US20120021955A1 - Anti-seizing agent, sensor and assembly including sensor - Google Patents
Anti-seizing agent, sensor and assembly including sensor Download PDFInfo
- Publication number
- US20120021955A1 US20120021955A1 US13/244,027 US201113244027A US2012021955A1 US 20120021955 A1 US20120021955 A1 US 20120021955A1 US 201113244027 A US201113244027 A US 201113244027A US 2012021955 A1 US2012021955 A1 US 2012021955A1
- Authority
- US
- United States
- Prior art keywords
- solid lubricant
- weight
- seizing
- oxide
- agent
- 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.)
- Abandoned
Links
- 239000000314 lubricant Substances 0.000 claims abstract description 96
- 239000007787 solid Substances 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 229910052582 BN Inorganic materials 0.000 claims abstract description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 9
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 8
- 239000002199 base oil Substances 0.000 claims description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000005751 Copper oxide Substances 0.000 claims description 13
- 229910000431 copper oxide Inorganic materials 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 13
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 10
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 10
- 229910000487 osmium oxide Inorganic materials 0.000 claims description 10
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 claims description 10
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 10
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 10
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 10
- 229910003438 thallium oxide Inorganic materials 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 description 87
- 239000002184 metal Substances 0.000 description 87
- 239000007789 gas Substances 0.000 description 31
- 238000012360 testing method Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 239000000344 soap Substances 0.000 description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 5
- -1 polyol ester Chemical class 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 239000000919 ceramic Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002788 crimping Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- OYPRJOBELJOOCE-BKFZFHPZSA-N Calcium-45 Chemical compound [45Ca] OYPRJOBELJOOCE-BKFZFHPZSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2201/053—Metals; Alloys used as base material
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- C10M2201/061—Carbides; Hydrides; Nitrides
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2201/0623—Oxides; Hydroxides; Carbonates or bicarbonates used as base material
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- C—CHEMISTRY; METALLURGY
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- C10M2201/066—Molybdenum sulfide
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- C10M2201/066—Molybdenum sulfide
- C10M2201/0663—Molybdenum sulfide used as base material
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- 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
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
- C10M2209/1013—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof used as base material
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
Definitions
- the present invention relates to an anti-seizing agent.
- the present invention relates to an anti-seizing agent for preventing seizing of parts that may be exposed to high temperatures of 500° C. or higher, and a sensor and an assembly including the sensor, using the anti-seizing agent.
- the metal part includes a metal shell of a gas sensor fitted to an exhaust pipe or the like of an internal combustion engine used to detect a specified gas component in a gas to be measured, and a metal shell of a temperature sensor fitted to an exhaust pipe or the like to detect the temperature of a gas to be measured.
- the anti-seizing agent examples include a paste-like anti-seizing agent comprising a lubricant base oil and a solid lubricant contained therein, and a paste-like anti-seizing agent comprising a grease obtained by semi-solidifying a lubricant base oil with a thickening agent, and a solid lubricant contained therein (for example, see Masahisa Matsunaga, et al., Handbooks of Solid Lubrication , pp. 409-416, Saiwai Shobo Co., (1978)).
- a solid lubricant comprising a metal such as copper, aluminum or nickel, as a main component, and according to need, molybdenum disulfide or graphite combined therewith, is widely used in a paste-like anti-seizing agent that is applied to a metal part that may be exposed to high temperatures of 500° C. or higher (for example, see JP-B-8-19435).
- a paste-like anti-seizing agent containing the above-noted metals is applied to the requisite portion of a metal part to thereby form a uniform intervening film on the metal part.
- the intervening film is present between the metal part and the other part.
- the uniform intervening film formed on the metal part is localized so as to be present on only one portion in between the metal part and the other part. In such a case, a site at which the metal part and the other part are in direct contact is present, and as a result, the anti-seizing effect is not obtained.
- an anti-seizing agent having sufficient seizing preventing performance for a sensor used under severe conditions at high temperature has hitherto not yet been achieved.
- an object of the present invention to provide an anti-seizing agent that can solve the above-noted problems of the prior art, a sensor and an assembly including the sensor. That is, an object of the present invention is to provide an anti-seizing agent capable of forming an intervening film over the entire contact area between a metal part and another part even when the metal part and the other part slide, and where the metal part is exposed to a high temperature of 500° C. or higher, and a sensor and an assembly including the sensor, using the anti-seizing agent.
- an anti-seizing agent comprising a first solid lubricant containing at least one of bismuth and a bismuth compound and a second solid lubricant containing at least one of graphite, molybdenum disulfide and boron nitride, wherein the anti-seizing agent satisfies 20 weight % ⁇ a ⁇ 90 weight % and 10 weight % ⁇ d ⁇ 80 weight %, in which the sum of the contents of the first solid lubricant and the second solid lubricant in the anti-seizing agent is taken as 100 weight %, and a represents the content of the first solid lubricant and d represents the content of the second solid lubricant.
- the contents of the first solid lubricant and the second solid lubricant satisfy the relationship 0.8 ⁇ a/d ⁇ 8.
- the first solid lubricant is one of bismuth and a bismuth compound
- the anti-seizing agent further contains an antioxidant comprising at least one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, the content of the antioxidant is e satisfies 10 parts by weight ⁇ e ⁇ 100 parts by weight.
- the anti-seizing agent further contains a lubricant base oil, or a lubricant base oil and a thickening agent, and when a sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, and the content b of the lubricant base oil, or the sum b of the contents of the lubricant base oil and the thickening agent when present satisfies 90 parts by weight ⁇ b ⁇ 400 parts by weight.
- the anti-seizing agent further contains an organic resin, wherein, when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, and the content of the organic resin is c, the relationship 90 parts by weight ⁇ c ⁇ 400 parts by weight is satisfied.
- the anti-seizing agent is preferably applied to a metal part.
- the anti-seizing agent is preferably applied to an outer surface of at least the fitting part of the metal shell.
- the anti-seizing agent is preferably present between an outer surface of the fitting part of the metal shell and a surface of the exhaust pipe that fits the fitting part when the sensor and the exhaust pipe are assembled, and after heating the fitting part to a temperature of 270° C. or higher, a bismuth component of the anti-seizing agent remains on a central portion of the outer surface of the fitting part.
- the anti-seizing agent of the invention provides an excellent anti-seizing effect, particularly to a metal part that may be exposed to a high temperature of 500° C. or higher, particularly to a fitting part of a metal shell of a sensor.
- the FIGURE is a cross sectional view of the gas sensor 1 according to an embodiment of the present invention.
- the anti-seizing agent of the present invention contains a first solid lubricant and a second solid lubricant.
- the first solid lubricant comprises at least one of bismuth and a bismuth compound, as a main component.
- the present inventors consider that the anti-seizing agent can prevent seizing of a metal part by the following mechanism.
- the anti-seizing agent is applied to a requisite portion of the metal part, to thereby form a uniform intervening film.
- the anti-seizing agent is localized to one portion, and as a result, becomes present on only one portion or in isolated portions in between the metal part and the other part such that there is direct contact at other portions.
- the bismuth compound of the first solid lubricant includes bismuth oxides. These compounds are commercially available, and have an average particle diameter of 100 ⁇ m or less, and preferably 30 ⁇ m or less.
