US20010027170A1 - Lubricant combination and process for the preparation thereof - Google Patents
Lubricant combination and process for the preparation thereof Download PDFInfo
- Publication number
- US20010027170A1 US20010027170A1 US09/769,321 US76932101A US2001027170A1 US 20010027170 A1 US20010027170 A1 US 20010027170A1 US 76932101 A US76932101 A US 76932101A US 2001027170 A1 US2001027170 A1 US 2001027170A1
- Authority
- US
- United States
- Prior art keywords
- lubricant
- particles
- bis
- process according
- combination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000314 lubricant Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract 3
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 23
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- LJZKUDYOSCNJPU-UHFFFAOYSA-N dotetracontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O LJZKUDYOSCNJPU-UHFFFAOYSA-N 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- BHIXMQGGBKDGTH-UHFFFAOYSA-N hexatetracontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O BHIXMQGGBKDGTH-UHFFFAOYSA-N 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- -1 arachinamide Chemical compound 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- YLWQQYRYYZPZLJ-UHFFFAOYSA-N 12-hydroxy-n-[2-(12-hydroxyoctadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC(O)CCCCCC YLWQQYRYYZPZLJ-UHFFFAOYSA-N 0.000 claims description 2
- QBRWHTJFGYJOBO-UHFFFAOYSA-N 2,2-dioctadecylhexanediamide Chemical compound CCCCCCCCCCCCCCCCCCC(C(N)=O)(CCCC(N)=O)CCCCCCCCCCCCCCCCCC QBRWHTJFGYJOBO-UHFFFAOYSA-N 0.000 claims description 2
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 claims description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 2
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 claims description 2
- WOQDVIVTFCTQCE-UHFFFAOYSA-N pentacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WOQDVIVTFCTQCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- 229940037312 stearamide Drugs 0.000 claims description 2
- RFNVCIBXKHIIJQ-UHFFFAOYSA-N tetratriacontanediamide Chemical group NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O RFNVCIBXKHIIJQ-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000012255 powdered metal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
-
- 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
- C10M5/00—Solid or semi-solid compositions containing as the essential lubricating ingredient mineral lubricating oils or fatty oils and their use
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/22—Carboxylic acids or their salts
- C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/68—Amides; Imides
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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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/06—Particles of special shape or size
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/1203—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/1213—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/1253—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
- C10M2207/163—Naphthenic acids 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/18—Tall oil acids
- C10M2207/183—Tall oil acids 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/20—Rosin acids
- C10M2207/203—Rosin acids 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/24—Epoxidised acids; Ester derivatives thereof
- C10M2207/243—Epoxidised acids; Ester derivatives thereof 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/08—Amides
- C10M2215/0806—Amides 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/10—Amides of carbonic or haloformic acids
- C10M2215/1006—Amides of carbonic or haloformic acids 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/28—Amides; Imides
- C10M2215/285—Amides; Imides 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
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- 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
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- 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
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- 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
- C10N2040/32—Wires, ropes or cables lubricants
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- 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
- C10N2040/34—Lubricating-sealants
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- 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
- C10N2040/36—Release agents or mold release agents
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- 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
- C10N2040/38—Conveyors or chain belts
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- 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
- C10N2040/40—Generators or electric motors in oil or gas winning field
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- 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
- C10N2040/42—Flashing oils or marking oils
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- 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
- C10N2040/44—Super vacuum or supercritical use
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- 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
- C10N2040/50—Medical uses
Definitions
- This invention relates to a lubricant combination for powder metallurgy and to the manufacture and use of this lubricant combination. More particularly the invention concerns a lubricant combination including at least two lubricants.
- Powdered metals for example, powdered iron
- powdered iron are used to make small, fairly intricate parts, for example, gears.
- the fabrication of such metallic parts by powdered metal technology involves the following steps:
- the powdered metal is blended with a lubricant and other additives to form a mixture
- the obtained mixture is poured into a mould and compacted to form a part using a high pressure, usually of the order of 200 to 1000 MPa,
- the part is subjected to a high temperature to decompose and remove the lubricant and to cause all the particles of metal in the part to sinter together
- Lubricants are added to metal powders for several reasons. One reason is that they facilitate the production of compacts for sintering by lubricating the interior of the powder during the compaction process. Through selection of proper lubricants higher densities, which is often required, can be obtained. Furthermore, the lubricants provide the necessary lubricating action that is needed to eject the compacted part out of the die. Insufficient lubrication will result in wear and scuffing at the die surface through the excessive friction during the ejection, resulting in premature die failure. The problems with insufficient lubrication can be solved in two ways; either by increasing the amount of the lubricant or by selecting more efficient lubricants.
