CN103391990B - Lubricants for use in processing, processing additive and working method - Google Patents
Lubricants for use in processing, processing additive and working method Download PDFInfo
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- CN103391990B CN103391990B CN201280010350.5A CN201280010350A CN103391990B CN 103391990 B CN103391990 B CN 103391990B CN 201280010350 A CN201280010350 A CN 201280010350A CN 103391990 B CN103391990 B CN 103391990B
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- lubricants
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- 238000012545 processing Methods 0.000 title claims abstract description 170
- 239000000314 lubricant Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims description 39
- 239000000654 additive Substances 0.000 title description 15
- 230000000996 additive effect Effects 0.000 title description 15
- 239000000463 material Substances 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000383 hazardous chemical Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 abstract description 79
- 238000005245 sintering Methods 0.000 abstract description 31
- 239000007787 solid Substances 0.000 abstract description 27
- 125000000524 functional group Chemical group 0.000 abstract description 23
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 16
- -1 amino, carboxyl Chemical group 0.000 abstract description 9
- 239000000523 sample Substances 0.000 description 47
- 239000003921 oil Substances 0.000 description 36
- 239000000126 substance Substances 0.000 description 24
- 238000005461 lubrication Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- 239000010687 lubricating oil Substances 0.000 description 14
- 239000002199 base oil Substances 0.000 description 13
- 230000007613 environmental effect Effects 0.000 description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000001678 elastic recoil detection analysis Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000010273 cold forging Methods 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 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 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/245—Soft metals, e.g. aluminum
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention provides the lubricants for use in processing of the excellent aluminium alloy such as sintering resistance etc.Lubricants for use in processing of the present invention, to form with by aluminum or aluminum alloy between coated of the processing apparatus by amorphousness carbon film coated and to contact with coated and between the machined surface of processed machined material, the feature of described lubricants for use in processing is, when entirety is set to 100 quality %, containing 8 ~ 50 quality % have comprise at least more than one surface functional group in carbonyl, amino, carboxyl or hydroxyl and molecular weight be 8000 ~ 1,000,000 macromolecular compound.Like this, the macromolecular compound that molecular weight is large is adsorbed on the amorphousness carbon film etc. of processing apparatus securely.Therefore, even if when forcing work to the aluminium alloy easily producing sintering etc., lubricant film also can stably be present between machined surface, can suppress their solid contact and sintering.
Description
Technical field
The present invention relates to the lubricants for use in processing forcing work, the processing additive used in this lubricants for use in processing and the working method using them of carrying out aluminum-based metal when not producing sintering etc.
Background technology
In order to need high working property with the component of low cost production high-quality.Such as, when carrying out forging, thinning processing, the cold plasticity processing such as drawing processing, require to increase deflection each time etc. and boost productivity, and, maintain the quality of machined surface and extend life-span of expensive processing apparatus.For this reason, it is important for realizing the reduction of the frictional coefficient between processing apparatus and machined material, improving sintering resistance.Therefore, in the past, the hard films having and reduce the effects such as frictional coefficient is set on the surface of the processing apparatus such as mould or uses various lubricants for use in processing (lubricating oil) or their combinations are processed.
But, at low temperatures to (following by aluminum or aluminum alloy, comprising aluminium interior suitably referred to as " aluminium alloy ") machined material that forms carries out forcing work (such as, the plastic working that expanded surface area rate is large) time, in lubricating method as above, easily produce sintering, be difficult to the life-span of guaranteeing processing quality or processing apparatus.Think this is because, aluminium alloy is compared with ferrous materials etc., and intensity is low and ductility is low.
In the past, in order to prevent this sintering, how to be pre-formed firmly solid lubrication overlay film (phosphate coating) on the surface of aluminium alloy.But the formation of solid lubrication overlay film needs the heat drying operation etc. of chemical conversion treatment (patent documentation 1 with reference to following) or metallic soap, and cost is high.In addition, solid lubrication overlay film is many containing P or Zn etc. as bad environmental element, in recent environmental problem, ites is desirable to suppress it to use.
Under these circumstances, the lubricants for use in processing of the aluminium alloy of alternative solid lubrication overlay film is proposed.Record about these contents is such as present in following patent documentation 2 ~ 5.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 10-237667 publication
Patent documentation 2: Japanese Patent Publication 6-51875 publication
Patent documentation 3: Japanese Patent No. 3812849 publications
Patent documentation 4: Japanese Unexamined Patent Publication 10-183151 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2004-358495 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2010-95792 publication
Summary of the invention
Invent problem to be solved
Patent documentation 2 proposes the cold forging of the aluminium alloy being added with lipid acid in mineral oil with lubricator.But, the highest also with regard to the lubricant of the about lipid acid of hundreds of for being added with molecular weight, aluminium alloy is forced can produce sintering man-hour at low temperatures.
Patent documentation 3 provides the lubricating oil of the plastic working being suitable for aluminium alloy DI tank.Same with the lubricant of patent documentation 2, the sintering resistance of this lubricating oil etc. are also insufficient.In addition, this lubricating oil uses the extreme pressure agent comprising sulphur (S) as bad environmental element, phosphorus (P), not preferred in environment.
Patent documentation 4 also provides the lubricating oil of the plastic working being suitable for aluminium alloy DI tank, but use in additive molecular weight be 900 ~ 1300 water-soluble lipid acid.But its sintering resistance is insufficient in the same manner as the situation of patent documentation 3.
Patent documentation 5 proposes to add in the cold-drawn of aluminium alloy and forms DLC overlay film in the drawing portion of fixture man-hour and inject the scheme of lubricating oil to this drawing portion.Lubricating oil is the lubricating oil being added with low-molecular-weight fatty acid ester or zinc phosphate etc. in mineral oil as used herein.This lubricating oil is also containing P, the Zn as bad environmental element, not preferred in environment.
In addition, although above-mentioned patent documentation 6 proposes the lubricant lubricant not being the processing being specifically designed to aluminium alloy being comprised the lower lipid acid of molecular weight ratio etc. and the technology being combined to carry out processing by the mould etc. containing Si amorphousness carbon film coated.