- the second solid lubricant comprises at least one of graphite, molybdenum disulfide and boron nitride.
- the present inventors consider that by further introducing the second solid lubricant, the second solid lubricant permeates simultaneously when bismuth permeates between the metal part and the other part, such that the second solid lubricant is present between the metal part and the other part. This makes it possible to further improve lubricating performance.
- the content a of the first solid lubricant and the content d of the second solid lubricant in the anti-seizing agent of the present invention satisfy 20 weight % ⁇ a ⁇ 90 weight % and 10 weight % ⁇ d ⁇ 80 weight % when a+d is taken as 100 weight %.
- a is less than 20 weight % (d exceeds 80 weight %), it becomes difficult to form the intervening film, and the anti-seizing effect deteriorates.
- a exceeds 90 weight % (d is less than 10 weight %), the amount of the second solid lubricant in the intervening film is too small, and the anti-seizing effect may not be obtained.
- the content a of the first solid lubricant and the content d of the second solid lubricant in the anti-seizing agent of the present invention preferably satisfy the relationship 0.8 ⁇ a/d ⁇ 8.
- a/d is less than 0.8, it is difficult to form the intervening film, and the anti-seizing effect may deteriorate.
- a/d exceeds 8 the amount of the second solid lubricant in the intervening film is too small, and the anti-seizing effect may not be obtained.
- the anti-seizing agent containing bismuth or a bismuth compound as the first solid lubricant when applied to a metal part, and such a metal part is exposed to a high temperature (for example, a temperature of 700° C. or higher), the metal part is oxidized, and in that case its strength deteriorates.
- a high temperature for example, a temperature of 700° C. or higher
- the present inventors consider that this is due to the following mechanism.
- bismuth in a metallic state
- oxidation reaction bismuth oxide
- the space between the metal part and the other part is an enclosed space, and bismuth oxide is easily reduced.
- the oxygen partial pressure in the enclosed space decreases
- the bismuth oxide that was the product of the oxidation reaction is reduced to bismuth metal (hereinafter also referred to as a reduction reaction).
- the bismuth resulting from the reduction reaction reacts with a passive film formed on a surface of the metal part to remove the passive film. As a result, the surface of the metal part from which the passive film has been removed is oxidized.
- the anti-seizing agent of the present invention preferably contains at least one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide.
- the oxide is preferably copper oxide.
- the content e of the oxide is preferably 10 parts by weight ⁇ e ⁇ 100 parts by weight when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight.
- e is less than 10 parts by weight, it is difficult to prevent the metal part from becoming oxidized.
- e exceeds 100 parts by weight, the component ratio of the first solid lubricant and the second solid lubricant decreases, and the anti-seizing effect may deteriorate.
- the anti-seizing agent of the invention can further contain a lubricant base oil, or a lubricant base oil and a thickening agent.
- a lubricant base oil examples include a mineral oil, a synthetic hydrocarbon oil, a polyalkylene glycol, a polyol ester, an alkyl-substituted diphenyl ether, and their mixed oils.
- the invention is not limited thereto.
- thickening agent for use in the anti-seizing agent of the present invention examples include a calcium sulfonate complex soap, lithium complex soap, calcium complex soap, lithium soap, calcium soap, organized bentonite, fine powdery silica, aliphatic diurea compounds, alicyclic diurea compounds, aromatic diurea compounds, triurea compounds and tetraurea compounds, suitable for use as a thickening agent for grease.
- the content b of the lubricant base oil, or the sum of the contents of the lubricant base oil and the thickening agent is 90 parts by weight ⁇ b ⁇ 400 parts by weight when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight.
- b is less than 90 parts by weight, fluidity of the anti-seizing agent is lost, and it is difficult to apply to a sliding surface of a part.
- b exceeds 400 parts by weight the effect of the solid lubricant is not exhibited, and therefore, it is difficult to obtain the anti-seizing effect.
- antioxidants examples include antioxidants, extreme-pressure additives, clean dispersants, rust preventives, putrefaction preventives, defoaming agents and diluents.
- the anti-seizing agent of the present invention can further contain an organic resin.
- the organic resin include bisphenol F epoxy resins, bisphenol A epoxy resins, silicone resins and TYRANNO resins (trade name of Ube Industries, Ltd., comprising titanocarbosilane and polyalkylphenylsiloxane).
- the invention is not limited thereto.
- the content c of the organic resin is 90 parts by weight ⁇ c ⁇ 400 parts by weight when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight.
- c is less than 90 parts by weight, fluidity of the anti-seizing agent is lost, and it is difficult to apply to a sliding surface of a part.
- c exceeds 400 parts by weight, the effect of the solid lubricant is not exhibited, and therefore, it is difficult to obtain the anti-seizing effect.
- antioxidants examples include ultraviolet absorbers, wetting dispersants, surface modifiers and curing agents.
- the anti-seizing agent of the present invention can be used in a screw portion of a nut member for fitting a gas sensor to an exhaust pipe as shown in JP-A-11-190720, or in a gas sensor 1 described hereinafter, as an anti-seizing agent.
- the gas sensor 1 of the present embodiment is an example of one embodiment, and the invention should not be construed as being limited thereto.
- the gas sensor 1 (oxygen sensor) is fitted to an exhaust pipe of automobiles and detects concentration of oxygen in an exhaust gas.
- the FIGURE is a sectional view showing the overall structure of the gas sensor 1 .
- the gas sensor 1 is provided with a sensor element 2 that is formed into a bottomed cylindrical shape having its leading end closed, a ceramic heater 3 inserted in the sensor element 2 , and a metal shell 4 that holds the sensor element 2 inside the metal shell 4 .
- a sensor element 2 that is formed into a bottomed cylindrical shape having its leading end closed
- a ceramic heater 3 inserted in the sensor element 2
- a metal shell 4 that holds the sensor element 2 inside the metal shell 4 .
- the sensor element 2 has a solid electrolyte body 21 having oxygen ion conductivity, an internal electrode 22 made of Pt or a Pt alloy formed on an inner surface of the solid electrolyte body 21 , and an external electrode 23 formed on an outer surface of the solid electrolyte body 21 .
- a flange portion 24 projecting toward an outer diameter direction is provided at a central position on an axial line of the sensor element 2 .
- the ceramic heater 3 is formed in a rod shape, and is provided with a heating portion 31 having a heating element inside thereof.
- the metal shell 4 has a screw portion 41 (corresponding to the fitting portion of the invention) for fitting the gas sensor 1 to the exhaust pipe, and a hexagonal portion 42 for engaging a fitting tool when fitting to the exhaust pipe.
- a gasket 5 is provided on the leading end side of the hexagonal portion 42 .
- the surface of the screw portion 41 is coated with the anti-seizing agent of the present invention, thereby preventing seizing with the exhaust pipe even when the screw portion is fitted to the exhaust pipe and the metal shell 4 is exposed to a high temperature.
- the metal shell 4 is provided with a fitting shoulder 43 projecting toward an inside diameter direction on an inner circumference of the leading end side, and a supporting member 7 made of alumina is supported on the fitting shoulder 43 through a packing 6 .