- the method of making the new lubricants more efficient involves the steps of
- the main objective of the first lubricant is to impart good lubricating properties to the powder, which will give higher densities and low ejection forces, whereas the main objective of the second lubricant is to provide a metal powder mixture having good powder properties, such as high flow rates and uniform filling of the die, which in turn gives high productivity and even density distribution in a compacted part.
- lubricants within the first group are fatty acid bis-amides, such as ethylene-bis-palmitinamide, ethylene-bis-stearamide, ethylene-bis-arachinamide, ethylene-bis-behenamide, hexylene-bis-palmitinamide, hexylene-bis-stearamide, hexylene-bis-arachinamide, hexylene-bis-behenamide, ethylene-bis-12-hydroxystearamide, distearyladipamide etc. and fatty acid monoamides, such as palmitinamide, stearamide, arachinamide, behenamide, oleiamide. Additionally the first lubricant may include a solid mixture of two or more lubricants.
- the second lubricant may be selected from the group consisting of metal soaps, such as zinc stearate, lithium stearate.
- the particles of the lubricant(s) are as close to spherical shape as possible as the spherical shape leads to the highest flow rate and apparent density.
- the first lubricant has an average particle size which is larger than that of the second lubricant. More particularly it is preferred that the average particle size of the first lubricant is 2-3 times larger than that of the second lubricant and most particularly the average particle size of the first lubricant is at least 15 ⁇ m and the second lubricant has an average particle size of at most 6 ⁇ m. Additionally it has been found that the amount of the first lubricant preferably should be between 60 and 90% by weight of the total lubricant combination.
- One way of providing conditions for adhering the lubricant particles involves heating the particles of the first and/or the second lubricant at a temperature and for a period of time sufficient for achieving a physical bonding between the particles of the first and the second lubricant.
- the concentration of the lubricant combination plus optional conventional solid lubricants is suitably in the range of 0.1 to 5% by weight, preferably from 0.3 to 1% by weight.
- Metal powders of interest is preferably an iron based powder.
- iron based powders are alloyed iron based powder, such as a prealloyed iron powder or an iron powder having the alloying elements diffusion-bonded to the iron particles.
- the iron based powder may also be a mixture of an essentially pure iron powder and the alloying elements, which are eg selected from the group consisting of Ni, Cu, cr, Mo, Mn, P, Si, V and W.
- the various amounts of the different alloying elements are between 0 and 10, preferably between 1 and 6% by weight of Ni, between 0 and 8, preferably between 1 and 5% by weight of cu, between 0 and 25, preferably between 0 and 12% by weight of Cr, between 0 and 5, preferably between 0 and 3 by weight of Mo, between 0 and 1, preferably between 0 and 0.6% by weight of P, between 0 and 5, preferably between 0 and 2% by weight of Si, between 0 and 3, preferably between 0 and 1% by weight of V and between 0 and 10, preferably between 0 and 4% by weight of W.
- the iron based powder may be an atomised powder or a sponge iron powder.
- the particle size of the iron based powder is selected depending on the final use of the sintered product.
- the lubricant combination according to the invention is thus a surface modified lubricant having a core of one first lubricant wherein the core surface is coated of particles of second lubricant.
- a comparison between this lubricant combination and a physical mixture of the same lubricants shows that the properties of the lubricant combination are superior. The same is true also for a molten and subsequently solidified mixture of the same lubricants.
- the following non limiting example illustrates the invention.
- Iron powder compositions were prepared by using lubricant compositions prepared by different methods.
- the lubricants were composed of the common recipe of 80% ethylene-bis-stearamide (EBS available as Hoechst Wachs from Clariant AG, Germany) having a melting point of about 145° C., and 20% zinc stearate (available from Megret, UK) having a melting point of about 130° C.