The present invention completes in view of situation as above.That is, even if its object is to provide the lubricants for use in processing that also can not produce sintering etc. when carrying out the large cold plasticity processing of degree of finish at the extreme pressure agent not being used as environmentally hazardous substance etc. to the machined material be made up of aluminium alloy.In addition, its object is also to be provided in the processing additive used in the preparation of this lubricants for use in processing and the working method using this processing additive.
For the method for dealing with problems
The present inventor conducts in-depth research to solve this problem, and repeatedly constantly grope, result, new discovery: by using the untapped macromolecular compound with very large molecular weight in lubricants for use in processing in the past, even if can make aluminium alloy sintering not occur and can carry out forcing work with low operating force when not using the extreme pressure agent etc. comprising bad environmental element.And by its achievement of development, complete the present invention of the following stated.
" lubricants for use in processing "
(1) lubricants for use in processing of the present invention to form with by aluminum or aluminum alloy between coated of the processing apparatus by amorphousness carbon film coated and to contact with this coated and between the machined surface of processed machined material, the feature of described lubricants for use in processing is, when entirety is set to 100 quality %, containing 8 ~ 50 quality % have comprise at least more than one surface functional group in carbonyl, amino, carboxyl or hydroxyl and molecular weight be 8000 ~ 1,000,000 macromolecular compound.
(2) lubricants for use in processing of the application of the invention, even if when machined material is made up of aluminium alloy (containing aluminium), this machined material and by the processing apparatus of amorphousness carbon film coated between also can not sinter, that can carry out high-quality with low operating force forces work.And, such excellent results just can obtain by means of only making lubricants for use in processing of the present invention (suitable to " between machined surface " below) between coated of the processing apparatus by amorphousness carbon film coated and the machined surface of machined material processed by it, different from the situation of solid lubrication overlay film, do not need chemical conversion treatment or heat drying process etc.
Therefore, even if under carrying out cold worked situation with large working modulus to aluminium alloy, also can realize the high life of the processing apparatus such as the simplification of complete processing, energy-saving and mould, and then the productivity that can realize Al-alloy products improves and cost degradation.
In addition, according to lubricants for use in processing of the present invention, even if when forcing work to aluminium alloy, do not need the extreme pressure agent etc. comprising bad environmental element up to the present used yet.Work of forcing described herein refers to and to comment on according to Toyota Central Research Institute Co R & D, Vol.28, being documented in use in the ball-passing test of the treated oil containing extreme pressure agent of No.3, P12-13 (1993.9) does not occur to sinter and can carry out the processing of the draft 8% (details as shown in the Examples) of the thinning processing of steel.Therefore, lubricants for use in processing of the present invention is also excellent in Environmental.
(3) lubricants for use in processing not yet clearly of the present invention shows the mechanism of such good characteristic, but thinks as follows with regard to present situation.The molecular weight of the macromolecular compound contained in lubricants for use in processing of the present invention is much larger than the base oil of the lubricants for use in processing formed in the past or additive.Therefore, for macromolecular compound of the present invention, the physical adsorption power being adsorbed on every 1 molecule on coated (specifically on amorphousness carbon film) of processing apparatus or the machined surface of machined material is large, and viscosity is also high.Therefore thinking, even if when forcing work to aluminium alloy, also not easily between machined surface, rupture of oil film occurring.In addition, the thickness of solid lubrication overlay film in the past etc. needs for approximate number μm, but because the molecular weight of macromolecular compound of the present invention is large, therefore the macromolecular compound of other macromolecular compounds and surface adsorption is wound around mutually, therefore can suppress the solid contact between machined surface.In addition, macromolecular compound is different from solid lubrication overlay film, and only adsorption film (liquid film), therefore thinks, easily follows the viscous deformation adding man-hour, also easily suppresses the solid contact between machined surface in this regard.
In addition, even if the adsorption film of macromolecular compound of the present invention (liquid film) produces small fracture in local, between machined surface, the excellent amorphousness carbon film such as sintering resistance, wearability, resistance to sliding can also be there is.This amorphousness carbon film can say that the spares as lubricants for use in processing or macromolecular compound plays function, the sintering (or generation of the adhesion of macroscopic view) that can effectively suppress to be caused by intermetallic solid contact, the increase of frictional coefficient.
At this, macromolecular compound not only dominant is adsorbed on the machined surface of coated or the machined material processing apparatus reasoningly, and is chemically adsorbed on amorphousness carbon film, can play very large adsorptivity thus.Thus, between machined surface, more not easily there is rupture of oil film.It should be noted that, the absorption of this chemical produces to be thought because macromolecular compound of the present invention has at least more than one the surface functional group comprised in carbonyl, amino, carboxyl or hydroxyl.Especially, when amorphousness carbon film is for containing Si amorphousness carbon film (DLC-Si film), produce between the Si-OH (silanol) being adsorbed on the Si on DLC-Si film of this chemical and the surface functional group of macromolecular compound.
In any case, according to lubricants for use in processing of the present invention, even if when by the forcing work of aluminium alloy, between machined surface, effect has a large shearing force, also can maintain the stable lubricant film (boundary film) comprising macromolecular compound between machined surface, what can realize sintering prevents the reduction with operating force.
" processing additive "
The present invention not only can be understood as lubricants for use in processing, it is also understood that the above-mentioned processing additive comprising macromolecular compound for using in its preparation.
" working method "
In addition, the present invention not only can be understood as lubricants for use in processing or processing additive, it is also understood that the working method for using them.Namely, the present invention can be a kind of working method, it is characterized in that, above-mentioned lubricants for use in processing is made to form with by aluminum or aluminum alloy between coated of the processing apparatus by amorphousness carbon film coated and to contact with this coated and between the machined surface of processed machined material, utilize this processing apparatus to process this machined material.
" other "
As long as no being particularly limited to, described in this manual " x ~ y " comprises lower value x and higher limit y.In addition, any number in the numerical value recorded in this specification sheets and the numerical range recorded in this manual can be set " a ~ b " such numerical range as new lower value or higher limit.