- the flange portion 24 of the sensor element 2 is supported on the supporting member 7 through a packing 8 .
- a filling member 9 is arranged between the inner surface of the metal shell 4 at the back-end side of the supporting member 7 and the outer surface of the sensor element 2 , and a sleeve 100 and a circular ring 110 are successively interpolated on the back-end side of the filling member 9 .
- a leading end side of an inner cylinder member 130 is inserted in the inside of the back-end side of the metal shell 4 .
- the inner cylinder member 130 is fixed to the metal shell 4 by crimping a back-end side 44 of the metal shell 4 in an inner leading end direction so that the leading end side contacts the circular ring 110 .
- a structure in which the filling member 9 is compressed and filled through the sleeve 100 is obtained by crimping the back-end side 44 of the metal shell 4 , and by means of this structure, the sensor element 2 is held inside the cylindrical metal shell 4 in an air-tight state.
- Plural air introduction holes 131 are formed on the back-end side of the inner cylinder member 130 with a predetermined distance along a circumferential direction.
- a cylindrical filter 140 is arranged so as to cover the air introduction holes 131 of the inner cylinder member 130 .
- an outer cylinder member 150 is arranged so as to cover the filter 140 .
- Plural air introduction holes 151 are formed on the position of the outer cylinder member 150 corresponding to the filter 140 with a predetermined distance along a circumferential direction.
- a separator 160 is arranged inside the inner cylinder member 130 .
- the separator 160 has a separator lead line through-hole 161 for inserting element lead wires 170 and 180 , and heater lead wires 190 and 200 penetrate from the leading end side to the back-end side.
- each of the lead wires 170 , 180 , 190 and 200 has a structure such that a conductive wire is covered with an insulation coating film comprising a resin, and the back-end side of the conductive wire is connected to a connector terminal provided on a connector.
- the leading end side of the conductive wire of the element lead wire 170 is crimped together with the back-end side of a terminal fitting 210 outwardly fitted to the outer surface of the sensor element 2
- the leading end side of the conductive wire of the element lead wire 180 is crimped together with the back-end side of the terminal fitting 220 press fitted to the inner surface of the sensor element 2 .
- the element lead wire 170 is electrically connected to the external electrode 23 of the sensor element 2
- the element lead wire 180 is electrically connected to the internal electrode 22 .
- the leading end sides of the conductive wires of the heater lead wires 190 and 200 are connected to a pair of terminal fittings 230 , respectively, joined to a heating element of the ceramic heater 3 .
- a sealing material 240 having excellent heat resistance comprising a fluorine rubber or the like is fixed to the back-end side of the separator 160 by crimping the outer cylinder member 150 .
- Four lead wire insertion holes 241 are formed on the sealing member 240 so as to penetrate in an axial line direction.
- Test Examples 1 to 33 were prepared by blending a first solid lubricant, a second solid lubricant, a lubricant base oil, a lubricant base oil plus a thickening agent, an organic resin, copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide in the blending proportions shown in Table 1.
- the preparation method of the Test Example is not particularly limited.
- the Test Example can generally be prepared by mixing and stirring a first solid lubricant, a second solid lubricant, a lubricant base oil, a lubricant base oil+a thickening agent, an organic resin, copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and if necessary, conducting dispersion treatment using a three-roll mill or a homogenizer.
- a first solid lubricant, a second solid lubricant, a lubricant base oil, a lubricant base oil plus a thickening agent, an organic resin, copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide are all commercially available, industrial products.
- the numerical value in Table 1 shows a blending proportion (weight % or part by weight).
- the average particle diameter of graphite in Table 1 is 30 ⁇ m or less.
- the metal shell 4 is made of SUS 430, and the sample nut is made of SUS 409L.
- This evaluation was conducted using a metal shell 4 prior to fitting to the gas sensor 1 , and by screwing the metal shell 4 (no gas sensor) into the nut.
- the metal shell 4 and the nut thus unified were then heated in an electric oven at 500° C. or 700° C. for 100 hours.
- the unified product was cooled to room temperature, and the metal shell 4 was loosened from the nut. This test procedure was applied to ten test samples.
- ⁇ Degree of seizing is 0%. O: Degree of seizing exceeds 0% but is 5% or less. ⁇ : Degree of seizing exceeds 5% but is 20% or less. X: Degree of seizing exceeds 20%.
- Test Examples 1 to 33 prepared as shown in Table 1 was applied to the screw portion 41 of the metal shell 4 used in the gas sensor 1 described above, and the metal shell 4 was screwed into a sample nut with a torque of 60 N ⁇ m.
- the metal shell 4 is made of SUS 430, and the sample nut is made of SUS 409L.
- This evaluation was conducted using a metal shell 4 prior to fitting to the gas sensor 1 , and by screwing the metal shell 4 (no gas sensor) into the nut.
- the metal shell 4 and the nut thus unified were then heated in an electric oven at 500° C. or 700° C. for 100 hours.
- the unified product was cooled to room temperature, and the metal shell 4 was loosened from the nut.
- the metal shell 4 was divided into halves, and a cross section of the screw portion 41 was subjected to component mapping with EDS (Energy Dispersive X-ray Spectroscopy). Of the component mappings, a thickness from which oxygen was detected was calculated as an oxide film thickness. An evaluation of an oxide film thickness of 20 ⁇ m or greater was graded X, and an oxide film thickness of less than 20 ⁇ m was graded o. The evaluation results are shown in Table 2.
- Test Example 16 the copper oxide content e was 9.4, and the corrosion resistance was poor.
- Test Example 23 the copper oxide content e was 109, and the corrosion resistance was poor.
- Test Example 24 the lubricant base oil content b was 80, and the workability was poor.
- the lubricant base oil content b was 462, and the corrosion resistance was poor.
- Test Example 29 the organic resin content c was 80, and the workability was poor.
- Test Example 33 the organic resin content c was 462, and the corrosion resistance was poor.
- the bismuth component was found to be present on substantially the entire outer surface thereof.
- the anti-seizing agent evenly covered the outer surface of the screw portion 41 .
- the anti-seizing agent covering the outer surface of the screw portion 41 became unevenly distributed. That is, relatively large amounts of the anti-seizing agent were present at the top of threads and at the bottom of the valleys of the screw portion 41 , while being scarce or lacking in the middle between the top of the threads and the bottom of the valleys of the screw portion 41 .
- the bismuth in the anti-seizing agent melts and penetrates the entire interface between the screw portion 41 and the nut, including the middle between the top of the threads and the bottom of the valleys of the screw portion 41 .
- the screw portion 41 and the nut are in direct contact, thereby preventing seizing between the screw portion 41 and the nut when sliding one surface against the other.
- the bismuth component of the anti-seizing agent remains on a central portion of the outer surface of the fitting part,” as used herein means that when the central portion surface of the outer surface (in the case of the screw portion 41 , the central portion on the surface between thread and valley) is subjected to EDS analysis, a peak of bismuth is observed, and therefore, the bismuth component is determined to be present.
