, solid state solutions of any thereof, and particulate mixtures of any thereof.
- metal boride such as, for example, titanium diboride, zirconium diboride, hafnium diboride, a tantalum boride, a tungsten boride (e.g., tungsten tetraboride), a silicon boride, solid state solutions of any thereof, and particulate mixtures of any thereof.
- the hard particles may comprise particle mixtures of any of the metal boride, a metal carbide, a metal nitride, a metal oxide, or a metal silicides described above.
- the hard particles may also comprise at least one mixed non-metal such as a metal carbonitride.
- the hard particles may comprise at least one metal carbonitride such as, for example, a boron carbonitride, a silicon carbonitride, a titanium carbonitride, a zirconium carbonitride, a hafnium carbonitride, a tungsten carbonitride, solid state solutions of any thereof, and particulate mixtures of any thereof.
- the hard particles may comprise a metal boride, a metal carbide, a metal nitride, a metal oxide, a metal silicide, solid state solutions of any thereof, mixed metal versions of any thereof, mixed non-metal versions of any thereof, or particulate mixtures of any thereof, wherein the constituent compounds are stoichiometric or non-stoichiometric.
- the hard particles may be functionalized.
- the hard particles may be functionalized with organic molecules or functional groups, inorganic molecules or functional groups, or both organic and inorganic molecules or functional groups, forming functionalized hard particles.
- the hard particles may be functionalized with catalysts, antioxidants, anti-corrosion agents, biocidal agents, or combinations of any thereof.
- antioxidants examples include, but are not limited to, antioxidants selected from the group consisting of hindered phenols, alkylated phenols, alkyi amines, aryl amines, 2,6-di- tert-butyl-4-methylphenol, 4,4'-di-tert-octyldiphenylamine, tert-butyl hydroquinone, tris(2,4-di-tert-butylphenyl)phosphate, phosphites, thioesters, or combinations of any thereof; anticorrosion agents selected from the group consisting of alkaline earth metal bisalkylphenolsulphonates, dithiophosphates, alkenylsuccinic acid half-amides, or combinations thereof; and biocidal agents material selected from the group consisting of alkyi benzothiazole, hydroxylamine benzothiazole, an amine salt of an alkyi succinic acid, an amine salt of an
- the hard particles may be functionalized with a dispersant agent.
- Suitable dispersant agents may comprise at least one material selected from the group consisting of amide compounds, borate compounds, and boride compounds.
- a dispersant agent may comprise at least one of succinimide and disodium octaborate tetrahydrate.
- a composition may comprise a plurality of hard particles and a plurality of lubricant nanoparticles.
- the lubricant nanoparticles may have an open architecture.
- open architecture or "open-ended architecture” refers to the morphology of particles comprising fissures, separations, or other discontinuities in the particles' outer surfaces which provide openings to the internal portions of the individual particles.
- open architecture or “open-ended architecture” refer to the morphology of the layered particles comprising inter-layer defects (e.g., shearing, buckling, folding, curling, and dislocating of constituent atomic and/or molecular layers) at the surface of the particles, which increase the inter-planar spacing between groupings of molecular layers, thereby providing fissures, separations, or other discontinuities in the particles' outer surfaces and openings to the internal portions of the particles.
- inter-layer defects e.g., shearing, buckling, folding, curling, and dislocating of constituent atomic and/or molecular layers
- layered particles refers to particles comprising generally parallel stacked molecular layers, wherein the inter-layer bonding comprises relatively weak bonding such van der Waals bonding, and wherein the intra-layer bonding comprises relatively strong bonding such as covalent bonding.
- layered particles include, but are not limited to, graphite particles, molybdenum disulfide particles, tungsten disulfide particles, niobium diselenide particles, hexagonal boron nitride particles, and carbon particles.
- open architecture and "open-ended architecture” exclude particle morphologies such as closed nano- tubes and fullerenes, which are characterized by closed particle surfaces lacking fissures, separations, or other discontinuities in the particles' outer surfaces.
- the term "closed architecture,” as used in this specification, refers to the morphology of particles lacking fissures, separations, or other discontinuities in the particles' outer surfaces and, therefore, lacking openings to the internal portions of the individual particles.
- the hard particles may comprise a closed architecture or an open architecture.
- compositions described in this specification may also comprise an organic medium intercalated in the lubricant nanoparticles.
- an organic medium may be integrated into the internal portions of individual lubricant nanoparticles by intercalating into the spaces formed by the fissures, separations, or other discontinuities in the outer surfaces of lubricant nanoparticles having an open architecture.
- the lubricant nanoparticles may be intercalated and encapsulated with an organic medium.
- the lubricant nanoparticles may comprise a lubricant material such as, for example, molybdenum disulfide, tungsten disulfide, hexagonal boron nitride, or graphite.
- a lubricant material such as, for example, molybdenum disulfide, tungsten disulfide, hexagonal boron nitride, or graphite.
- the compositions described in this specification may comprise molybdenum disulfide nanoparticles, tungsten disulfide nanoparticles, hexagonal boron nitride nanoparticles, graphite nanoparticles, or combinations of any thereof, as lubricant nanoparticles, which may optionally be encapsulated and/or intercalated with an organic medium.
- the organic medium may comprise at least one material selected from the group consisting of oil mediums, grease mediums, alcohol mediums, composite oils, canola oil, vegetable oil, soybean oil, corn oil, rapeseed oil, ethyl and methyl esters of rapeseed oil, monoglycerides, distilled monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, hydrocarbon oils, n-hexadecane, phospholipids, lecithins, and combinations of any thereof.
- the organic medium may comprise an oil medium such as, for example, a composite oil, canola oil, a vegetable oil, soybean oil, corn oil, a hydrocarbon oil, a mineral oil, or combinations of any thereof.
- compositions and methods described in this specification may comprise, among other components, lubricant nanoparticles which may comprise nano-sheets.
- Nano-sheets are further described, for example, in U.S. Patent Application No. 14/173,369, filed February 5, 2014, which is incorporated by reference into this specification.