Accompanying drawing explanation
Fig. 1 is the chart illustrating oil soluble macromolecular compound of the present invention and chemical structural formula thereof.
Fig. 2 is the chart illustrating water-soluble high-molecular compound of the present invention and chemical structural formula thereof.
Fig. 3 is the sketch chart of ball-passing test device.
Fig. 4 is the pyrolysis gas chromatography figure of the thermolysis GC/MS of sample No.A81.
Embodiment
Enumerate working of an invention mode to be described in more detail the present invention.The content illustrated in this manual can not only be applicable to lubricants for use in processing of the present invention or processing additive, and can also be applicable to the working method etc. using them.One or more formation optional from this specification sheets can be attached in above-mentioned formation of the present invention.In addition, if the formation relevant to working method can be interpreted as that method limits product (productbyprocess), the formation relevant to thing (machining object) can also be become.It should be noted that, which kind of embodiment is best according to use object or require performance etc. and different.
" macromolecular compound "
(1) molecular weight of macromolecular compound of the present invention is 8000 ~ 1,000,000.When this molecular weight is too small, above-mentioned effect of the present invention is not enough.On the other hand, molecular weight can increase, but is not easy to obtain the excessive macromolecular compound of molecular weight.Therefore, the molecular weight of macromolecular compound is preferably about 10,000 ~ about 900,000, and more preferably about 30,000 ~ about 850,000.
Such macromolecular compound can be obtained by known method.Such as, macromolecular compound with so-called monomer be initial by chemical reaction synthetic polymer.As this synthetic method, usually extensively there will be a known by the polymerization based on chain reaction, the polycondensation based on step reaction, addition polymerization, addition condensation and the situation of synthesizing.Further, the molecular weight of macromolecular compound can be regulated arbitrarily by the selection of the temperature, catalytic amount, chain tra nsfer dosage, chain reaction number of times (Even Lock returns number) the etc. when selection of such as monomer, polymerization or control.By such method, the macromolecular compound of any molecular weight can be obtained.And, macromolecular compound of the present invention commercially available towards the mechanicals of other purposes as structured material (solid) or viscosity modifier (liquid) etc. at least partially.Therefore, the large macromolecular compound of molecular weight of the present invention is easily realized.
Macromolecular compound of the present invention has at least more than one the surface functional group comprised in carbonyl, amino, carboxyl or hydroxyl.According to the kind of surface functional group, this macromolecular compound can be oil soluble or water-soluble.Therefore, macromolecular compound of the present invention can be the oil soluble macromolecular compound with carbonyl and/or amino, also can be the water-soluble high-molecular compound with carboxyl and/or hydroxyl in addition.
(2) as an example of oil soluble macromolecular compound (major portion), the polymethacrylate (PMA) shown in Fig. 1, olefin copolymer (OCP), polyisobutene (PIB) etc. are representative.In addition, styrene-isoprene block polymerization hydride (SDC) etc. is also had.These polymkeric substance can be used alone, and also can mix multiple use.Polymkeric substance is the polymkeric substance of monomer, but the hydrocarbon forming this monomer can be any one in alkane, alkene, alkynes, naphthenic hydrocarbon, aromatic hydrocarbons etc.Can be any one in straight-chain (just), branched (different), ring-type at the alkyl etc. of end bonding.
Up to the present such polymkeric substance is not also used in lubricants for use in processing, but known as full-bodied viscosity index improving agent etc., commercially available have multiple.Certainly, not commercially available polymkeric substance or the polymkeric substance developed alone also can be used as macromolecular compound of the present invention.
Oil soluble macromolecular compound with such polymkeric substance for major portion, also there is carbonyl (-C (=O)-), amino (-NH2,-NHR,-NRR ': R, R ' is hydrocarbon), the surface functional group such as carboxyl (-C (=O)-OH) or hydroxyl (-OH).As long as such surface functional group is at least more than one, but also can be multiple or multiple.Carbonyl can be the arbitrary form such as aldehyde, ketone, carboxylic acid, ester, acid amides.As mentioned above, think that such surface functional group can improve adsorptivity, the especially chemical adsorptivity of oil soluble macromolecular compound.
At this, when macromolecular compound of the present invention is the oil soluble macromolecular compound with carbonyl, its molecular weight is preferably 60,000 ~ 1,000,000, is more preferably 80,000 ~ 800,000, and more preferably 100,000 ~ 600,000.In addition, when macromolecular compound of the present invention is the oil soluble macromolecular compound with carbonyl and amino, molecular weight is preferably 30,000 ~ 1,000,000, is more preferably 50,000 ~ 500,000, and more preferably 80,000 ~ 350,000.
(3) as an example of water-soluble high-molecular compound (major portion), the polyacrylic acid (PA) shown in Fig. 2, sodium polyacrylate, polyvinyl alcohol (PVA) etc. are representative.These polymkeric substance both can be used alone, and also can mix multiple use.In this case, the monomer of formation polymkeric substance can be any one in alkane, alkene, alkynes, naphthenic hydrocarbon, aromatic hydrocarbons etc.In addition, can be any one in straight-chain (just), branched (different), ring-type at the alkyl etc. of end bonding.
Water-soluble high-molecular compound is also in the same manner as oil soluble macromolecular compound, and commercially available have multiple, can obtain the desired water-soluble high-molecular compound with various molecular weight at lower cost.Certainly, not commercially available polymkeric substance or the polymkeric substance developed alone also can be used as water-soluble high-molecular compound of the present invention.
Water-soluble high-molecular compound also with such polymkeric substance for major portion, also there is the surface functional groups such as aforesaid carboxyl, hydroxyl, carbonyl or amino.As long as such surface functional group is at least more than one, but also can be multiple or multiple.
When molecular compound of the present invention is the water-soluble high-molecular compound with carboxyl and/or hydroxyl, molecular weight is preferably 8000 ~ 1,000,000, is more preferably 20,000 ~ 900,000, and more preferably 100,000 ~ 850,000.