- the total lubricant content was 0.8% by weight in all cases.
- the iron powder was ASC 100.29 (available from Höganäs AB, Sweden) and 0.5% by weight of graphite was mixed with the iron powder and lubricant.
- the first lubricant composition was prepared by micronizing the two ingredients separately down to average particle sizes below 30 ⁇ m and subsequently admixing to the iron powder mixture.
- the second lubricant composition was prepared by first melting together and solidifying the lubricants, followed by micronization and admixing to the iron powder mixture as described above.
- the third lubricant was prepared by adhering the zinc stearate particles to the surface of the EBS through heating of EBS particles to temperatures where partial melting of added zinc stearate particles occurs. A stable mechanical bond between the particles was thus achieved, with the larger EBS particles essentially covered by smaller zinc stearate particles. Also in this case the particle size was below about 30 ⁇ m.
- the Filling index is a measure of the relative difference in filling density (FD) between two cavities of different geometry; While the length and the depth of the cavities are the same (30 mm and 30 mm respectively), one cavity has a width of 13 mm and the other a width of 2 mm. The wider cavity gives larger filling density, and the filling index is defined as:
- the Filling index is approximately the same as the relative difference in green density obtained when a powder is pressed in a cavity having cavities of the same geometry as described above, i.e. with sections of different slit widths, e.g. 13 and 2 mm.
- TABLE 1 Apparent Filling Hall Flow Density Index (s/50 g) (g/cm 3 ) (%) Lubricant according to the 26.6 3.18 6.67 present invention Physical mixture of EBS/Zinc No flow 3.09 7.65 Stearate Molten, solidified and 30.5 3.07 8.34 micronized mixture of EBS/Zinc Stearate
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Description
- This invention relates to a lubricant combination for powder metallurgy and to the manufacture and use of this lubricant combination. More particularly the invention concerns a lubricant combination including at least two lubricants.
- Powdered metals, for example, powdered iron, are used to make small, fairly intricate parts, for example, gears. The fabrication of such metallic parts by powdered metal technology involves the following steps:
- the powdered metal is blended with a lubricant and other additives to form a mixture,
- the obtained mixture is poured into a mould and compacted to form a part using a high pressure, usually of the order of 200 to 1000 MPa,
- the part is ejected from the mould,
- the part is subjected to a high temperature to decompose and remove the lubricant and to cause all the particles of metal in the part to sinter together
- and the part is cooled, after which it is ready for use.
- Lubricants are added to metal powders for several reasons. One reason is that they facilitate the production of compacts for sintering by lubricating the interior of the powder during the compaction process. Through selection of proper lubricants higher densities, which is often required, can be obtained. Furthermore, the lubricants provide the necessary lubricating action that is needed to eject the compacted part out of the die. Insufficient lubrication will result in wear and scuffing at the die surface through the excessive friction during the ejection, resulting in premature die failure. The problems with insufficient lubrication can be solved in two ways; either by increasing the amount of the lubricant or by selecting more efficient lubricants. By increasing the amount of lubricant, an undesired side effect is however encountered in that the gain in density through better “internal lubrication” is reversed by the increasing volume of the lubricant. The better choice would then be to select more efficient lubricants. This has however been found to be a difficult task as efficient lubricants tend to have negative effects on the powder properties of the mixture.
- Another possibility would be to look for new ways to combine or use presently used lubricants in order to make them more efficient. The present invention concerns such a new combination of presently used lubricants. The concept of the invention is of course not limited to presently used and known lubricant but is applicable also to future lubricants.
- According to the invention the method of making the new lubricants more efficient involves the steps of
- selecting a first and a second lubricant powder
- mixing the lubricant powders and
- subjecting the mixture to conditions for adhering the particles of the second lubricant to the particles of the first lubricant in order to form a lubricant combination of aggregate particles having a core of the first lubricant, the surface of the core being coated with particles of the second lubricant.
- The main objective of the first lubricant is to impart good lubricating properties to the powder, which will give higher densities and low ejection forces, whereas the main objective of the second lubricant is to provide a metal powder mixture having good powder properties, such as high flow rates and uniform filling of the die, which in turn gives high productivity and even density distribution in a compacted part.