Abstract
An anti-seizing agent including: a first solid lubricant containing at least one of bismuth and a bismuth compound; and a second solid lubricant containing at least one of graphite, molybdenum disulfide and boron nitride. The anti-seizing agent satisfies the relationships 20 weight %≦a≦90 weight % and 10 weight %≦d≦80 weight %, in which a sum of the contents of the first solid lubricant and the second solid lubricant in the anti-seizing agent is taken as 100 weight %, and a represents a content of the first solid lubricant and d represents a content of the second solid lubricant.
Description
- This application is a Rule 53(b) Divisional of U.S. patent application Ser. No. 11/604,760 filed Nov. 28, 2006, which claims benefit to Japanese Patent Application No. 2005-341440 filed Nov. 28, 2005 and Japanese Patent Application No. 2006-259640 filed Sep. 25, 2006. The above-noted applications are incorporated herein by reference in their entirety.
- 1. Field of the Invention
- The present invention relates to an anti-seizing agent. Particularly, the present invention relates to an anti-seizing agent for preventing seizing of parts that may be exposed to high temperatures of 500° C. or higher, and a sensor and an assembly including the sensor, using the anti-seizing agent.
- 2. Description of the Related Art
- An anti-seizing agent is often applied to a screw portion of a metal part to prevent seizing, and the part is then used for fabrication. The metal part includes a metal shell of a gas sensor fitted to an exhaust pipe or the like of an internal combustion engine used to detect a specified gas component in a gas to be measured, and a metal shell of a temperature sensor fitted to an exhaust pipe or the like to detect the temperature of a gas to be measured. Examples of the anti-seizing agent include a paste-like anti-seizing agent comprising a lubricant base oil and a solid lubricant contained therein, and a paste-like anti-seizing agent comprising a grease obtained by semi-solidifying a lubricant base oil with a thickening agent, and a solid lubricant contained therein (for example, see Masahisa Matsunaga, et al., Handbooks of Solid Lubrication, pp. 409-416, Saiwai Shobo Co., (1978)).
- Conventionally, a solid lubricant comprising a metal such as copper, aluminum or nickel, as a main component, and according to need, molybdenum disulfide or graphite combined therewith, is widely used in a paste-like anti-seizing agent that is applied to a metal part that may be exposed to high temperatures of 500° C. or higher (for example, see JP-B-8-19435).
- The mechanism which allows these metals to prevent seizing is considered to be as follows. A paste-like anti-seizing agent containing the above-noted metals is applied to the requisite portion of a metal part to thereby form a uniform intervening film on the metal part. When the metal part is fabricated with another part, the intervening film is present between the metal part and the other part. As a result, when the metal part is exposed to high temperatures and then disassembled from the other part (when the metal part and the other part slide), seizing between the metal part and the other part is prevented by the lubricating action due to the softness of the metals constituting the intervening film.
- 3. Problems to be Solved by the Invention
- However, when the metal part is fabricated with another part, the uniform intervening film formed on the metal part is localized so as to be present on only one portion in between the metal part and the other part. In such a case, a site at which the metal part and the other part are in direct contact is present, and as a result, the anti-seizing effect is not obtained.
- For this reason, there is a need for an anti-seizing agent which forms an intervening film over the entire surface between a metal part and the other part even when the metal part and the other part slide, thereby exhibiting the desired anti-seizing effect.
- In particular, an anti-seizing agent having sufficient seizing preventing performance for a sensor used under severe conditions at high temperature has hitherto not yet been achieved.
- It is therefore an object of the present invention to provide an anti-seizing agent that can solve the above-noted problems of the prior art, a sensor and an assembly including the sensor. That is, an object of the present invention is to provide an anti-seizing agent capable of forming an intervening film over the entire contact area between a metal part and another part even when the metal part and the other part slide, and where the metal part is exposed to a high temperature of 500° C. or higher, and a sensor and an assembly including the sensor, using the anti-seizing agent.
- The above object of the present invention has been achieved by providing an anti-seizing agent comprising a first solid lubricant containing at least one of bismuth and a bismuth compound and a second solid lubricant containing at least one of graphite, molybdenum disulfide and boron nitride, wherein the anti-seizing agent satisfies 20 weight %≦a≦90 weight % and 10 weight %≦d≦80 weight %, in which the sum of the contents of the first solid lubricant and the second solid lubricant in the anti-seizing agent is taken as 100 weight %, and a represents the content of the first solid lubricant and d represents the content of the second solid lubricant.
- In a preferred embodiment, the contents of the first solid lubricant and the second solid lubricant satisfy the relationship 0.8≦a/d≦8.
- In yet another preferred embodiment, the first solid lubricant is one of bismuth and a bismuth compound, the anti-seizing agent further contains an antioxidant comprising at least one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, the content of the antioxidant is e satisfies 10 parts by weight≦e≦100 parts by weight.
- In yet another preferred embodiment, the anti-seizing agent further contains a lubricant base oil, or a lubricant base oil and a thickening agent, and when a sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, and the content b of the lubricant base oil, or the sum b of the contents of the lubricant base oil and the thickening agent when present satisfies 90 parts by weight≦b≦400 parts by weight.
- In yet another preferred embodiment, the anti-seizing agent further contains an organic resin, wherein, when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, and the content of the organic resin is c, the relationship 90 parts by weight≦c≦400 parts by weight is satisfied.
- The anti-seizing agent is preferably applied to a metal part.
- In particular, in a sensor having a detecting element that detects the state of a gas to be measured, and a metal shell that holds the detecting element, the metal shell having a fitting part that fits the detecting element to an exhaust pipe when exposing the detecting element to a gas to be measured, the anti-seizing agent is preferably applied to an outer surface of at least the fitting part of the metal shell.
- Further, in an assembly including a sensor having a detecting element that detects a state of gas to be measured, and a metal shell that holds the detecting element; and an exhaust pipe that fits a fitting part formed on the metal shell of the sensor to expose the detecting element to a gas to be measured, the anti-seizing agent is preferably present between an outer surface of the fitting part of the metal shell and a surface of the exhaust pipe that fits the fitting part when the sensor and the exhaust pipe are assembled, and after heating the fitting part to a temperature of 270° C. or higher, a bismuth component of the anti-seizing agent remains on a central portion of the outer surface of the fitting part.
- The anti-seizing agent of the invention provides an excellent anti-seizing effect, particularly to a metal part that may be exposed to a high temperature of 500° C. or higher, particularly to a fitting part of a metal shell of a sensor.
- The FIGURE is a cross sectional view of the
gas sensor 1 according to an embodiment of the present invention. - Reference numerals used to identify various structural features in the drawings include the following.
- 1 Gas sensor
- 2 Gas sensor element
- 3 Heater
- 4 Metal shell
- 7 Supporting member
- 9 Filling member
- 100 Sleeve
- 120 Protector
- 130 Inner cylinder member
- 140 Filter
- 150 Outer cylinder member
- 160 Separator
- 240 Sealing member
- 136 Filter part
- 200, 300 Filter covering member
- 201, 301 Covering part
- 202, 302 Opening
- 203, 303 Insertion portion
- The anti-seizing agent of the present invention contains a first solid lubricant and a second solid lubricant.