(4) with regard to macromolecular compound of the present invention, can utilize various polymkeric substance, its constitution element does not limit.But, macromolecular compound is not preferably containing bad environmental element (Cl, P, S etc.).That is, macromolecular compound of the present invention is preferably only made up of elements such as carbon (C), hydrogen (H), oxygen (O), nitrogen (N), not containing element in addition.Illustrative macromolecular compound of the present invention (polymkeric substance) forms by C, H, O, N etc. and does not contain bad environmental element.
" lubricants for use in processing "
(1) lubricants for use in processing of the present invention can be only made up of above-mentioned macromolecular compound, but the large macromolecular compound of molecular weight is generally high viscosity, is difficult to directly as lubricants for use in processing process.Therefore preferably the material of macromolecular compound is added with as lubricants for use in processing using in the base oil or water etc. of suitable viscosity.If oil soluble macromolecular compound, then taking base oil as solvent, if water-soluble high-molecular compound, is then solvent with water.
Macromolecular compound addition in a solvent (use level) except according to lubricants for use in processing to the kind/characteristic of the method, solvent and the macromolecular compound that supply between machined surface except difference, also different according to processing conditions (proterties etc. of the kind/characteristic of the processing such as deflection, operating force, temperature atmosphere, processing apparatus or machined material, amorphousness carbon film or machined surface) etc.
But, when lubricants for use in processing entirety is set to 100 quality %, macromolecular compound preferably containing 8 ~ 50 quality %, is more preferably 15 ~ 45 quality %, more preferably 25 ~ 40 quality %.When macromolecular compound is very few, effect is not enough, and time too much, the viscosity of lubricants for use in processing rises and treatability is declined.It should be noted that, any one during lubricants for use in processing can be the spraying of lubricants for use in processing or inflow, processing apparatus or the impregnating of machined material in lubricants for use in processing to the supply between machined surface.
In addition, if be added with the lubricants for use in processing of oil soluble macromolecular compound in base oil, then preferred kinetic viscosity at 40 DEG C is adjusted to about 5mm
2/ s ~ about 300mm
2/ s, is more preferably about 10mm
2/ s ~ about 250mm
2/ s, more preferably about 15mm
2/ s ~ about 200mm
2/ s.
(2) base oil that lubricants for use in processing uses is not particularly limited, and mineral oil, synthetic oil, grease etc. can be used alone or in combination.Mineral oil has such as paraffinic, cycloalkane etc.Synthetic oil has the hydride, isoparaffin, alkylbenzene, alkylnaphthalene, diester, polyol ester, polyether polyols, dialkyl diphenyl ether, polyphenylene oxide etc. of the hydride of such as poly-alpha-olefin, poly-alpha-olefin, isobutylene oligomer, isobutylene oligomer.Can be used in mineral oil or in synthetic oil, suitably be mixed with the base oil of different sorts material.It should be noted that, base oil itself is not also preferably containing bad environmental element.That is, base oil also preferably major portion to be made up of C and H and rest part is only made up of any one in O or N.
(3), when lubricants for use in processing of the present invention is only made up of solvent and macromolecular compound, cost degradation can be realized, therefore preferably.But, in order to improve processibility further or improve specific function, can at random containing the additive beyond macromolecular compound.Such additive such as has extreme pressure agent and wear-resistant dose etc., but does not all preferably comprise the bad environmental elements such as Cl, S, P, Mo.
" processing apparatus "
Processing apparatus is formed by forming amorphousness carbon film on the surface of base material.
(1) base material
The base material of processing apparatus selects the material, shape etc. that are suitable for machining kinds.Such as, as long as its material can form amorphousness carbon film on surface can be then the metal such as carbon steel, steel alloy, cast iron, aluminium alloy, also can be the pottery systems such as aluminum oxide, silicon nitride, silicon carbide, superhard alloy.
(2) amorphousness carbon film
The amorphousness carbon film be formed on the base material of processing apparatus is so-called diamond-like carbon film (hereinafter referred to as " DLC film ").Be formed in the not restriction such as composition, film, characteristic (hardness, Young's modulus, peel resistance etc.) of the DLC film on the surface of processing apparatus, but certainly preferably possess the suitable characteristic corresponding with the purposes of processing apparatus.
At this, the characteristic of DLC film is affected because of its composition and manufacture method.Such as, because the content of C, H and Si etc., electronic orbit are sp
2the C atom of hybridized orbital is (hereinafter referred to as " Csp
2") with electronic orbit be sp
3the C atom of hybridized orbital is (hereinafter referred to as " Csp
3") there is ratio etc. and the characteristic of DLC film changed.
This DLC film be preferably containing Si containing Si amorphousness carbon film (hereinafter referred to as " DLC-Si film ").DLC-Si film is hard coat and Frictional Slipping characteristic is also excellent.Therefore, when the surface of processing apparatus is coated by DLC-Si film, the raising of sintering resistance, the reduction of operating force, the high life etc. of processing apparatus can be realized, therefore preferably.
When enumerating an example of composition of DLC film (comprising DLC-Si film below), when film entirety is set to 100 atom %, preferably comprise the H of 0 ~ 40 atom %, more preferably 5 ~ 35 atom %, further preferred 10 ~ 30 atom %, rest part is C.If be DLC-Si film, then preferably also comprise the Si of 2 ~ 30 atom %, further preferred 4 ~ 20 atom %.
H can improve the toughness of DLC film, and can improve the adaptation with base material.But, when H is very few, its effect is not enough, and when H is too much, DLC film is softened on the contrary, makes the life-span of processing apparatus, the decline of Frictional Slipping characteristic.Si is effective with the formation of the silanol (-Si-OH) of the adsorptivity of raising macromolecular compound to the hardening of DLC film.When Si is very few, its effect is not enough, and when Si is too much, DLC film overvulcanization, makes Frictional Slipping characteristic decline on the contrary.