- Examples of lubricants within the first group are fatty acid bis-amides, such as ethylene-bis-palmitinamide, ethylene-bis-stearamide, ethylene-bis-arachinamide, ethylene-bis-behenamide, hexylene-bis-palmitinamide, hexylene-bis-stearamide, hexylene-bis-arachinamide, hexylene-bis-behenamide, ethylene-bis-12-hydroxystearamide, distearyladipamide etc. and fatty acid monoamides, such as palmitinamide, stearamide, arachinamide, behenamide, oleiamide. Additionally the first lubricant may include a solid mixture of two or more lubricants.
- The second lubricant may be selected from the group consisting of metal soaps, such as zinc stearate, lithium stearate.
- It is preferred that the particles of the lubricant(s) are as close to spherical shape as possible as the spherical shape leads to the highest flow rate and apparent density.
- It is furthermore preferred that the first lubricant has an average particle size which is larger than that of the second lubricant. More particularly it is preferred that the average particle size of the first lubricant is 2-3 times larger than that of the second lubricant and most particularly the average particle size of the first lubricant is at least 15 μm and the second lubricant has an average particle size of at most 6 μm. Additionally it has been found that the amount of the first lubricant preferably should be between 60 and 90% by weight of the total lubricant combination.
- One way of providing conditions for adhering the lubricant particles involves heating the particles of the first and/or the second lubricant at a temperature and for a period of time sufficient for achieving a physical bonding between the particles of the first and the second lubricant.
- When mixed with metal powders, the concentration of the lubricant combination plus optional conventional solid lubricants, is suitably in the range of 0.1 to 5% by weight, preferably from 0.3 to 1% by weight.
- Metal powders of interest is preferably an iron based powder. Examples of iron based powders are alloyed iron based powder, such as a prealloyed iron powder or an iron powder having the alloying elements diffusion-bonded to the iron particles. The iron based powder may also be a mixture of an essentially pure iron powder and the alloying elements, which are eg selected from the group consisting of Ni, Cu, cr, Mo, Mn, P, Si, V and W. The various amounts of the different alloying elements are between 0 and 10, preferably between 1 and 6% by weight of Ni, between 0 and 8, preferably between 1 and 5% by weight of cu, between 0 and 25, preferably between 0 and 12% by weight of Cr, between 0 and 5, preferably between 0 and 3 by weight of Mo, between 0 and 1, preferably between 0 and 0.6% by weight of P, between 0 and 5, preferably between 0 and 2% by weight of Si, between 0 and 3, preferably between 0 and 1% by weight of V and between 0 and 10, preferably between 0 and 4% by weight of W.
- The iron based powder may be an atomised powder or a sponge iron powder.
- The particle size of the iron based powder is selected depending on the final use of the sintered product.
- The lubricant combination according to the invention is thus a surface modified lubricant having a core of one first lubricant wherein the core surface is coated of particles of second lubricant. A comparison between this lubricant combination and a physical mixture of the same lubricants shows that the properties of the lubricant combination are superior. The same is true also for a molten and subsequently solidified mixture of the same lubricants. The following non limiting example illustrates the invention.
- Iron powder compositions were prepared by using lubricant compositions prepared by different methods. The lubricants were composed of the common recipe of 80% ethylene-bis-stearamide (EBS available as Hoechst Wachs from Clariant AG, Germany) having a melting point of about 145° C., and 20% zinc stearate (available from Megret, UK) having a melting point of about 130° C. The total lubricant content was 0.8% by weight in all cases. The iron powder was ASC 100.29 (available from Höganäs AB, Sweden) and 0.5% by weight of graphite was mixed with the iron powder and lubricant.
- The first lubricant composition was prepared by micronizing the two ingredients separately down to average particle sizes below 30 μm and subsequently admixing to the iron powder mixture.
- The second lubricant composition was prepared by first melting together and solidifying the lubricants, followed by micronization and admixing to the iron powder mixture as described above.
- The third lubricant was prepared by adhering the zinc stearate particles to the surface of the EBS through heating of EBS particles to temperatures where partial melting of added zinc stearate particles occurs. A stable mechanical bond between the particles was thus achieved, with the larger EBS particles essentially covered by smaller zinc stearate particles. Also in this case the particle size was below about 30 μm.