- the term "nano-sheets” refers to planar-shaped particles having a thickness dimension of less than 500 nanometers and an aspect ratio (defined as the ratio of the largest length/width dimension to the thickness dimension) of at least 2.
- nano-sheets may have a thickness dimension of less than 100 nanometers and an aspect ratio of at least 10.
- Nano-sheets may have a thickness dimension of less than 50 nanometers and an aspect ratio of at least 20. Nano-sheets may have a thickness dimension of less than 25 nanometers and an aspect ratio of at least 40. Nano-sheets may have a thickness dimension of less than 10 nanometers and an aspect ratio of at least 100. Nano-sheets may have a thickness dimension corresponding to approximately one unit cell dimension and such nano-sheets may be referred to as molecular nano-sheets. Nano-sheets may have length and width dimensions of less than 1000 nanometers.
- Molecular nano-sheets are a sub-genus of nano-sheets in which the thickness dimensions of the nano-sheets correspond to approximately one unit cell dimension.
- Molecular nano-sheets may be, but are not necessarily, crystalline molecular structures.
- molecular nano-sheets may have length and width dimensions of less than or equal to 1000 nanometers, 500 nanometers, or 100 nanometers.
- molecular nano-sheets may have a thickness dimension corresponding to approximately one unit cell dimension.
- a molecular nano-sheet may comprise a single layer of any layered nanoparticle (e.g., a graphite/graphene molecular nano-sheet, a molybdenum disulfide molecular nano-sheet, a tungsten disulfide molecular nano- sheet, a niobium diselenide molecular nano-sheet, or a hexagonal boron nitride molecular nano-sheet).
- any layered nanoparticle e.g., a graphite/graphene molecular nano-sheet, a molybdenum disulfide molecular nano-sheet, a tungsten disulfide molecular nano- sheet, a niobium diselenide molecular nano-sheet, or a hexagonal boron nitride molecular nano-sheet.
- the crystal structure of a material i.e., the spatial arrangement of the atoms forming a crystal
- a unit cell is the smallest molecular unit that a crystal can be divided into using crystallographic symmetry operations.
- a unit cell is the simplest repeating unit in a crystalline material.
- Unit cells stacked in three-dimensional space describe the bulk arrangement of atoms of a crystalline material.
- molybdenum disulfide predominantly exists in a hexagonal crystal form characterized by M0S 2 layers in which the molybdenum atoms have trigonal prismatic coordination of six sulfur atoms with two molecules per unit cell.
- the molybdenum disulfide crystal structure comprises a tri-layer having one planar hexagonal layer of molybdenum atoms interspersed between two planar layers of sulfur atoms forming an intra-molecular covalently bonded S-Mo-S molecular layer.
- Bulk molybdenum disulfide comprises relatively weak inter- molecular van der Waals bonds between the adjacent sulfur atoms of stacked S-Mo- S molecular layers.
- FIG. 10(A) two intra-molecular covalently bonded S-Mo-S molecular layers 10 are shown with inter-molecular van der Waals bonds 17 between the adjacent sulfur atoms 1 1 of the two stacked S-Mo-S molecular layers 10.
- the molybdenum atoms 13 and the sulfur atoms 1 1 form the tri-layer comprising one planar hexagonal layer of molybdenum atoms 13 interspersed between two planar layers of sulfur atoms 1 1 and forming covalent bonds 15.
- the molybdenum disulfide unit cell has a thickness dimension of approximately 3.241 angstroms across the S- Mo-S molecular layer.
- a molybdenum disulfide molecular nano-sheet may comprise a molybdenum disulfide crystal having a thickness dimension corresponding to the thickness of the covalently bonded S-Mo-S molecular layer (without adjoining inter- molecular van der Waals bonded layers, i.e., approximately 3.241 angstroms) and, in some embodiments, length and width dimensions of less than or equal to 1000 nanometers.
- a tungsten disulfide molecular nano-sheet may comprise a tungsten disulfide crystal having a thickness dimension corresponding to the thickness of the covalently bonded S-W-S molecular layer (without adjoining inter-molecular van der Waals bonded layers) and, in some embodiments, length and width dimensions of less than or equal to 1000 nanometers.
- the crystal structure of hexagonal boron nitride is characterized by hexagonal coordination between three nitrogen atoms and three boron atoms forming adjacent six-sided rings that form intra-molecular covalently-bonded monolayers that are atomically thin (i.e. , having a thickness dimension of a single atom).
- FIG 1 1 three intra-molecular covalently bonded B-N molecular layers 20 are shown with inter-molecular van der Waals bonds 27 between the adjacent B- N molecular layers 20.
- the boron atoms 23 and the nitrogen atoms 21 form the mono-layer comprising the hexagonal atomic orientation within a single plane and forming the covalent bonds 25.
- the hexagonal boron nitride crystal structure comprises B-N molecular mono-layers
- bulk hexagonal boron nitride comprises relatively weak inter-molecular van der Waals bonds between the adjacent B-N molecular mono-layers. Therefore, a hexagonal boron nitride molecular nano-sheet may comprise a hexagonal boron nitride crystal having a single atomic thickness dimension and, in some embodiments, length and width dimensions of less than or equal to 1000 nanometers.
- a graphite molecular nano-sheet may comprise a graphene crystal having a single atomic thickness dimension and, in some embodiments, length and width dimensions of less than or equal to 1000 nanometers.
- nano-sheets may comprise a material such as, for example, molybdenum disulfide, tungsten disulfide, niobium diselenide, hexagonal boron nitride, graphite/graphene, metals such as copper or silver, inorganic compounds such as calcium carbonate, polymers such as PTFE, or dithiophosphate compounds.
- the nano-sheets may comprise molecular nano-sheets comprising a material such as, for example, molybdenum disulfide, tungsten disulfide, niobium diselenide, hexagonal boron nitride, or graphene.
- compositions described in this specification may comprise molybdenum disulfide nano-sheets, tungsten disulfide nano-sheets, niobium diselenide nano-sheets, hexagonal boron nitride nano-sheets, graphite nano-sheets, graphene molecular nano-sheets, metal (e.g. , copper) nano-sheets, inorganic compound (e.g., calcium carbonate) nano-sheets, polymer (e.g. , PTFE) nano- sheets, nano-sheets comprising dithiophosphate compounds, or combinations of any thereof.