- The first solid lubricant comprises at least one of bismuth and a bismuth compound, as a main component. The present inventors consider that the anti-seizing agent can prevent seizing of a metal part by the following mechanism. The anti-seizing agent is applied to a requisite portion of the metal part, to thereby form a uniform intervening film. When the metal part is fabricated with another part, the anti-seizing agent is localized to one portion, and as a result, becomes present on only one portion or in isolated portions in between the metal part and the other part such that there is direct contact at other portions. However, when the metal part is exposed to a high temperature, bismuth in the anti-seizing agent melts and permeates over the entire interface between the metal part and the other part, thereby again forming an intervening film. This makes it possible to prevent seizing by the lubricating action of the intervening film when sliding the metal part against the other part.
- The bismuth compound of the first solid lubricant includes bismuth oxides. These compounds are commercially available, and have an average particle diameter of 100 μm or less, and preferably 30 μm or less.
- The second solid lubricant comprises at least one of graphite, molybdenum disulfide and boron nitride. The present inventors consider that by further introducing the second solid lubricant, the second solid lubricant permeates simultaneously when bismuth permeates between the metal part and the other part, such that the second solid lubricant is present between the metal part and the other part. This makes it possible to further improve lubricating performance.
- The content a of the first solid lubricant and the content d of the second solid lubricant in the anti-seizing agent of the present invention satisfy 20 weight %≦a≦90 weight % and 10 weight %≦d≦80 weight % when a+d is taken as 100 weight %. When a is less than 20 weight % (d exceeds 80 weight %), it becomes difficult to form the intervening film, and the anti-seizing effect deteriorates. On the other hand, when a exceeds 90 weight % (d is less than 10 weight %), the amount of the second solid lubricant in the intervening film is too small, and the anti-seizing effect may not be obtained.
- The content a of the first solid lubricant and the content d of the second solid lubricant in the anti-seizing agent of the present invention preferably satisfy the relationship 0.8≦a/d≦8. When a/d is less than 0.8, it is difficult to form the intervening film, and the anti-seizing effect may deteriorate. On the other hand, when a/d exceeds 8, the amount of the second solid lubricant in the intervening film is too small, and the anti-seizing effect may not be obtained.
- Of the anti-seizing agents of the present invention, when the anti-seizing agent containing bismuth or a bismuth compound as the first solid lubricant is applied to a metal part, and such a metal part is exposed to a high temperature (for example, a temperature of 700° C. or higher), the metal part is oxidized, and in that case its strength deteriorates.
- The present inventors consider that this is due to the following mechanism. When exposed to a high temperature of 700° C. or higher, bismuth (in a metallic state) is oxidized to form a bismuth oxide (hereinafter also referred to as an oxidation reaction). However, the space between the metal part and the other part is an enclosed space, and bismuth oxide is easily reduced. When the oxygen partial pressure in the enclosed space decreases, the bismuth oxide that was the product of the oxidation reaction is reduced to bismuth metal (hereinafter also referred to as a reduction reaction). The bismuth resulting from the reduction reaction reacts with a passive film formed on a surface of the metal part to remove the passive film. As a result, the surface of the metal part from which the passive film has been removed is oxidized.
- Therefore, when bismuth or a bismuth oxide is present as the first solid lubricant, the anti-seizing agent of the present invention preferably contains at least one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide. By employing such an oxide, an oxygen component is supplied to the enclosed space, to thereby prevent the oxygen partial pressure in the enclosed space from lowering. Consequently, the reduction reaction can be suppressed. As a result, oxidation of the metal part can be prevented. Considering safety in production, cost and the like, the oxide is preferably copper oxide. The content e of the oxide is preferably 10 parts by weight≦e≦100 parts by weight when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight. When e is less than 10 parts by weight, it is difficult to prevent the metal part from becoming oxidized. On the other hand, when e exceeds 100 parts by weight, the component ratio of the first solid lubricant and the second solid lubricant decreases, and the anti-seizing effect may deteriorate.
- The anti-seizing agent of the invention can further contain a lubricant base oil, or a lubricant base oil and a thickening agent. Examples of the lubricant base oil include a mineral oil, a synthetic hydrocarbon oil, a polyalkylene glycol, a polyol ester, an alkyl-substituted diphenyl ether, and their mixed oils. However, the invention is not limited thereto.
- Examples of the thickening agent for use in the anti-seizing agent of the present invention include a calcium sulfonate complex soap, lithium complex soap, calcium complex soap, lithium soap, calcium soap, organized bentonite, fine powdery silica, aliphatic diurea compounds, alicyclic diurea compounds, aromatic diurea compounds, triurea compounds and tetraurea compounds, suitable for use as a thickening agent for grease.
- The content b of the lubricant base oil, or the sum of the contents of the lubricant base oil and the thickening agent is 90 parts by weight≦b≦400 parts by weight when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight. When b is less than 90 parts by weight, fluidity of the anti-seizing agent is lost, and it is difficult to apply to a sliding surface of a part. On the other hand, when b exceeds 400 parts by weight, the effect of the solid lubricant is not exhibited, and therefore, it is difficult to obtain the anti-seizing effect.
- Examples of other additives that may be contained in the anti-seizing agent include antioxidants, extreme-pressure additives, clean dispersants, rust preventives, putrefaction preventives, defoaming agents and diluents.
- The anti-seizing agent of the present invention can further contain an organic resin. Examples of the organic resin include bisphenol F epoxy resins, bisphenol A epoxy resins, silicone resins and TYRANNO resins (trade name of Ube Industries, Ltd., comprising titanocarbosilane and polyalkylphenylsiloxane). However, the invention is not limited thereto.
- The content c of the organic resin is 90 parts by weight≦c≦400 parts by weight when the sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight. When c is less than 90 parts by weight, fluidity of the anti-seizing agent is lost, and it is difficult to apply to a sliding surface of a part. On the other hand, when c exceeds 400 parts by weight, the effect of the solid lubricant is not exhibited, and therefore, it is difficult to obtain the anti-seizing effect.
- Examples of other additives that may be contained in the anti-seizing agent include ultraviolet absorbers, wetting dispersants, surface modifiers and curing agents.