- After mixing, the powder properties of the iron powder compositions were characterised, including the Hall Flow, Apparent density and the Filling index. The Filling index is a measure of the relative difference in filling density (FD) between two cavities of different geometry; While the length and the depth of the cavities are the same (30 mm and 30 mm respectively), one cavity has a width of 13 mm and the other a width of 2 mm. The wider cavity gives larger filling density, and the filling index is defined as:
- Filling Index (%)=(Fdmax−FDmin)/Fdmax
- Theoretically, the Filling index is approximately the same as the relative difference in green density obtained when a powder is pressed in a cavity having cavities of the same geometry as described above, i.e. with sections of different slit widths, e.g. 13 and 2 mm.
TABLE 1 Apparent Filling Hall Flow Density Index (s/50 g) (g/cm3) (%) Lubricant according to the 26.6 3.18 6.67 present invention Physical mixture of EBS/Zinc No flow 3.09 7.65 Stearate Molten, solidified and 30.5 3.07 8.34 micronized mixture of EBS/Zinc Stearate - From the results presented in Table 1, it is evident that the modification of the EBS lubricant with zinc stearate according to the present invention gives valuable advantages in powder properties compared with conventional methods of physical mixing of the separate components into a powder mixture, or by adding a melted together and micronized lubricant composition. The flow rate is increased and the apparent density is raised. Furthermore, a more even filling is experienced, which is expected to give a more even density distribution in a complex pressed part compared with mixture made with conventional lubricants containing EBS or some other cohesive lubricants as a main constituent.
Claims (10)
Applications Claiming Priority (4)
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SE9904367A SE9904367D0 (en) | 1999-12-02 | 1999-12-02 | Lubricant combination and process for the preparation thereof |
SE9904367 | 1999-12-02 | ||
SE9904367-1 | 1999-12-03 | ||
PCT/SE2000/002397 WO2001040416A1 (en) | 1999-12-02 | 2000-12-01 | Lubricant combination and process for the preparation thereof |
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PCT/SE2000/002397 Continuation WO2001040416A1 (en) | 1999-12-02 | 2000-12-01 | Lubricant combination and process for the preparation thereof |
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US20010027170A1 true US20010027170A1 (en) | 2001-10-04 |
US6413919B2 US6413919B2 (en) | 2002-07-02 |
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US09/769,321 Expired - Lifetime US6413919B2 (en) | 1999-12-02 | 2001-01-26 | Lubricant combination and process for the preparation thereof |
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US (1) | US6413919B2 (en) |
EP (1) | EP1252274B1 (en) |
JP (2) | JP4572050B2 (en) |
KR (1) | KR100738739B1 (en) |
CN (1) | CN1225526C (en) |
AU (1) | AU2035401A (en) |
BR (1) | BR0015951B1 (en) |
CA (1) | CA2394183C (en) |
DE (1) | DE60026167T2 (en) |
ES (1) | ES2254254T3 (en) |
MX (1) | MXPA02005448A (en) |
RU (1) | RU2254362C2 (en) |
SE (1) | SE9904367D0 (en) |
TW (1) | TW524849B (en) |
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WO2015177300A1 (en) * | 2014-05-23 | 2015-11-26 | Höganäs Ab (Publ) | New product |
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SE9904367D0 (en) * | 1999-12-02 | 1999-12-02 | Hoeganaes Ab | Lubricant combination and process for the preparation thereof |
US7150775B2 (en) | 2001-05-21 | 2006-12-19 | React-Nti, Llc | Powder metal mixture including micronized cellulose fibers |
US7261759B2 (en) * | 2001-05-21 | 2007-08-28 | React-Nti, Llc | Powder metal mixture including micronized starch |
US7153594B2 (en) * | 2002-12-23 | 2006-12-26 | Höganäs Ab | Iron-based powder |