- metal e.g. , copper
- inorganic compound e.g., calcium carbonate
- polymer e.g. , PTFE
- nano-sheets comprising dithiophosphate compounds, or combinations of any thereof.
- layered materials such as, for example, molybdenum disulfide, tungsten disulfide, niobium diselenide, hexagonal boron nitride, and graphite, may form nano-sheets (e.g., planar-shaped particles having a thickness dimension of less than 500 nanometers and an aspect ratio of at least 2) or molecular nano-sheets (e.g., crystalline molecular structures comprising a thickness dimension corresponding to approximately one unit cell dimension).
- nano-sheets e.g., planar-shaped particles having a thickness dimension of less than 500 nanometers and an aspect ratio of at least 2
- molecular nano-sheets e.g., crystalline molecular structures comprising a thickness dimension corresponding to approximately one unit cell dimension.
- molecular nano-sheets are a sub-genus of nano-sheets.
- the nano-sheets and/or nanoparticles may be functionalized.
- the nano-sheets and/or nanoparticles may be functionalized with organic molecules or functional groups, inorganic molecules or functional groups, or both organic and inorganic molecules or functional groups, forming functionalized nano-sheets and/or nanoparticles.
- the nano-sheets and/or nanoparticles may be functionalized with catalysts, antioxidants, anti-corrosion agents, biocidal agents, or combinations of any thereof.
- antioxidants examples include, but are not limited to, antioxidants selected from the group consisting of hindered phenols, alkylated phenols, alkyl amines, aryl amines, 2,6-di- tert-butyl-4-methylphenol, 4,4'-di-tert-octyldiphenylamine, tert-butyl hydroquinone, tris(2,4-di-tert-butylphenyl)phosphate, phosphites, thioesters, or combinations of any thereof; anticorrosion agents selected from the group consisting of alkaline earth metal bisalkylphenolsulphonates, dithiophosphates, alkenylsuccinic acid half-amides, or combinations thereof; and biocidal agents material selected from the group consisting of alkyi benzothiazole, hydroxylamine benzothiazole, an amine salt of an alkyi succinic acid, an amine salt of an
- the nano-sheets and/or nanoparticles may be functionalized with a dispersant agent.
- Suitable dispersant agents may comprise at least one material selected from the group consisting of amide compounds, borate compounds, and boride compounds.
- a dispersant agent may comprise at least one of succinimide and disodium octaborate tetrahydrate.
- the nano-sheets and/or nanoparticles may be coated and/or encapsulated with an organic medium.
- an organic medium may be chemically or physically adsorbed onto nano-sheets and/or nanoparticles or otherwise chemically or physically bonded to nano-sheets and/or nanoparticles.
- nanoparticles may be encapsulated and/or intercalated with an organic medium.
- organic medium refers to hydrophobic/oleophilic substances and carbon-based compounds.
- the organic medium may comprise at least one material selected from the group consisting of oil media, grease media, alcohol media, composite oils, mineral oils, synthetic oils, canola oil, vegetable oil, soybean oil, corn oil, rapeseed oil, ethyl and methyl esters of rapeseed oil, monoglycerides, distilled monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, hydrocarbon oils, n-hexadecane, phospholipids, lecithins, amide compounds, boron-containing compounds, dithiophosphate compounds, and combinations of any thereof.
- suitable dithiophosphate compounds that may comprise an organic medium include, but are not limited to, zinc dialkyl dithiophosphate (ZDDP) and molybdenum dithiophosphate (MoDTP), which may be used alone or in combination with any other organic medium such as an oil medium.
- the organic medium may comprise an oil medium such as, for example, a composite oil, a mineral oil, a synthetic oil, canola oil, a vegetable oil, soybean oil, corn oil, a hydrocarbon oil, a mineral oil, or combinations of any thereof.
- compositions described in this specification may also comprise a secondary solid lubricant material such as, for example, polytetrafluoroethylene, soft metals, silver, lead, nickel, copper, cerium fluoride, zinc oxide, silver sulfate, cadmium iodide, lead iodide, barium fluoride, tin sulfide, zinc phosphate, zinc sulfide, mica, boron nitrate, borax, fluorinated carbon, zinc phosphide, boron, or combinations of any thereof.
- the secondary solid lubricant material may comprise nanoparticles.
- the secondary solid lubricant nanoparticles may have an average primary particle size of less than or equal to 1000 nanometers, and in some embodiments, less than or equal to 500 nanometers, less than or equal to 400 nanometers, less than or equal to 300 nanometers, less than or equal to 200 nanometers, less than or equal to 100 nanometers, less than or equal to 75 nanometers, less than or equal to 50 nanometers, or less than or equal to 25 nanometers.
- the compositions described in this specification may also comprise a base lubricant material.
- the hard particles and the lubricant nanoparticles may be dispersed in the base lubricant material.
- the base lubricant material may comprise a material such as, for example, an oil, a grease, a polymer, a plastic, a gel, a paste, a wax, a silicone, a hydrocarbon oil, a vegetable oil, corn oil, peanut oil, canola oil, soybean oil, a mineral oil, a paraffin oil, a synthetic oil, a petroleum gel, a petroleum grease, a hydrocarbon gel, a hydrocarbon grease, a lithium based grease, a fluorocarbon based grease, silicon based grease, ethylenebistearamide, or combinations of any thereof.
- the base lubricant material may comprise at least one material selected from the group consisting of an oil, a grease, a plastic, a gel, a wax, a silicone, and combinations of any thereof.
- the base lubricant material may comprise an oil or a grease.
- the base lubricant material may comprise at least one material selected from the group consisting of a mineral oil, a paraffin oil, a synthetic oil, a petroleum grease, a hydrocarbon grease, a lithium based grease, or combinations of any thereof.
- the compositions described in this specification may also comprise an emulsifier.