For the Csp in C
2with Csp
3ratio, when the total C atomicity in DLC film is set to 100%, Csp
2be preferably 20 ~ 90%, more preferably 60 ~ 75%.By there is Csp
2, the toughness of DLC film increases, and Frictional Slipping characteristic can improve.But, Csp
2time very few, its effect is not enough, Csp
2time too much, DLC film occurs softening, therefore not preferred.
In addition, the C amount in DLC film and Si amount can be passed through electron beam microanalyzer (EPMA), x-ray photoelectron spectrum analysis (XPS), Rutherford backscattering method (RBS) etc. and carry out quantitatively.In addition, H amount can be undertaken quantitatively by elastic recoil detection analysis method (ERDA).ERDA be to the helium ion beam of film surface irradiation 2MeV and the hydrogen ion utilizing semiconductor detector to detect to eject from film to measure the method for the hydrogen concentration in film.In addition, Csp
2amount, Csp
3amount can have quantitative Magic angle spinning superpower decoupling method (HD-MAS) by utilizing solid NMR to carry out is carried out quantitatively.
The film of DLC film can use CVD or the PVD methods such as such as plasma CVD method, ion plating method, sputtering method.As one example, when being described using the situation of direct-current plasma CVD method, first, reactant gases and carrier gas is imported to the vacuum oven being configured with processing apparatus (base material) is interior.Then, it is made to discharge in this vacuum oven and generate plasma body.Then, C, CH, Si etc. after making plasma body ionize are attached on coated of processing apparatus.Form the DLC film of hard thus.As the reactant gases now used, there is methane (CH
4), acetylene (C
2h
2), benzene (C
6h
6) etc. the gas of hydrocarbon.In addition, when forming DLC-Si film, Si (CH can also be used
3)
4[TMS], SiH
4, SiCl
4, SiH
2f
4deng silicon compound gas and hydrogen.Carrier gas can use the rare gas elementes such as argon gas.
When amorphousness carbon film is containing Si amorphousness carbon film, by forming silane alcohol layer in its surface, make to comprise the above-mentioned macromolecular compound with the surface functional group of polarity by surface bonding or the absorption securely containing Si amorphousness carbon film.It should be noted that, this macromolecular compound is not limited to water-soluble high-molecular compound, also can be oil soluble macromolecular compound.When having the oil soluble macromolecular compound of aforesaid surface functional group, when comprising micro-moisture in lubricants for use in processing, silane alcohol layer is easily generating containing on Si amorphousness carbon film, therefore preferably.It should be noted that, the moisture in lubricants for use in processing is preferably more than 10ppm when entirety being set to 100 quality %.
The thickness of DLC film (comprising DLC-Si film) is preferably 0.1 ~ 6 μm, more preferably 0.3 ~ 3 μm.When this thickness is too small, the weather resistance of DLC film reduces, and when thickness is excessive, reduces with the adaptation of base material, peel resistance.In addition, the hardness of DLC film is preferably more than 10GPa, is more preferably more than 15GPa, more preferably more than 20GPa.When this hardness is too small, the weather resistance of DLC film reduces, therefore not preferred.
" working method "
Said processing is in the present invention preferably the plastic workings such as forging, thinning, drawing, punching press, rolling, extruding, drawing, rolling.Especially preferably the present invention is used for large (such as, the draft: the plastic workings such as thinning processing 5 ~ 15%), drawing processing, forging of working modulus or enlarged areas rate.In addition, said processing in the present invention can be the processing such as cutting, shearing, perforate.It should be noted that, as long as processing apparatus corresponds to the kind of processing, can be various mould (comprising drift, punch die etc.), also can be cutting tool etc.
In addition, said processing in the present invention can be cold working, also can be hot-work.As long as in the scope (such as room temperature ~ 200 DEG C) that DLC film and lubricants for use in processing not too go bad, then processing temperature does not limit.It should be noted that, the form of machined material etc. are restriction not, and can be starting material, also can be intermediate materials, can also be end article.
Embodiment
Enumerate embodiment to be more specifically described the present invention.
" preparation of lubricants for use in processing "
(1) sample No.A00 ~ A111 (oil system lubricants for use in processing)
As shown in table 1, add various oil soluble macromolecular compound (additive) in base oil (sample No.A00), preparing with aluminium alloy is the multiple lubricants for use in processing of object.
Base oil uses without adding mineral oil (サ ン パ ー 110/ Japanese サ Application oil Co., Ltd. system).The kinetic viscosity of this base oil is 20.2mm at 40 DEG C
2/ second.The structure (major portion and functional group) of the oil soluble macromolecular compound of each sample and molecular weight (Mw) are shown in Table 1 in the lump.It should be noted that, as the polymethacrylate of the major portion of oil soluble macromolecular compound or olefin copolymer chemical structure as shown in Figure 1.
The addition of oil soluble macromolecular compound relative to base oil is also shown in Table 1 in the lump so that lubricants for use in processing entirety is set to 100 quality %.It should be noted that, in table 1, sample No.A00 and sample No.A01 are identical lubricants for use in processing, and sample No.A60 and sample No.A61 are identical lubricants for use in processing.
The kind of the functional group of oil soluble macromolecular compound, quantity and molecular weight carry out regulating, determining as follows.First, as the molecular weight of oil soluble macromolecular compound, measure the weight-average molecular weight based on gel permeation chromatography (GPC).Using appts now and condition determination as follows.
Device: LC-20AD (Shimadzu Scisakusho Ltd's system)
Chromatographic column: ShodexKF-806 × 2 piece, KF-802 × 1 piece
Or K-802 × 1 piece, K-806 × 2
Measure temperature: room temperature ~ 40 DEG C
Sample solution: the THF solution of 0.2 quality % or the trichloromethane of 0.3 quality %
Solution injection rate: 150 μ l
Proofing unit: RI-detector
Standard: polystyrene
Then, about functional group's (carbonyl, amino, hydroxyl) of oil soluble macromolecular compound, determined by infrared spectroscopic analysis and nucleus magnetic resonance (NMR).