US7329302B2 (en) * | 2004-11-05 | 2008-02-12 | H. L. Blachford Ltd./Ltee | Lubricants for powdered metals and powdered metal compositions containing said lubricants |
US8075710B2 (en) | 2005-06-15 | 2011-12-13 | Höganäs Ab | Soft magnetic composite materials |
JP5388581B2 (en) * | 2005-12-30 | 2014-01-15 | ホガナス アクチボラゲット | Lubricants for powder metallurgy compositions |
DE602006018532D1 (en) | 2006-03-24 | 2011-01-05 | Postech Acad Ind Found | STATIONARY PHASE AND PILLAR USING CUCURBITURIL-BOUNDED SILVER GEL, AND METHOD FOR SEPARATING TAXOL USING THE PILLAR |
JP5170390B2 (en) * | 2007-03-22 | 2013-03-27 | Jfeスチール株式会社 | Iron-based mixed powder for powder metallurgy |
JP2010007176A (en) * | 2008-05-27 | 2010-01-14 | Jfe Steel Corp | Iron-based powdery mixture for powder metallurgy |
JP5223547B2 (en) * | 2008-09-05 | 2013-06-26 | Jfeスチール株式会社 | Iron-based mixed powder for powder metallurgy |
EP2370220B1 (en) | 2008-11-26 | 2017-01-04 | Höganäs Ab (publ) | Lubricant for powder metallurgical compositions |
JP5856018B2 (en) * | 2012-06-29 | 2016-02-09 | 八弘綱油株式会社 | High drop point semi-solid composition |
JP5841089B2 (en) * | 2013-03-13 | 2016-01-13 | 株式会社豊田中央研究所 | Molding powder, lubricant concentrated powder, and method for producing metal member |
WO2015035515A1 (en) | 2013-09-12 | 2015-03-19 | National Research Council Of Canada | Lubricant for powder metallurgy and metal powder compositions containing said lubricant |
CN103554141B (en) * | 2013-10-15 | 2015-10-21 | 中南大学 | A kind of core-shell rare-earth complexes and its preparation method and application |
KR102248462B1 (en) * | 2020-09-08 | 2021-05-06 | 장기태 | Lubricant and manufacturing method for the same |
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JP3509540B2 (en) * | 1997-03-19 | 2004-03-22 | Jfeスチール株式会社 | Iron-based powder mixture for powder metallurgy excellent in fluidity and moldability, method for producing the same, and method for producing a compact |
JP3903520B2 (en) * | 1997-04-14 | 2007-04-11 | Jfeスチール株式会社 | Iron-based powder mixture for powder metallurgy and method for producing the same |
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JP4018223B2 (en) * | 1998-02-19 | 2007-12-05 | 株式会社神戸製鋼所 | Composite lubricant for powder metallurgy, mixed powder for powder metallurgy with excellent dimensional stability, and method for producing a sintered product using the mixed powder |
SE9904367D0 (en) * | 1999-12-02 | 1999-12-02 | Hoeganaes Ab | Lubricant combination and process for the preparation thereof |
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Cited By (3)
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WO2015177300A1 (en) * | 2014-05-23 | 2015-11-26 | Höganäs Ab (Publ) | New product |
CN106660118A (en) * | 2014-05-23 | 2017-05-10 | 霍加纳斯股份有限公司 | New product |
US20170189959A1 (en) * | 2014-05-23 | 2017-07-06 | Hoganas Ab (Publ) | New product |
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RU2254362C2 (en) | 2005-06-20 |
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DE60026167D1 (en) | 2006-04-27 |
EP1252274B1 (en) | 2006-02-22 |
KR100738739B1 (en) | 2007-07-18 |
KR20020068362A (en) | 2002-08-27 |
US6413919B2 (en) | 2002-07-02 |
BR0015951B1 (en) | 2011-07-12 |
JP2010265454A (en) | 2010-11-25 |
JP2003515661A (en) | 2003-05-07 |
SE9904367D0 (en) | 1999-12-02 |
ES2254254T3 (en) | 2006-06-16 |
WO2001040416A1 (en) | 2001-06-07 |
JP4572050B2 (en) | 2010-10-27 |
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DE60026167T2 (en) | 2006-08-10 |
CN1402772A (en) | 2003-03-12 |
BR0015951A (en) | 2002-08-06 |
TW524849B (en) | 2003-03-21 |
EP1252274A1 (en) | 2002-10-30 |
MXPA02005448A (en) | 2002-11-29 |
CN1225526C (en) | 2005-11-02 |
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