- the emulsifier may comprise at least one material selected from the group consisting of lecithins, phospholipids, soy lecithins, detergents, distilled monoglycerides, monoglycerides, diglycerides, acetic acid esters of monoglycendes, organic acid esters of monoglycendes, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, compounds containing phosphorous, compounds containing sulfur, compounds containing nitrogen, or combinations of any thereof.
- the emulsifier may comprise a compound containing phosphorous.
- the emulsifier may comprise a phospholipid.
- the emulsifier may comprise a lecithin.
- compositions described in this specification may also comprise one or more of an antioxidant, an anticorrosion agent, or a biocidal.
- the compositions may comprise at least one antioxidant material selected from the group consisting of hindered phenols, alkylated phenols, alkyl amines, aryl amines, 2,6-di-tert-butyl-4-methylphenol, 4,4'-di-tert- octyldiphenylamine, tert-butyl hydroquinone, tris(2,4-di-tert-butylphenyl)phosphate, phosphites, thioesters, or combinations of any thereof.
- compositions may comprise at least one anticorrosion agent selected from the group consisting of alkaline earth metal bisalkylphenolsulphonates, dithiophosphates, alkenylsuccinic acid half-amides, or combinations thereof.
- the compositions may comprise at least one biocidal material selected from the group consisting of alkyl benzothiazole, hydroxylamine benzothiazole, an amine salt of an alkyl succinic acid, an amine salt of an alkenyl succinic acid, a partial alkyl ester of an alkyl succinic acid, a partial alkyl ester of an alkenyl succinic acid, or combinations of any thereof.
- compositions described in this specification may be used to formulate a lubricant.
- compositions comprising hard particles, lubricant nanoparticles, and an organic medium intercalated in the lubricant nanoparticles may be used as performance-enhancing additives to off-the-shelf liquid based lubricants.
- lubricant compositions may comprise hard particles and lubricant nanoparticles dispersed in a lubricant base material as described above, wherein a separate organic medium is intercalated in the lubricant nanoparticles.
- Lubricant compositions comprising hard particles, lubricant nanoparticles, and an organic medium intercalated in the lubricant nanoparticles, in accordance with the embodiments described in this specification, will provide a synergistically enhanced combination of simultaneous surface polishing and surface lubrication that reduces, minimizes, or eliminates pitting corrosion in mechanical systems, in situ, under operating conditions.
- a gear oil for automotive or other mechanical gearing applications may be formulated to comprise hard particles, lubricant nanoparticles, and an organic medium intercalated in the lubricant nanoparticles, where the gear oil provides improved wear protection and reduced pitting, decreasing frictional energy losses and improving energy utilization efficiency (e.g., fuel efficiency in automotive and racing applications).
- compositions formulated to comprise hard particles, lubricant nanoparticles, and an organic medium intercalated in the lubricant nanoparticles may effectively operate under high load, high temperature, and high speed conditions, and may provide improved lubrication and pitting resistance under elastohydrodynamic, boundary, and mixed lubrication regimes.
- Such improvements may be realized by the addition of additives to off-the- shelf liquid phase lubricants, where the additives comprise hard particles, lubricant nanoparticles, and an organic medium intercalated in the lubricant nanoparticles.
- a composition may comprise, in weight percent based on total weight of the particles in the composition, from 1 % to 99% hard particles, and from 1 % to 99% lubricant nanoparticles, or any sub-ranges subsumed therein, such as, for example, 5% to 95% hard particles, and from 5% to 95% lubricant nanoparticles.
- compositions and methods comprising lubricant nanoparticles and an organic medium may be made from solid lubricant starting materials.
- solid lubricants may include, but are not limited to, layered materials such as, for example, chalcogenides, like molybdenum disulfide, tungsten disulfide, or a combination thereof.
- layered materials include graphite or intercalated graphite.
- solid lubricants that may be used alone or in combination with the layered materials include, but are not limited to polytetrafluoroethylene (e.g., Teflon®), hexagonal boron nitride, soft metals (such as, for example, silver, lead, nickel, copper), cerium fluoride, zinc oxide, silver sulfate, cadmium iodide, lead iodide, barium fluoride, tin sulfide, zinc phosphate, zinc sulfide, mica, boron nitrate, borax, fluorinated carbon, zinc phosphide, boron, or a combination thereof.
- polytetrafluoroethylene e.g., Teflon®
- hexagonal boron nitride such as, for example, silver, lead, nickel, copper
- soft metals such as, for example, silver, lead, nickel, copper
- cerium fluoride zinc oxide
- silver sulfate cadmi
- Fluorinated carbons may be, without limitation, carbon-based materials such as graphite which has been fluorinated to improve its aesthetic characteristics.
- Such materials may include, for example, a material such as CF X wherein x ranges from about 0.05 to about 1 .2.
- CF X CF X wherein x ranges from about 0.05 to about 1 .2.
- Such a material is produced, for example, by Allied Chemical under the trade name Accufluor.
- the methods of making the lubricant nanoparticles encapsulated and/or intercalated with the organic medium may include, for example, the milling of a solid lubricant feed material.
- the solid lubricant feed material may be capable of being milled to particles comprising an average primary particle size of about 500 nanometers (submicron size) to about 10 nanometers.
- the particles may have an average primary particle size of less than or equal to about 500 nanometers, less than or equal to about 100 nanometers, less than or equal to about 75 nanometers, and less than or equal to about 50 nanometers.
- the milling may result in milled lubricant particles comprising a mixture, the mixture comprising particles having an average primary particle size of less than or equal to about 500 nanometers, plus larger particles.
- the milling may include, among other techniques, ball milling and chemo-mechanical milling. Examples of ball milling may include dry ball milling, wet ball milling, and combinations thereof. Ball milling may refer to an impaction process that may include two interacting objects where one object may be a ball, a rod, 4 pointed pins ⁇ jack shape), or other shapes. Chemo- mechanical milling may refer to an impaction process that may form an integrated complex between the organic medium and the nanoparticles. As a result of chemo- mechanical milling, the organic medium may coat, encapsulate, and/or intercalate the nanoparticles. In various embodiments, chemo-mechanical milling may be performed using a ball milling technique.