- The anti-seizing agent of the present invention can be used in a screw portion of a nut member for fitting a gas sensor to an exhaust pipe as shown in JP-A-11-190720, or in a
gas sensor 1 described hereinafter, as an anti-seizing agent. Thegas sensor 1 of the present embodiment is an example of one embodiment, and the invention should not be construed as being limited thereto. The gas sensor 1 (oxygen sensor) is fitted to an exhaust pipe of automobiles and detects concentration of oxygen in an exhaust gas. The FIGURE is a sectional view showing the overall structure of thegas sensor 1. - As shown in the FIGURE, the
gas sensor 1 is provided with asensor element 2 that is formed into a bottomed cylindrical shape having its leading end closed, aceramic heater 3 inserted in thesensor element 2, and ametal shell 4 that holds thesensor element 2 inside themetal shell 4. Of directions along the axis of thesensor element 2 shown in the FIGURE, the side toward the leading end to be exposed to a gas to be measured (exhaust gas) (closed side, downside in the drawing) is called a “leading end side,” and the side toward the direction opposite the above side (upside in the drawing) is called a “back-end side.” - The
sensor element 2 has asolid electrolyte body 21 having oxygen ion conductivity, aninternal electrode 22 made of Pt or a Pt alloy formed on an inner surface of thesolid electrolyte body 21, and an external electrode 23 formed on an outer surface of thesolid electrolyte body 21. Aflange portion 24 projecting toward an outer diameter direction is provided at a central position on an axial line of thesensor element 2. Theceramic heater 3 is formed in a rod shape, and is provided with aheating portion 31 having a heating element inside thereof. - The
metal shell 4 has a screw portion 41 (corresponding to the fitting portion of the invention) for fitting thegas sensor 1 to the exhaust pipe, and ahexagonal portion 42 for engaging a fitting tool when fitting to the exhaust pipe. Agasket 5 is provided on the leading end side of thehexagonal portion 42. The surface of thescrew portion 41 is coated with the anti-seizing agent of the present invention, thereby preventing seizing with the exhaust pipe even when the screw portion is fitted to the exhaust pipe and themetal shell 4 is exposed to a high temperature. - The
metal shell 4 is provided with afitting shoulder 43 projecting toward an inside diameter direction on an inner circumference of the leading end side, and a supportingmember 7 made of alumina is supported on thefitting shoulder 43 through apacking 6. Theflange portion 24 of thesensor element 2 is supported on the supportingmember 7 through apacking 8. A fillingmember 9 is arranged between the inner surface of themetal shell 4 at the back-end side of the supportingmember 7 and the outer surface of thesensor element 2, and asleeve 100 and acircular ring 110 are successively interpolated on the back-end side of the fillingmember 9. - A
double protector 120 made of a metal, having plural gas inlet holes 121, is fitted to the leading end side of themetal shell 4. - A leading end side of an
inner cylinder member 130 is inserted in the inside of the back-end side of themetal shell 4. Theinner cylinder member 130 is fixed to themetal shell 4 by crimping a back-end side 44 of themetal shell 4 in an inner leading end direction so that the leading end side contacts thecircular ring 110. A structure in which the fillingmember 9 is compressed and filled through thesleeve 100 is obtained by crimping the back-end side 44 of themetal shell 4, and by means of this structure, thesensor element 2 is held inside thecylindrical metal shell 4 in an air-tight state. - Plural air introduction holes 131 are formed on the back-end side of the
inner cylinder member 130 with a predetermined distance along a circumferential direction. Acylindrical filter 140 is arranged so as to cover the air introduction holes 131 of theinner cylinder member 130. Further, anouter cylinder member 150 is arranged so as to cover thefilter 140. Plural air introduction holes 151 are formed on the position of theouter cylinder member 150 corresponding to thefilter 140 with a predetermined distance along a circumferential direction. - A
separator 160 is arranged inside theinner cylinder member 130. Theseparator 160 has a separator lead line through-hole 161 for insertingelement lead wires wires - Further, each of the
lead wires element lead wire 170 is crimped together with the back-end side of aterminal fitting 210 outwardly fitted to the outer surface of thesensor element 2, and the leading end side of the conductive wire of theelement lead wire 180 is crimped together with the back-end side of the terminal fitting 220 press fitted to the inner surface of thesensor element 2. In this manner, theelement lead wire 170 is electrically connected to the external electrode 23 of thesensor element 2, and theelement lead wire 180 is electrically connected to theinternal electrode 22. On the other hand, the leading end sides of the conductive wires of theheater lead wires terminal fittings 230, respectively, joined to a heating element of theceramic heater 3. - A sealing
material 240 having excellent heat resistance comprising a fluorine rubber or the like is fixed to the back-end side of theseparator 160 by crimping theouter cylinder member 150. Four lead wire insertion holes 241 are formed on the sealingmember 240 so as to penetrate in an axial line direction. - The present invention is described in greater detail by reference to the following Examples and Comparative Examples, but those are illustrative embodiments, and the invention should not be construed as being limited thereto.
- Test Examples 1 to 33 were prepared by blending a first solid lubricant, a second solid lubricant, a lubricant base oil, a lubricant base oil plus a thickening agent, an organic resin, copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide in the blending proportions shown in Table 1. The preparation method of the Test Example is not particularly limited. The Test Example can generally be prepared by mixing and stirring a first solid lubricant, a second solid lubricant, a lubricant base oil, a lubricant base oil+a thickening agent, an organic resin, copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and if necessary, conducting dispersion treatment using a three-roll mill or a homogenizer.
- A first solid lubricant, a second solid lubricant, a lubricant base oil, a lubricant base oil plus a thickening agent, an organic resin, copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide are all commercially available, industrial products.
-