It should be noted that, the lubricants for use in processing of sample No.00 ~ A111 is not all containing environmentally hazardous substance.That is, these lubricants for use in processing are in fact only made up of C, H, O or N, do not comprise as the metal (Zn etc.) of bad environmental element, heavy metal (Mo etc.), S, P, Cl etc.
(2) sample No.B11 ~ B51 (water system lubricants for use in processing)
As shown in table 2, in distilled water, add various water-soluble high-molecular compound (additive), preparing with aluminium alloy is the multiple lubricants for use in processing of object.
The structure (major portion and functional group) of each water-soluble high-molecular compound and molecular weight (Mw) are shown in Table 2 in the lump.As the polyacrylic acid of the major portion of water-soluble high-molecular compound, sodium polyacrylate or polyvinyl alcohol chemical structure as shown in Figure 2.
The addition of water-soluble high-molecular compound relative to distilled water is also shown in Table 2 in the lump so that lubricants for use in processing entirety is set to 100 quality %.It should be noted that, in table 2, sample No.B20 and sample No.B21 are identical lubricants for use in processing.
The kind of the functional group of water-soluble high-molecular compound, quantity and molecular weight also carry out regulating, determining in the same manner as aforesaid method.But, in the mensuration of the weight-average molecular weight of the water-soluble high-molecular compound based on GPC, adopt: chromatographic column: ShodexOHpak (SB-G+SB-803HQ+SB-802HQ), sample solution: the 0.2 quality %NaCl aqueous solution, solution injection rate: 100 μ l.
It should be noted that, the lubricants for use in processing of sample No.B11 ~ B51 is not all containing environmentally hazardous substance.That is, these lubricants for use in processing are in fact only made up of C, H, O or Na, do not comprise as the metal (Zn etc.) of bad environmental element, heavy metal (Mo etc.), S, P, Cl etc.
(3) sample No.C11 ~ C21 and sample No.D10 ~ 20
Prepare the lubricating oil in the past of molecular weight and commercially available processing lubricating oil.They are shown in Table 3.It should be noted that, sample No.C20 and sample No.C21 are identical processing lubricating oil.In addition, the commercially available oil shown in sample No.D10 is cold forging lubricating oil (goods name: FW439A, manufacturers: Shin Nihon Oil Co., Ltd).Commercially available oil shown in sample No.D20 is cold forging lubricating oil (goods name: タ イ タ ン ホ ー マ ー CCD220, manufacturers: chemical engineering Co., Ltd. of Toyota).
(4) sample No.E10 and E11
Prepare the sample relevant to solid lubrication overlay film.Solid lubrication overlay film is not the mobility overlay film (liquid film) utilizing the lubricants for use in processing be coated on mould (processing apparatus) etc. to be formed, but anchors at the illiquidity overlay film on the surface of machined material.It is also shown in Table 3 in the lump.
This solid lubrication overlay film is formed as follows.In the most surface (inner peripheral surface) of the machined material be made up of aluminium alloy (base material), first, silicon fluorination method is used to form the chemical conversion treatment overlay film be made up of aluminum fluoride.Thereon, carry out heat drying and form the metallic soap overlay film of zinc phosphate and the metallic soap overlay film of sodium stearate successively.On the surface of machined material, so form the solid lubrication overlay film of 3-tier architecture.In addition, even if this solid lubrication overlay film is known as also carrying out the lubricating method of cold forging etc. to aluminium alloy under utilizing lubrication wet goods to be in the past difficult to the strict condition tackled.
" evaluation method of processibility "
(1) ball-passing test
In the present embodiment, by the ball-passing test carrying out friction resistance (operating force) between mould when thinning processing waits and machined material and sintering resistance etc. can be evaluated alternatively, the oilness (processibility) of each lubricants for use in processing is evaluated.The summary of the testing apparatus 10 used in this ball-passing test as shown in Figure 3.Testing apparatus 10 is made up of container 1, drift 2, stripper punch 3 and ball 5.Container 1 is provided with in central authorities
the master mold (punch die) of the steel (JISSKH51) of the communicating pores 1a of 30mm.In this communicating pores 1a, energy intercalation or insertion become the machined material 4 of the cylindrical shape of the object of thinning processing.Drift 2 will be pressed into the inner cylinder portion 4a of setting machined material 4 in the container 1 as the ball 5 of male model.When this drift 2 moves, machined material 4 carries out thinning processing by ball 5.Stripper punch 3 supports the machined material 4 be pressed into by this drift 2 from below, and machined material 4 is remained on prescribed position.
The loadometer (not shown) of the pressing-in force (operating force) that measurement applies to drift 2 is provided with above drift 2.In addition, above drift 2, be also provided with the displacement gauge (not shown) of its amount of movement of measurement.Like this, ball 5 is pressed into and to machined material 4 carry out thinning add man-hour operating force and displacement measure via drift 2 simultaneously.
(2) machined material (workpiece)
As machined material 4, prepare external diameter:
29.9mm, internal diameter:
15.0mm, the cylinder material of the aluminium alloy (JISA6061) of height 50mm (wherein, thinning length 38mm).Machined material for test is implemented in an ar atmosphere the anneal of heating in 410 DEG C × 2 hours.
(3) ball (processing apparatus)
As above-mentioned ball 5, prepare
the steel ball (high speed tool steel: AISIM50) of 16.67mm.Below, be referred to as " untreated ball ".Also prepare the ball (hereinafter referred to as " DLC-Si film ball ") forming DLC-Si film on this untreated ball.The film forming of this DLC-Si film uses direct-current plasma CVD device, at methane (CH
4) with the mixed gas (unstripped gas) of tetramethylsilane (TMS) in carry out plasma discharge.Throughput ratio is now CH
4: TMS=1:100 (total pressure: 500Pa).Like this, the DLC-Si film that thickness is 2 μm is obtained.This DLC-Si film consist of C:66 atom %, H:30 atom %, Si:4 atom %.It should be noted that, the Si content in this film utilizes electron probe micro-analysis method (EPMA) to carry out quantitatively.In addition, H content is undertaken quantitatively by elastic recoil detection analysis method (ERDA).