- the solid lubricant feed may be dry milled and then wet milled.
- An emulsifier may be mixed with a lubricant base material and added to the wet milled particles.
- Dry milling may refer to particles that have been milled in the presence of a vacuum, a gas, or a combination thereof.
- Wet milling may refer to particles that have been milled in the presence of a liquid.
- the lubricant nanoparticle composition may further comprise an organic medium.
- organic mediums include, but are not limited to, oil mediums, grease mediums, alcohol mediums, or combinations thereof.
- Specific examples of organic mediums include, but are not limited to, composite oil, canola oil, vegetable oils, soybean oil, corn oil, ethyl and methyl esters of rapeseed oil, distilled monoglycerides, monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, n- hexadecane, hydrocarbon oils, phospholipids, or a combination thereof. Many of these organic media may be environmentally acceptable.
- compositions described in this specification may contain emulsifiers, surfactants, or dispersants.
- emulsifiers may include, but are not limited to, emulsifiers having a hydrophilic-lipophilic balance (HLB) from about 2 to about 7; a HLB from about 3 to about 5; or a HLB of about 4.
- HLB hydrophilic-lipophilic balance
- emulsifiers may include, but are not limited to, lecithins, soy lecithins, phospholipids lecithins, detergents, distilled monoglycerides, monoglycerides, diglycerides, acetic acid esters of monoglycerides, organic acid esters of monoglycerides, sorbitan esters of fatty acids, propylene glycol esters of fatty acids, polyglycerol esters of fatty acids, compounds containing phosphorous, compounds containing sulfur, compounds containing nitrogen, or a combination thereof.
- a method of making a composition such as, for example, a lubricant additive or a primary lubricant formulation, is described.
- the composition may be used as an additive dispersed in a lubricant base material or as a component of a primary lubricant formulation.
- lubricant base materials may include, but are not limited to, oils, greases, plastics, gels, sprays, or a combination thereof.
- bases may include, but are not limited to, hydrocarbon oils, vegetable oils, corn oil, peanut oil, canola oil, soybean oil, mineral oil, paraffin oils, synthetic oils, petroleum gels, petroleum greases, hydrocarbon gels, hydrocarbon greases, lithium based greases, fluoroether based greases, ethylenebistearamide, waxes, silicones, or a combination thereof.
- a method of lubricating or coating an object that is part of an end application with a composition comprising hard particles, lubricant nanoparticles, and an organic medium. Further described is a method of lubricating an object by employing the composition comprising hard particles, lubricant nanoparticles, and an organic medium as a delivery or carrier mechanism.
- a catalyst delivery or carrier system comprises hard particles, lubricant nanoparticles, an organic medium, and a catalyst material.
- the catalyst material may be functionalized onto the surface of the hard particles, lubricant nanoparticles, or both.
- the catalyst material may be intercalated or otherwise integrated into the lubricant nanoparticles.
- Figure 1 illustrates a method of preparing nanoparticle based lubricants or compositions.
- a solid lubricant feed is introduced via line 210 to a ball milling processor 215. Ball milling is carried out in the processor 215 and the solid lubricant feed is milled to comprise particles having an average primary particle size of less than or equal to about 1000 nanometers, less than or equal to about 500 nanometers, less than or equal to about 100 nanometers, less than or equal to about 80 nanometers, or less than or equal to about 50 nanometers.
- the ball milling may result in milled solid lubricant particles comprising a mixture, the mixture comprising particles having an average particle dimension of less than or equal to about 1000 nanometers or less than or equal to about 500 nanometers, plus larger particles.
- the ball milling may be high energy ball milling, medium energy ball milling, or combinations thereof. Additionally, in various embodiments the ball milling may be carried out in a vacuum, in the presence of a gas, in the presence of a liquid, in the presence of a second solid, or combinations thereof.
- the nanoparticle composition may be removed from the processor via line 220.
- the nanoparticle composition may be a nanoparticle based lubricant.
- the ball milling may comprise a first ball milling and at least one more subsequent ball millings, or ball milling and/or other processing as appropriate.
- the ball milling may comprise dry milling followed by wet milling.
- Figure 2 illustrates a further method 100 of preparing nanoparticle based lubricants and other compositions where dry milling is followed by wet milling.
- Feed 1 10 introduces a solid lubricant feed into a ball milling processor 1 15 where dry ball milling, such as in a vacuum or in air, reduces the solid lubricant feed to particles having an average dimension of the size described above.
- Line 120 carries the dry milled particles to a wet milling processor 125.
- the dry milled particles are combined with a composite oil or an organic medium prior to entering the wet milling processor 125.
- the organic medium and dry milled particles may be combined in the wet milling processor 125.
- the dry milling and wet milling may be carried out in a single processor where the organic medium is supplied to the single processor for wet milling after initially carrying out dry milling.
- the balls in the ball milling apparatus may be coated with the organic medium to incorporate the organic medium in the lubricant nanoparticles.
- line 130 carries the wet milled particles to a container 135, which may be a sonication device.
- line 130 may carry a mixture comprising lubricant nanoparticles, organic medium, and a complex comprising the lubricant nanoparticles combined with an organic medium.
- a lubricant base material may be fed to the container 135 via line 150.
- the base may be supplied to the wet milling processor 125 and the mixing, which may include sonicating, may be carried out in the wet milling processor 125.
- the lubricant nanoparticle composition may be employed as an additive and dispersed in the lubricant base material.
- a lubricant base material may be paired with a lubricant nanoparticle composition according to the ability of the base material and the lubricant nanoparticle composition to blend appropriately. In such cases the lubricant nanoparticle composition may enhance the performance characteristics of the base.
- an emulsifier may be mixed with the lubricant base material. Emulsifiers may further enhance dispersion of the lubricant nanoparticle composition in the lubricant base material.
- the emulsifier may be selected to enhance the dispersion stability of a nanoparticle composition in a base.
- An emulsifier may also be supplied to the container 135 via line 140. In some embodiments, the emulsifier and base are combined in the container 135 prior to introduction of the wet milled particles.
- Prior mixing of the emulsifier with the base material may enhance dispersion upon addition of complexes of lubricant nanoparticles and organic medium and/or lubricant nanoparticles by homogeneously dispersing the complexes/nanoparticles.
- the mixing of the emulsifier and base may comprise sonicating.
- the emulsifier may be supplied to the wet milling processor 125 and the mixing, which may include sonicating, may be carried out in the wet milling processor 125.
- the lubricant removed from the container 135 via line 120 may be a blend comprising the wet milled particles, organic medium, and base.
- the blend may further comprise an emulsifier.
- antioxidants or anticorrosion agents may be milled with the lubricant nanoparticles or added to prior milled lubricant nanoparticles.
- antioxidants include, but are not limited to, hindered phenols, alkylated phenols, alkyl amines, aryl amines, 2,6-di-tert-butyl-4-methylphenol, 4,4'-di-tert- octyldiphenylamine, tert-Butyl hydroquinone, tris(2,4-di-tert-butylphenyl)phosphate, phosphites, thioesters, or combinations of any thereof.
- anticorrosion agents include, but are not limited to, alkaline-earth metal bisalkylphenolsulphonates, dithiophosphates, alkenylsuccinic acid half-amides, or combinations of any thereof.
- biocidals may be milled with the lubricant nanoparticles or added to prior milled lubricant nanoparticles.
- biocidals may include, but are not limited to, alkyl or hydroxylamine benzotriazole, an amine salt of a partial alkyl ester of an alkyl, alkenyl succinic acid, or a combination thereof.
- further processing of wet milled particles may comprise removal of oils that are not a part of a complex with the solid lubricant particles.
- Such methods may be suitable for applications that benefit from use of dry particles of solid lubricant, such as coating applications.
- Oil and/or other liquids can be removed from wet milled particles to produce substantially dry solid lubricant particles and complexes having intercalated organic media.
- Such wet milling followed by drying may produce a lubricant with reduced tendency to agglomerate.
- an agent such as acetone or other suitable solvent, may be added that dissolves oils that are not a part of a complex with the particles, followed by a drying process such as supercritical drying, to produce a substantially dry lubricant comprising particles treated by milling in an organic medium.
- Ball milling conditions may vary and, in particular, conditions such as temperature, milling time, and size and materials of the balls and vials may be manipulated.
- ball milling may be carried out from about 12 hours to about 50 hours, from about 36 hours to about 50 hours, from about 40 hours to about 50 hours, or for about 48 hours ( ⁇ 1 hour, ⁇ 2 hours, or ⁇ 3 hours).
- Ball milling may be conducted at room temperature or elevated temperatures.
- the benefits of increasing milling time may comprise at least one of increasing the time for the organic medium and lubricant nanoparticles to interact, integrate, and complex; and producing finer sizes, better yield of nanoparticles, more uniform shapes, and more passive surfaces.
- An example of ball milling equipment suitable for carrying out the described milling includes the SPEX CertiPrep model 8000D, along with hardened stainless steel vials and hardened stainless steel grinding balls, but any type of ball milling apparatus may be used.
- a stress of 600-650 MPa, a load of 14.9 N, and a strain of 10 "3 -10 "4 per second may be used.
- the proportions of the components in a nanoparticle based lubricant or other composition may contribute to performance of the composition, such as the composition's dispersion stability and ability to resist agglomeration.
- suitable ratios of lubricant nanoparticles to organic medium may be about 1 part particles to about 4 parts organic medium by weight, about 1 part particles to about 3 parts organic medium by weight, about 3 parts particles to about 8 parts organic medium by weight, about 2 parts particles to about 4 parts organic medium by weight, about 1 part particles to about 2 parts organic medium by weight, or about 1 part particles to about 1 .5 parts organic medium by weight.
- Suitable ratios of organic medium to emulsifier in a composition including the lubricant nanoparticles may be about 1 part organic medium to less than or equal to about 1 part emulsifier, about 1 part organic medium to about 0.5 parts emulsifier by weight, or from about 0.4 to about 1 part emulsifier for about 1 part organic medium by weight.
- the amount of lubricant nanoparticle composition (by weight) sonicated or dispersed in a lubricant base materials may comprise from about 0.25% to about 5%, about 0.5% to about 3%, about 0.5% to about 2%, or about 0.75% to about 2%, based on total weight of the composition.
- the amount of emulsifier (by weight) sonicated or dissolved in a lubricant base material may comprise from about 0.5% to about 10%, from about 4% to about 8%, from about 5% to about 6%, or from about 0.75% to about 2.25%, based on total weight of the composition.
- compositions described in this specification may be used, without limitation, as lubricants, coatings, delivery mechanisms, or combinations of any thereof.
- the compositions may be used, without limitation, as an additive dispersed in a base oil or other lubricant composition.
- the compositions may also be used, without limitation, to lubricate a boundary lubrication regime.
- a boundary lubrication regime may be a lubrication regime where the average lubricant film thickness may be less than the composite surface roughness and the surface asperities may come into contact with each other under relative motion. During the relative motion of two surfaces with lubricants in various applications, three different lubrication stages may occur, and the boundary lubrication regime may be the most severe condition in terms of temperature, pressure and speed.
- Mating parts may be exposed to severe contact conditions of high load, low velocity, extreme pressure (for example, 1 -2 GPa), and high local temperature (for example, 150-300 degrees C).
- the boundary lubrication regime may also exist under lower pressures and low sliding velocities or high temperatures. In the boundary lubrication regime, the mating surfaces may be in direct physical contact.
- compositions may further be used, without limitation, as a lubricant or coating in machinery applications, manufacturing applications, mining applications, aerospace applications, automotive applications, pharmaceutical applications, medical applications, dental applications, cosmetic applications, food product applications, nutritional applications, health related applications, bio-fuel applications or a combination thereof.
- a lubricant or coating in machinery applications manufacturing applications, mining applications, aerospace applications, automotive applications, pharmaceutical applications, medical applications, dental applications, cosmetic applications, food product applications, nutritional applications, health related applications, bio-fuel applications or a combination thereof.
- Specific examples of uses in end applications include, without limitation, machine tools, bearings, gears, camshafts, pumps, transmissions, piston rings, engines, power generators, pin-joints, aerospace systems, mining equipment, manufacturing equipment, or a combination thereof.
- Further specific examples of uses may be, without limitation, as an additive in lubricants, greases, gels, compounded plastic parts, pastes, powders, emulsions, dispersions, or combinations thereof.
- compositions may also be used as a lubricant that employs the lubricant nanoparticle composition as a delivery mechanism in pharmaceutical applications, medical applications, dental applications, cosmetic applications, food product applications, nutritional applications, health related applications, bio-fuel applications, or a combination thereof.
- the various compositions and methods may also be used, without limitation, in hybrid inorganic- organic materials.
- Examples of applications using inorganic-organic materials include, but are not limited to, optics, electronics, ionics, mechanics, energy, environment, biology, medicine, smart membranes, separation devices, functional smart coatings, photovoltaic and fuel cells, photocatalysts, new catalysts, sensors, smart microelectronics, micro-optical and photonic components and systems for nanophotonics, innovative cosmetics, intelligent therapeutic vectors that combined targeting, imaging, therapy, and controlled release of active molecules, and nanoceramic-polymer composites.
- the ball milling process may create a close caged dense oval shaped architecture (similar to a football shape or fullerene type architecture). This may occur when solid lubricant feed materials are milled in a gas or vacuum.
- Figure 7(A) shows the close caged dense oval shaped architecture of molybdenum disulfide nanoparticles that have been ball milled in air for 48 hours.
- the ball milling process may create an open architecture (as described above), which may be encapsulated and/or intercalated with an organic medium. This may occur when solid lubricant feed materials are milled in a gas or vacuum followed by milling in an organic medium.
- Figure 7(B) shows the open architecture of molybdenum disulfide nanoparticles that have been ball milled in air for 48 hours followed by ball milling in canola oil for 48 hours.
- the tribological performance of the nanoparticle based lubricant may be improved.
- the tribological performance may be measured by evaluating different properties.
- An anti-wear property may be a lubricating fluid property that has been measured using the industry standard Four-Ball Wear (ASTM D4172) Test.
- the Four-Ball Wear Test may evaluate the protection provided by a lubricant under conditions of pressure and sliding motion. Placed in a bath of the test lubricant, three fixed steel balls may be put into contact with a fourth ball of the same grade in rotating contact at preset test conditions.
- Lubricant wear protection properties may be measured by comparing the average wear scars on the three fixed balls. The smaller the average wear scar, the better the protection.
- Extreme pressure properties may be lubricating fluid properties that have been measured using the industry standard Four-Ball Wear (ASTM D2783) Test. This test method may cover the determination of the load-carrying properties of lubricating fluids. The following two determinations may be made: 1 ) load-wear index (formerly Mean-Hertz load) and 2) weld load (kg).
- the load-wear index may be the load-carrying property of a lubricant. It may be an index of the ability of a lubricant to minimize wear at applied loads.
- the weld load may be the lowest applied load in kilograms at which the rotating ball welds to the three stationary balls, indicating the extreme pressure level that the lubricants can withstand.
- the coefficient of friction may be a lubricating fluid property that has been measured using the industry standard Four-Ball Wear (ASTM D4172) Test.
- COF may be a dimensionless scalar value which describes the ratio of the force of friction between two bodies and the force pressing them together.
- the coefficient of friction may depend on the materials used. For example, ice on metal has a low COF, while rubber on pavement has a high COF.
- a common way to reduce friction may be by using a lubricant which is placed between two surfaces.
- compositions described in this specification may have a wear scar diameter of about 0.4 mm to about 0.5 mm.
- the composition may have a COF of about 0.06 to about 0.08.
- the composition may have a weld load of about 150 kg to about 350 kg.
- the composition may have a load wear index of about 20 to about 40. The values of these tribological properties may change depending on the amount of lubricant nanoparticle composition sonicated or dissolved in the lubricant base material.
- Ball milling was performed in a SPEX 8000D machine using hardened stainless steel vials and balls.
- M0S 2 Alfa Aesar, 98% pure, 700 nm average primary particle size
- canola oil canola oil (Crisco) were used as the starting materials in a ratio of 1 part M0S 2 (10 grams) to 2 parts canola oil (20 grams). The ball to powder weight ratio was 2 to 1 .
- M0S 2 was ball milled for 48 hours in air followed by milling in canola oil for 48 hrs at room temperature. The nanoparticles were about 50 nm after ball milling.
- Table 1 summarizes milling conditions and resultant particle morphologies.
- Figure 3 shows TEM micrographs of the as-available (700 nm), air milled, and hybrid milled (48 hrs in air medium followed by 48 hours in oil medium) M0S 2 nanoparticles.
- Figure 3(A) represents micron-sized particle chunks of the as- available M0S 2 sample off the shelf.
- Figure 3(B) represent agglomerates of lubricant nanoparticles when milled in the air medium.
- Figure 3(B) clearly demonstrates size reduction in air milled M0S 2 . Higher magnification (circular regions) revealed formation of the disc shaped nanoparticles after milling in the air medium.
- the particle size was reduced to less than 30 nm after milling in air and hybrid conditions. Regardless of the occasionally observed clusters, the average size of the clusters is less than or equal to 200 nm.
- Hybrid milled samples were dispersed in paraffin oil (from Walmart) and remained suspended without settling. However, the dispersion was not uniform after a few weeks. To stabilize the dispersion and extend the anti-wear properties, phospholipids were added. Around 2% by weight of soy lecithin phospholipids (from American Lecithin) was added in the base oil.
- FIGS 4 and 5 show the XRD and XPS spectra of M0S 2 before and after ball milling, respectively.
- XRD spectra revealed no phase change as well as no observable amorphization in the M0S 2 after milling. This observation is consistent with the continuous platelets observed throughout the nanoparticle matrix in TEM analysis for milled material. Broadening of peaks (FWHM) was observed in XRD spectra of M0S 2 ball milled in air and hybrid media, respectively. The peak broadening may be attributed to the reduction in particle size.
- the estimated grain size is 6 nm. This follows the theme of ball milling where clusters consist of grains and sub-grains of the order of 10 nm.
- Wear scar diameter (WSD, mm) of each stationary ball was quantified in both vertical and horizontal directions. The average value of WSD from 3 independent tests was reported within ⁇ 0.03 mm accuracy.
- Figure 6(A) shows the average wear scar measurements for paraffin oil without a nanoparticle additive, paraffin oil with micron sized M0S 2 , paraffin oil with MoS 2 that was milled in air for 48 hours, and paraffin oil with MoS 2 that was milled in air for 48 hours followed by milling in canola oil for 48 hours.
- Figure 6(B) shows the load wear index for paraffin oil without a nanoparticle additive, paraffin oil with micron sized M0S 2 , paraffin oil with M0S 2 that was milled in air for 48 hours, and paraffin oil with M0S 2 that was milled in air for 48 hours followed by milling in canola oil for 48 hours.
- Figure 6(C) shows the COF for paraffin oil without a nanoparticle additive, paraffin oil with micron sized M0S 2 , paraffin oil with M0S 2 that was milled in air for 48 hours, and paraffin oil with M0S 2 that was milled in air for 48 hours followed by milling in canola oil for 48 hours.
- Figure 6(D) shows the extreme pressure data for paraffin oil with micron sized M0S 2 , paraffin oil with M0S 2 that was milled in air for 48 hours, and paraffin oil with M0S 2 that was milled in air for 48 hours followed by milling in canola oil for 48 hours.
- the nanoparticle additive was present in the amount of 1 % by weight.
- FIG. 8 Comparison of wear scar diameters for different additives in paraffin oil are graphically depicted in Figure 8.
- One additive is crystalline molybdenum disulfide (c- MoS2).
- Another additive is molybdenum disulfide nanoparticles that were ball milled in air (n-MoS2).
- Another additive is molybdenum disulfide nanoparticles that were ball milled in air followed by ball milling in canola oil and to which a phospholipid emulsifier was added (n-MoS2+Emulsifier).
- FIG. 9(a) depicts the base case of paraffin oil without a nanoparticle additive.
- Figure 9(b) depicts paraffin oil with the molybdenum disulfide nanoparticles and the emulsifier. It shows the early evidences of molybdenum (Mo)-sulfur (S)- phosphorous (P) in the wear track.
- Iron (Fe) is seen in Figures 9(a) and 9(b), as it is the material of the balls (52100 steel) in the four-ball test.
- the molybdenum and sulfur peaks coincide and are not distinguishable because they have the same binding energy. Elemental mapping also showed similar results.
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CN105670756A (en) * | 2016-03-01 | 2016-06-15 | 安徽振海重工机械有限公司 | Valve lubricating grease and preparation method thereof |
CN106635256A (en) * | 2016-09-28 | 2017-05-10 | 贵州特力达纳米碳素科技有限公司 | Lubricant additive and preparation method thereof |
CN106541224B (en) * | 2016-10-28 | 2019-01-15 | 北京工业大学 | A kind of no copper facing specific coatings welding wire nano lubricating oil and preparation method thereof |
CN106566594A (en) * | 2016-11-04 | 2017-04-19 | 上海中真润滑油有限公司 | Preparation method for molybdenum disulfide nano-sheet modified perfluoropolyether oil |
CN106675730B (en) * | 2016-12-23 | 2019-08-27 | 诺泰生物科技(合肥)有限公司 | A kind of volatile-type pipe expanding oil and its preparation method |
US11434381B2 (en) * | 2017-03-06 | 2022-09-06 | Bic-Violex Sa | Coating |
CN108246339B (en) * | 2018-03-09 | 2020-07-10 | 合肥工业大学 | Preparation method and application of covalent organic framework/carbon nitride composite material |
AT16480U1 (en) * | 2018-04-20 | 2019-10-15 | Plansee Composite Mat Gmbh | Target and method of making a target |
CN108929742B (en) * | 2018-08-31 | 2020-12-15 | 清华大学 | Nano molybdenum disulfide lubricating oil and preparation method thereof |
CN112296345B (en) * | 2019-07-23 | 2022-02-18 | 富兰克科技(深圳)股份有限公司 | Preparation method of self-dispersible nano-copper with long organic carbon chain, nano-copper preparation and application thereof |
CN110499205B (en) * | 2019-09-17 | 2022-03-25 | 南方科技大学 | Oil-soluble slurry dispersed with graphene oxide, and preparation method and application thereof |
US11459522B2 (en) * | 2020-03-03 | 2022-10-04 | Centurion Technologies, LLC | Oilfield drilling lubricant for water-based and oil-based systems |
CN114349918B (en) * | 2022-01-25 | 2023-04-14 | 西北工业大学 | Fluoropolymer modified Ti 3 C 2 T x MXene lubricating oil additive and preparation method and application thereof |
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US20080287326A1 (en) * | 2000-12-12 | 2008-11-20 | Zhiqiang Zhang | Lubricants with enhanced thermal conductivity containing nanomaterial for automatic transmission fluids, power transmission fluids and hydraulic steering applications |
US20060258875A1 (en) * | 2005-05-10 | 2006-11-16 | Clementine Reyes | Methods for manufacturing supported nanocatalysts and methods for using supported nanocatalysts |
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US9023771B2 (en) * | 2006-01-31 | 2015-05-05 | Nissan Motor Co., Ltd. | Nanoparticle-containing lubricating oil compositions |
US7994105B2 (en) * | 2007-08-11 | 2011-08-09 | Jagdish Narayan | Lubricant having nanoparticles and microparticles to enhance fuel efficiency, and a laser synthesis method to create dispersed nanoparticles |
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US8486870B1 (en) * | 2012-07-02 | 2013-07-16 | Ajay P. Malshe | Textured surfaces to enhance nano-lubrication |
US8476206B1 (en) * | 2012-07-02 | 2013-07-02 | Ajay P. Malshe | Nanoparticle macro-compositions |
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