TABLE 1 Test Example 1 2 3 4 5 6 7 8 9 10 11 Bismuth*1 7 10 18 20 20 20 20 Bismuth oxide*2 20 20 0 20 Graphite*3 33 30 22 20 20 Molybdenum disulfide*4 20 20 20 Boron nitride*5 20 20 20 Mineral oil*6 45 45 45 45 45 45 45 Calcium sulfonate complex soap*7 5 5 5 5 5 5 5 Bisphenol F epoxy resin*8 40.2 40.2 40.2 40.2 Amine adduct curing agent*9 1.8 1.8 1.8 1.8 Dicyandiamide curing agent*10 2.7 2.7 2.7 2.7 Reactive diluent*11 5.3 5.3 5.3 5.3 Copper oxide*12 10 10 10 10 10 10 10 10 10 10 10 Thallium oxide*13 Iridium oxide*14 Osmium oxide*14 Rhodium oxide*14 Ruthenium oxide*14 a 17.5 25 45 50 50 50 50 50 50 50 50 d 82.5 75 55 50 50 50 50 50 50 50 50 a/d 0.2 0.3 0.8 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 e 25 25 25 25 25 25 25 25 25 25 25 b 125 125 12 125 125 125 125 0 0 0 0 c 0 0 0 0 0 0 0 125 125 125 125 Test Example 12 13 14 15 16 17 18 19 20 21 22 Bismuth*1 30 35 36 37 16 16 16 16 16 Bismuth oxide*2 16 16 Graphite*3 10 5 4 3 16 16 16 16 16 Molybdenum disulfide*4 16 Boron nitride*5 16 Mineral oil*6 45 45 45 45 57 56 53 53 34 Calcium sulfonate complex soap*7 5 5 5 5 8 7 7 7 4 Bisphenol F epoxy resin*8 48.2 48.2 Amine adduct curing agent*9 2.2 2.2 Dicyandiamide curing agent*10 3.2 3.2 Reactive diluent*11 6.4 6.4 Copper oxide*12 10 10 10 10 3 5 8 8 8 8 30 Thallium oxide*13 Iridium oxide*14 Osmium oxide*14 Rhodium oxide*14 Ruthenium oxide*14 a 75 87.5 90 92.5 50 50 50 50 50 50 50 d 25 12.5 10 7.5 50 50 50 50 50 50 50 a/d 3.0 7.0 9.0 12.3 1.0 1.0 1.0 1.0 1.0 1.0 1.0 e 25 25 25 25 9.4 15.6 25 25 25 25 93.8 b 125 125 125 125 203.1 196.9 187.5 187.5 0 0 118.8 c 0 0 0 0 0 0 0 0 187.5 187.5 0 Test Example 23 24 25 26 27 28 29 30 31 32 33 Bismuth*1 16 25 23 10 8 8 25 23 10 9 8 Bismuth oxide*2 Graphite*3 16 25 23 10 9 8 25 23 10 9 8 Molybdenum disulfide*4 Boron nitride*5 Mineral oil*6 30 35 39 62 64 65 Calcium sulfonate complex soap*7 3 5 5 8 8 8 Bisphenol F epoxy resin*8 32.5 35.5 56.3 57.9 59.5 Amine adduct curing agent*9 1.4 1.5 2.5 2.6 2.7 Dicyandiamide curing agent*10 2.2 2.4 3.8 3.9 4 Reactive diluent*11 4.2 4.6 7.4 7.6 7.8 Copper oxide*12 35 10 10 10 10 10 10 10 10 10 10 Thallium oxide*13 Iridium oxide*14 Osmium oxide*14 Rhodium oxide*14 Ruthenium oxide*14 a 50 50 50 50 50 50 50 50 50 50 50 d 50 50 50 50 50 50 50 50 50 50 50 a/d 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 e 109.4 20 21.7 50 55.6 62.5 20 21.7 50 55.6 62.5 b 103.1 80 95.7 350 400 462.5 0 0 0 0 0 c 0 0 0 0 0 0 80 95.7 350 400 462.5 *1Product of Sumitomo Metal Mining Co., Ltd. *2Product of Nissan Kagaku Sangyo Co., Ltd. *3Scale-like graphite *4Product of IPROS Corporation *5DENKA BORON NITRIDE HGP, a product of Denki Kagaku Kogyo K.K. *6SNH-46, a product of Sankyo Yuka Kogyo K.K. *7G-2000, a product of Krompton *8EPICRON 830S, a product of Dainippon Ink and Chemicals, Incorporated *9AMICURE PN-23, a product of Ajinomoto Fine-Techno Co., Inc. *10AMICURE AH-154, a product of Ajinomoto Fine-Techno Co., Inc. *11Alkylene monoglycidyl ether having viscosity at 25° C. of 6.5 to 9.0 mPa · s and an epoxy equivalent of 280 to 320 g/eq. *12Cupric oxide, a product of Nissan Kagaku Sangyo Co., Ltd. *13Commercially available reagent (made in USA) *14Commercially available reagent (made in Japan). - The numerical value in Table 1 shows a blending proportion (weight % or part by weight). The average particle diameter of graphite in Table 1 is 30 μm or less.
- (Evaluation of Workability)
- An evaluation was conducted in which about 60 mg of each of the anti-seizing agents of Test Examples 1 to 33 shown in Table 1 above were applied to the
screw portion 41 of themetal shell 4 used in thegas sensor 1 described above. The evaluation results are shown in Table 2. - (Evaluation of Anti-Seizing Effect)
- About 60 mg of the anti-seizing agent was applied to the
screw portion 41 of themetal shell 4 used in thegas sensor 1 described above, and themetal shell 4 was screwed into a sample nut with a torque of 60 N·m. Themetal shell 4 is made of SUS 430, and the sample nut is made of SUS 409L. This evaluation was conducted using ametal shell 4 prior to fitting to thegas sensor 1, and by screwing the metal shell 4 (no gas sensor) into the nut. Themetal shell 4 and the nut thus unified were then heated in an electric oven at 500° C. or 700° C. for 100 hours. The unified product was cooled to room temperature, and themetal shell 4 was loosened from the nut. This test procedure was applied to ten test samples. The proportion of the number ofmetal shells 4 exhibiting seizing is expressed by percentage, and indicated as a degree of seizing (%). The term “exhibiting seizing” indicates a state in which when themetal shell 4 is loosened by hand using a torque trench, themetal shell 4 is not unscrewed from the nut. In this case, when themetal shell 4 is loosened with further strong force, the thread of thescrew portion 41 of themetal shell 4 is crushed. The evaluation was conducted on the basis of the degree of seizing as follows. - ⊚: Degree of seizing is 0%.
O: Degree of seizing exceeds 0% but is 5% or less.
Δ: Degree of seizing exceeds 5% but is 20% or less.
X: Degree of seizing exceeds 20%. - The evaluation results of Test Examples 1 to 33 are shown in Table 2.
- (Evaluation of Corrosion Resistance)
- About 60 mg of each of Test Examples 1 to 33 prepared as shown in Table 1 was applied to the
screw portion 41 of themetal shell 4 used in thegas sensor 1 described above, and themetal shell 4 was screwed into a sample nut with a torque of 60 N·m. Themetal shell 4 is made of SUS 430, and the sample nut is made of SUS 409L. This evaluation was conducted using ametal shell 4 prior to fitting to thegas sensor 1, and by screwing the metal shell 4 (no gas sensor) into the nut. Themetal shell 4 and the nut thus unified were then heated in an electric oven at 500° C. or 700° C. for 100 hours. The unified product was cooled to room temperature, and themetal shell 4 was loosened from the nut. Themetal shell 4 was divided into halves, and a cross section of thescrew portion 41 was subjected to component mapping with EDS (Energy Dispersive X-ray Spectroscopy). Of the component mappings, a thickness from which oxygen was detected was calculated as an oxide film thickness. An evaluation of an oxide film thickness of 20 μm or greater was graded X, and an oxide film thickness of less than 20 μm was graded o. The evaluation results are shown in Table 2. -
TABLE 2 Test Example 1 2 3 4 5 6 7 8 9 10 11 Seizing 500° C. Δ Δ ⊚ ⊚ ◯ ◯ ◯ ⊚ ◯ ⊚ ◯ Seizing 700° C. Δ ◯ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚ ⊚ ⊚ Corrosion resistance ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Workability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Example 12 13 14 15 16 17 18 19 20 21 22 Seizing 500° C. ⊚ ◯ Δ Δ ⊚ ⊚ ⊚ ◯ ◯ ◯ ◯ Seizing 700° C. ⊚ ⊚ ◯ Δ ⊚ ⊚ ⊚ ◯ ⊚ ◯ ◯ Corrosion resistance ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Workability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Test Example 23 24 25 26 27 28 29 30 31 32 33 Seizing 500° C. Δ — ◯ ◯ ◯ Δ — ◯ ◯ ◯ Δ Seizing 700° C. ◯ — ◯ ◯ ◯ ◯ — ⊚ ⊚ ◯ ◯ Corrosion resistance ◯ — ◯ ◯ ◯ ◯ — ◯ ◯ ◯ ◯ Workability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ - In the seizing agents of Test Examples 1 to 33 of the present invention using at least one of bismuth and bismuth oxide as the first solid lubricant; graphite, molybdenum disulfide or boron nitride as the second solid lubricant; a mineral oil as the lubricant base oil, a grease obtained by thickening the mineral oil with calcium sulfonate complex soap as a thickening agent, or bisphenol F epoxy resin; and at least one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, Test Example 1 having a graphite content of as large as d=82.4, exhibited a poor anti-seizing effect. In Test Example 15 where the bismuth content was as large as a=92.5, the anti-seizing effect was also found to be poor. In Test Example 2, the ratio of graphite to bismuth was a/d=0.3, and the anti-seizing effect was slightly poor. In Test Example 14 the ratio of graphite to bismuth was a/d=9, and the anti-seizing effect was slightly poor. In Test Example 16 the copper oxide content e was 9.4, and the corrosion resistance was poor. In Test Example 23 the copper oxide content e was 109, and the corrosion resistance was poor. In Test Example 24 the lubricant base oil content b was 80, and the workability was poor. In Test Example 28 the lubricant base oil content b was 462, and the corrosion resistance was poor. In Test Example 29 the organic resin content c was 80, and the workability was poor. In Test Example 33 the organic resin content c was 462, and the corrosion resistance was poor.