(4) test conditions
Above-mentioned various lubricants for use in processing are applied to processing apparatus (ball 5) and above carry out ball-passing test.In addition, ball-passing test is carried out similarly about the machined material being formed with solid lubrication overlay film.Now, the draft of machined material 4 is 8%.Draft: the processing of 8% normally produces the strict processing of sintering.Specifically, when the inner peripheral surface of machined material 4 is not formed aforesaid solid lubrication overlay film, be produced the strict of sintering like that to force work in the past.In addition, draft (R) is the ratio of the cross-sectional area minimizing along with the machined material 4 of processing, obtains as follows (with reference to Fig. 3).
Draft R=(Db
2-Di
2) × 100/ (Dc
2-Di
2)
Db: the external diameter of ball 5
Dc: the internal diameter of container 1
Di: the internal diameter (before processing) of machined material 4
The supply of the lubricants for use in processing in ball-passing test is carried out (about using, whole test of lubricants for use in processing is all same) as follows.First, in the mixed solution of acetone 50%, hexane 50%, ultrasonic cleaning, degreaser drying are carried out to ball 5 and machined material 4.Then, lubricants for use in processing is dripped from the inner peripheral surface top of machined material 4.This machined material 4 is inserted in container 1.Then, in ball 5, suction pipe is also utilized to drip lubricants for use in processing from its top.This ball 5 is placed on the inner peripheral surface top of machined material 4.Like this, between machined surface, lubricants for use in processing is supplied.
When above-mentioned test, the press-in length (thinning length) of ball 5 is 38mm, and the press-in speed (trial speed) of ball 5 is initial velocity 200mm/s.It should be noted that, this press-in speed due to ball 5 from machined material 4 by time the resistance to deformation that produces and be decelerated to final speed 180mm/s (all same about whole tests).
" test "
Each sample of lubricants for use in processing or solid lubrication overlay film and DLC-Si film ball or untreated ball is had to carry out above-mentioned ball-passing test and the results are shown in table 1 ~ 3 of obtaining by for combination." ultimate load " in table determines the biggest ball loading of pressing in acting on drift 2.In either event, all pass through as the ball processing apparatus and can not stop in midway.But observe the ball after ball-passing test or machined material, result creates sintering.The situation not observing sintering is denoted as zero (without sintering), the situation observing sintering is denoted as × (having sintering), and is shown in the lump in table 1 ~ 3.Way produces sintered balls in test it should be noted that, even if also can throughly be sheared under state owing to being attached to ball in a part for machined material.
" evaluation "
(1) lubricants for use in processing etc. in the past
First, as shown in the sample No.C11 ~ D20 of table 3, when using lubricants for use in processing in the past, ultimate load during ball press-in all reaches more than 50kN and creates sintering.This in the untreated situation in surface of processing apparatus (ball 5) from needless to say, when there is DLC-Si film in its surface too.
On the other hand, as shown in the sample No.E10 of table 3 and sample No.E11, when the surface of machined material is formed with solid lubrication overlay film, ultimate load is about 40kN and does not produce sintering.From needless to say this exists DLC-Si film on the surface processing apparatus (ball 5), in its surperficial untreated situation too.Think that its reason is, solid lubrication overlay film is combined in the surface of machined material securely and has ductility, the lubricant film formed from by lubricants for use in processing (liquid) is in the past different, not easily produce failure of lubricating film, effectively can suppress machined material and the solid contact processing apparatus.
So known, when forcing work with low temperature to aluminium alloy, lubricants for use in processing in the past can produce sintering.This is formed with the DLC-Si film with resistance to sintering and effects such as friction minimizing etc. on the surface processing apparatus and when lubricants for use in processing has the functional group on the surface being easily adsorbed on this processing apparatus too.Therefore known, up to the present, only form solid lubrication overlay film on the surface of machined material and work is forced to aluminium alloy.
(2) situation of oil system lubricants for use in processing
Then, result as shown in Table 1 shows, when use adds oil soluble macromolecular compound large for molecular weight to obtain in base oil lubricants for use in processing, the further reduction compared with the situation of above-mentioned solid lubrication overlay film of ultimate load when ball can be made to be pressed into, can avoid the generation (sample No.A41, sample No.A51, A61 and A81 ~ A101) sintered.
These are all the situations being formed with amorphousness carbon film (DLC-Si film) on the surface of processing apparatus, and the molecular weight with surface functional group that namely lubricants for use in processing contains more than 8 quality % is the situation of the oil soluble macromolecular compound of more than 30,000.Especially, when the surface functional group of oil soluble macromolecular compound is carbonyl, its molecular weight is more than 60,000, when being more than 100,000 further, ultimate load significantly reduces and sinters.In addition, when the surface functional group of oil soluble macromolecular compound be carbonyl and amino, its molecular weight is more than 30,000, when being more than 50,000 further, ultimate load significantly reduces and sinters.
When being compared with sample No.A71 ~ A101 by sample No.A11 ~ A62, because molecular weight is same degree, when using the oil soluble macromolecular compound also except carbonyl with amino, ultimate load can be reduced further.By shown in Figure 4 for the pyrolysis gas chromatography figure (decomposition temperature: 550 DEG C) of the high molecular thermolysis GC/MS used in Sample A 81.Observe two kinds of carbonyls (in figure I, IV) and two kinds of amino (in figure II, III), the adsorption site therefore in known polymer exists multiple.Think that in two kinds of amino, there is a large amount of type III amino is make boundary film firmly major cause.Think this is because, compared with single carbonyl or single amino, by making both and depositing, the adsorptivity of oil soluble macromolecular compound in processing apparatus (especially DLC-Si film) improves.Therefore, when not having amino, adsorption site reduces and lubricity is reduced.
(3) situation of water system lubricants for use in processing
In addition, result as shown in Table 2 shows, when using the lubricants for use in processing added to by water-soluble high-molecular compound large for molecular weight in distilled water, ultimate load when ball also can be made to be pressed into reduces further than ultimate load when above-mentioned solid lubrication overlay film, can avoid the generation (sample No.B11 and B21 ~ B51) sintered.These situations be also similarly on the surface of processing apparatus, be formed with amorphousness carbon film (DLC-Si film), the molecular weight with carboxyl or hydroxyl that lubricants for use in processing contains more than 8 quality % is more than 8000, is the situation of the water-soluble high-molecular compound of more than 10,000 further.
(4) sample No.A60 is known compared with sample No.B21 with sample No.A61 or sample No.B20, even if when using identical lubricants for use in processing to process, whether there is DLC-Si film according to the surface at processing apparatus, also can there is noticeable change in the generation of sintering and ultimate load.Think that reason is as described below.DLC-Si film be present in processing apparatus surperficial time, powerful bonding force can be produced between DLC-Si film and the surface functional group of macromolecular compound, macromolecular compound is adsorbed on DLC-Si film securely, even if formation work in-process also there will not be the stable lubricant film of film rupture between machined surface.Further, even if lubricant film is at local fracture, the excellent DLC-Si film such as sintering resistance also can as film for subsequent use.
In addition, sample No.B11 is known compared with sample No.B51, when the molecular weight of macromolecular compound increases, even if reduce its addition, also can ultimate load be reduced.Say it on the contrary, even the macromolecular compound that molecular weight is relatively little, when addition is increased, also can reduce ultimate load and avoid sinter generation.But relatively can think according to both, in order to effectively reduce ultimate load, avoid sintering, the increase of the molecular weight of macromolecular compound is effective especially.
(5) use the lubricants for use in processing of sample No.A01 and sample No.A81 and the processing apparatus (ball 5) that is DLC film by surface coating from DLC-Si membrane change, similarly carry out ball-passing test, carry out the evaluation of processibility.The results are shown in table 4.It should be noted that, in table 4, corresponding to sample No.A01 and sample No.A81, adopt sample No.A02 and sample No.A82 respectively.In addition, above-mentioned DLC film is hydrogeneous DLC film (the H amount: 26%) formed by the coated process of commercially available DLC (Japan ITF Co., Ltd, ジ ア ス コ ー ト HT).
The ultimate load of sample No.A02 and sample No.A82 is 80kN and 29kN.They are roughly the same with the ultimate load of sample No.A81 with sample No.A01 respectively.Can confirm thus, even if make the surface of processing apparatus change to DLC film from DLC-Si film, also can obtain substantially same lubricity.
Label declaration
1 container 1
2 drifts 2
3 stripper punches
4 machined materials
5 balls
Claims (6)
1. a working method, it is characterized in that, lubricants for use in processing is made to form with by aluminum or aluminum alloy between coated of the processing apparatus by amorphousness carbon film coated and to contact with this coated and between the machined surface of processed machined material, this processing apparatus is utilized to process this machined material
Described lubricants for use in processing when entirety is set to 100 quality %, containing 8 ~ 50 quality % there is carboxyl or there is carboxyl and hydroxyl and molecular weight be 8000 ~ 1,000,000 water-soluble high-molecular compound.
2. working method according to claim 1, wherein, described lubricants for use in processing is not containing more than one the environmentally hazardous substance had in chlorine (Cl), phosphorus (P) or sulphur (S).
3. working method according to claim 1, wherein, described lubricants for use in processing is only made up of more than one in carbon (C), hydrogen (H), oxygen (O) or nitrogen (N).
4. working method according to claim 1, wherein, described amorphousness carbon film for containing silicon (Si) and rest part by C and H form containing Si amorphousness carbon film.
5. the working method according to claim 1 or 4, wherein, described in be processed as plastic working.
6. working method according to claim 5, wherein, described in be processed as cold plasticity processing.
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| JP2011-038664 | 2011-02-24 | ||
| JP2011038664 | 2011-02-24 | ||
| PCT/JP2012/054257 WO2012115142A1 (en) | 2011-02-24 | 2012-02-22 | Lubricant for machining, additive for machining, and machining method |
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| CN105001949B (en) * | 2015-06-05 | 2018-04-24 | 上海贝能环保科技有限公司 | A kind of biodegradation environmental protection near dry cutting liquid and preparation method thereof |
| CN106635303A (en) * | 2016-09-21 | 2017-05-10 | 广西大学 | Cold extrusion lubricant composition for 625 alloy tubular product |
| JP7033399B2 (en) * | 2017-05-15 | 2022-03-10 | 日産自動車株式会社 | Sliding mechanism |
| CN111088105A (en) * | 2019-11-12 | 2020-05-01 | 常州海纳金属助剂有限公司 | Formula and preparation method of fully-synthetic metal working fluid capable of improving lubricity |
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| CN102191116A (en) * | 2010-03-19 | 2011-09-21 | 株式会社丰田中央研究所 | Processing oil, additive for processing oil, and processing method |
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| JPH1150083A (en) * | 1997-07-30 | 1999-02-23 | Sugimura Kagaku Kogyo Kk | Lubricant for metal plastic working |
| JP2004358495A (en) * | 2003-06-03 | 2004-12-24 | Nissan Motor Co Ltd | Jig for cold drawing and lubricating oil composition used therefor |
| JP2004359813A (en) * | 2003-06-04 | 2004-12-24 | Honda Motor Co Ltd | Water-soluble lubricant film-forming agent and method of molding processing |
| JP2007136511A (en) * | 2005-11-18 | 2007-06-07 | Toyota Central Res & Dev Lab Inc | Cold working method |
| JP5436751B2 (en) * | 2006-10-13 | 2014-03-05 | 株式会社Ｕａｃｊ | Method for expanding metal pipe, pipe expanding jig used therefor, and lubricating oil used therefor |
| JP2010095792A (en) * | 2008-09-19 | 2010-04-30 | Toyota Central R&D Labs Inc | Amorphous carbon-coated member and method for working metallic material |
| CN102369268A (en) * | 2009-03-31 | 2012-03-07 | 出光兴产株式会社 | Machining fluid for brittle material and machining fluid for hard material |
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| WO2012115142A1 (en) | 2012-08-30 |
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