- When the screw portion of the
gas sensor 1 was analyzed, the bismuth component was found to be present on substantially the entire outer surface thereof. Before the screw portion of thegas sensor 1 and the nut were fastened, the anti-seizing agent evenly covered the outer surface of thescrew portion 41. However, when the screw portion was fitted to the nut, the anti-seizing agent covering the outer surface of thescrew portion 41 became unevenly distributed. That is, relatively large amounts of the anti-seizing agent were present at the top of threads and at the bottom of the valleys of thescrew portion 41, while being scarce or lacking in the middle between the top of the threads and the bottom of the valleys of thescrew portion 41. After being heated to a temperature of 270° C. or higher, i.e. 700° C., the bismuth in the anti-seizing agent melts and penetrates the entire interface between thescrew portion 41 and the nut, including the middle between the top of the threads and the bottom of the valleys of thescrew portion 41. As a result, there is no area where thescrew portion 41 and the nut are in direct contact, thereby preventing seizing between thescrew portion 41 and the nut when sliding one surface against the other. The term “the bismuth component of the anti-seizing agent remains on a central portion of the outer surface of the fitting part,” as used herein means that when the central portion surface of the outer surface (in the case of thescrew portion 41, the central portion on the surface between thread and valley) is subjected to EDS analysis, a peak of bismuth is observed, and therefore, the bismuth component is determined to be present. - This application is based on Japanese Patent Application JP 2005-341440, filed Nov. 28, 2005, and Japanese Patent Application JP 2006-259640, filed Sep. 25, 2006, the entire contents of which are hereby incorporated by reference, the same as if set forth at length.
Claims (7)
1. An anti-seizing agent comprising:
a first solid lubricant containing at least one of bismuth and a bismuth compound; and
a second solid lubricant containing at least one of graphite, molybdenum disulfide and boron nitride,
wherein the anti-seizing agent satisfies 20 weight %≦a≦90 weight % and 10 weight %≦d≦80 weight %, in which a sum of the contents of the first solid lubricant and the second solid lubricant in the anti-seizing agent is taken as 100 weight %, and a represents the content of the first solid lubricant and d represents the content of the second solid lubricant.
2. The anti-seizing agent as claimed in claim 1 , wherein the contents of the first solid lubricant and the second solid lubricant satisfy 0.8≦a/d≦8.
3. The anti-seizing agent as claimed in claim 1 , wherein the first solid lubricant is one of bismuth and a bismuth compound, the anti-seizing agent further comprises an antioxidant comprising at least one of copper oxide, thallium oxide, iridium oxide, osmium oxide, rhodium oxide and ruthenium oxide, and when a sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, a content of the antioxidant e satisfies 10 parts by weight≦e≦100 parts by weight.
4. The anti-seizing agent as claimed in claim 1 , further comprising a lubricant base oil, or further comprising a lubricant base oil and a thickening agent, wherein, when a sum of the contents of the first solid lubricant and the second solid lubricant is taken 100 parts by weight, a sum b of the contents of lubricant base oil and the thickening agent which is optionally present satisfies 90 parts by weight≦b≦400 parts by weight.
5. The anti-seizing agent as claimed in claim 1 , further comprising an organic resin, wherein, when a sum of the contents of the first solid lubricant and the second solid lubricant is taken as 100 parts by weight, and a content of the organic resin is c, the relationship 90 parts by weight≦c≦400 parts by weight is satisfied.
6. (canceled)
7. (canceled)
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US13/244,027 US20120021955A1 (en) | 2005-11-28 | 2011-09-23 | Anti-seizing agent, sensor and assembly including sensor |
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JP2005341440 | 2005-11-28 | ||
JP2005-341440 | 2005-11-28 | ||
JP2006259640A JP2007169596A (en) | 2005-11-28 | 2006-09-25 | Seizure-preventing agent, sensor and sensor-attaching structure |
JP2006-259640 | 2006-09-25 | ||
US11/604,760 US8518862B2 (en) | 2005-11-28 | 2006-11-28 | Anti-seizing agent, sensor and assembly including sensor |
US13/244,027 US20120021955A1 (en) | 2005-11-28 | 2011-09-23 | Anti-seizing agent, sensor and assembly including sensor |
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US13/244,027 Abandoned US20120021955A1 (en) | 2005-11-28 | 2011-09-23 | Anti-seizing agent, sensor and assembly including sensor |
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JP (1) | JP2007169596A (en) |
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JP5048293B2 (en) * | 2005-11-28 | 2012-10-17 | 日本特殊陶業株式会社 | Sensor and sensor mounting structure |
JP2007169596A (en) | 2005-11-28 | 2007-07-05 | Ngk Spark Plug Co Ltd | Seizure-preventing agent, sensor and sensor-attaching structure |
-
2006
- 2006-09-25 JP JP2006259640A patent/JP2007169596A/en not_active Withdrawn
- 2006-11-23 BR BRPI0604741A patent/BRPI0604741B1/en active IP Right Grant
- 2006-11-28 DE DE102006056127A patent/DE102006056127A1/en not_active Ceased
- 2006-11-28 US US11/604,760 patent/US8518862B2/en active Active
- 2006-11-28 FR FR0655139A patent/FR2893950B1/en active Active
-
2010
- 2010-08-09 FR FR1056513A patent/FR2945047B1/en active Active
-
2011
- 2011-09-23 US US13/244,027 patent/US20120021955A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9428708B2 (en) | 2011-09-30 | 2016-08-30 | Ngk Spark Plug Co., Ltd. | Lubricating coating composition and attachment component for internal combustion engine |
US9410468B2 (en) | 2013-04-30 | 2016-08-09 | Ngk Spark Plug Co., Ltd. | Temperature sensor attachment member treated with dry film lubricant |
Also Published As
Publication number | Publication date |
---|---|
US20070123436A1 (en) | 2007-05-31 |
FR2893950B1 (en) | 2010-10-08 |
FR2945047A1 (en) | 2010-11-05 |
DE102006056127A1 (en) | 2007-06-06 |
FR2945047B1 (en) | 2011-12-09 |
FR2893950A1 (en) | 2007-06-01 |
BRPI0604741A (en) | 2007-11-06 |
BRPI0604741B1 (en) | 2016-03-08 |
US8518862B2 (en) | 2013-08-27 |
JP2007169596A (en) | 2007-07-05 |
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Legal Events
Date | Code | Title | Description |
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |