EP2995674B1 - Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage - Google Patents
Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage Download PDFInfo
- Publication number
- EP2995674B1 EP2995674B1 EP14184415.9A EP14184415A EP2995674B1 EP 2995674 B1 EP2995674 B1 EP 2995674B1 EP 14184415 A EP14184415 A EP 14184415A EP 2995674 B1 EP2995674 B1 EP 2995674B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulphate
- forming
- flat steel
- steel product
- coating
- 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.)
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- 229910000831 Steel Inorganic materials 0.000 title claims description 83
- 239000010959 steel Substances 0.000 title claims description 83
- 238000000034 method Methods 0.000 title claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000011248 coating agent Substances 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 17
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims 6
- 239000001166 ammonium sulphate Substances 0.000 claims 4
- 239000005569 Iron sulphate Substances 0.000 claims 2
- 239000001164 aluminium sulphate Substances 0.000 claims 2
- 235000011128 aluminium sulphate Nutrition 0.000 claims 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 18
- 239000000314 lubricant Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 238000007493 shaping process Methods 0.000 description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910000358 iron sulfate Inorganic materials 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- VCPQWWKLNIMKND-UHFFFAOYSA-L zinc hydroxy sulfate Chemical compound [Zn++].OOS([O-])(=O)=O.OOS([O-])(=O)=O VCPQWWKLNIMKND-UHFFFAOYSA-L 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- -1 Eisen-Sulfat Chemical compound 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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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
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/06—Metal compounds
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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
- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic 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
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/18—Ammonia
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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
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
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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
- C10N2010/16—Groups 8, 9, or 10
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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
- 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
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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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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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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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
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- 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
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
- C10N2040/246—Iron or steel
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/015—Dispersions of solid lubricants
- C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/08—Solids
Definitions
- the invention relates to the use of an aqueous solution which contains a sulfate from the group "aluminum sulfate, ammonium sulfate, iron sulfate, magnesium sulfate".
- the invention also relates to a method for producing a component by shaping a flat steel product in a shaping machine.
- the flat steel product to be formed is placed in a forming machine and then shaped by the machine into the respective component.
- the shaping can be carried out as cold shaping, i.e. as shaping at temperatures below the recrystallization temperature of the respective steel of the flat steel products, or as hot shaping, i.e. as shaping at working temperatures which are above the recrystallization temperature.
- a typical example of such a forming process is deep drawing, in which the flat steel product to be formed is pressed into a die by means of a stamp.
- the shape of the die and stamp determine the shape that the flat steel product receives from the forming process.
- This friction can be very different locally, in particular when shaping flat steel products, because the material of the flat steel product is deformed differently in sections in the course of the shaping and thus the material of the flat steel product flows locally with different degrees of strength during the shaping. Therefore, especially in the production of complex shaped components by deep drawing or comparable cold forming processes, in which large degrees of forming are usually achieved and complex shapes are mapped, there are dynamically changing frictional states, in which static and sliding friction can alternate.
- the frictional forces that occur in particular during cold forming can be so high that they are interfere with the continuous flow of the shaping process and can cause incorrect molding of the component to be molded. At the same time, the unavoidable friction causes considerable tool wear.
- Flat steel products in which a zinc or aluminum-based protective coating protecting the actual steel flat product is applied to the actual steel flat product, are particularly critical.
- the surfaces that come into contact with one another during the forming process are coated with lubricants.
- the lubricant can be applied both to the flat steel product to be formed and to the surfaces of the tool that come into contact with the flat steel product.
- lubricants based on mineral oil are used as lubricants for cold forming, to which various additives, such as sulfur-containing, phosphorus-containing or chlorine-containing additives, can be added to optimize their lubricating effect.
- various additives such as sulfur-containing, phosphorus-containing or chlorine-containing additives
- coating agents for cold forming which are based on mineral oil or similar hydrocarbons, are in the DE 101 15 696 A1 described. These coating agents include lubricants based on paraffin or naphthenic or ester oils based on plants or animals.
- Coating agents based on carbonic acid esters are known.
- the coating compositions contain one or more components which are selected from the group of the mono- and / or diesters of mono- or oligophosphoric acids, triglycerides and fatty acid methyl esters. These components are primarily intended to replace hydrocarbons in mineral oil or other petroleum distillates.
- an aqueous solution for treating the surface of a ferrous metal product which contains aluminum sulfate, boric acid or a boric acid precursor and polycarboxylic acid or a salt.
- the coating applied at elevated temperature and low pH is said to facilitate the sliding behavior of the product during wire drawing.
- a solution which contains oxalic acid, fluoroboric acid or a salt thereof and an oxidizing agent.
- the pH of the solution can vary from 0.7 - 2.0.
- the oxidizing agent can be sodium chlorate and a soluble salt of a polyvalent metal that is less noble than iron. This can be an aluminum sulfate, for example.
- a coating formed from this solution can serve as a lubricant for the plastic deformation of flat steel products or can be used in combination with oils to improve the corrosion resistance.
- a lubricant for non-cutting metal forming which contains at least 5% by weight of at least one powdered sulfate, which is selected from the group "calcium sulfate and barium sulfate" and has an average particle size of ⁇ 100 ⁇ m and contains at least one conventional lubricant , the is selected from the group "inorganic solid lubricants, organic solid lubricants and organic liquid lubricants”.
- the lubricant can contain stearic acid.
- a water-based lubricant which contains a water-soluble inorganic salt, a homogeneously dispersed solid lubricant, at least one homogeneously emulsified substance selected from "mineral oils, animal and vegetable oils and fats, synthetic oils", a surfactant and water, for which Weight ratios of the individual components apply to certain requirements.
- the lubricant is said to be particularly suitable for use in the cold forming of metals.
- an aqueous coating solution which should be suitable as a coating of sheets for pressing and punching and contains 10-21% by weight NaCl and 10-21% by weight FeSO4.
- adhering black oxides (Fe3O4) on forgings made of ferrous metal can be prevented by briefly immersing the red-hot parts in an aqueous solution made of iron or another metal sulfate. Immersion forms a light oxide film that can be easily removed in an acidic pickling bath or by electrolytic means.
- the object of the invention was to name coating agents, which, on the one hand, enable optimized tribological conditions when forming flat steel products while minimizing the need for lubricants and, on the other hand, are harmless with regard to their impact on the environment.
- this object has been achieved by the use of an aqueous solution which contains a sulfate selected from the group "aluminum sulfate, ammonium sulfate, iron sulfate, magnesium sulfate" as the coating agent to improve the tribological behavior of a flat steel product when forming in a forming machine.
- a sulfate selected from the group "aluminum sulfate, ammonium sulfate, iron sulfate, magnesium sulfate”
- flat steel product includes all rolled products whose length is much greater than their thickness. Which includes Steel strips and sheets as well as cuts and blanks obtained from them.
- the flat steel products to be cold-formed according to the invention include so-called thin sheets, i.e. H. Sheets with a thickness of less than 4 mm, in particular 0.4 - 3.5 mm, typically 0.5 - 3 mm, which can be formed into a component in the cold or hot rolled state.
- DIN EN 10130 uncoated thin sheets
- DIN EN 10346 thin sheets provided with a corrosion protection coating
- Examples include the soft steels for forming with material numbers 1.0226, 1.0350, 1.0355, 1.0306, 1.0322, 1.0853.
- the sulfates contained in an aqueous solution provided according to the invention as a coating agent for flat steel products lead to a significant improvement in the tribological conditions when forming flat steel products.
- lubricating properties can be achieved which are equivalent to the properties achieved with conventional lubricants of the type described at the beginning. This effect is basically independent of whether the forming is carried out as cold or hot forming.
- the coating compositions according to the invention have proven to be particularly effective sulfates used in the cold forming of steel flat products.
- the sulfates contained in an aqueous solution used according to the invention as a coating material to improve the friction conditions during the shaping are distinguished by good environmental compatibility and can be applied in a simple manner to the respective flat steel product.
- the sulfates used according to the invention can be just as easily removed from the steel components obtained after the shaping process. At the same time, coating residues remaining on the steel component disrupt the processes that usually go through after the forming in the further processing of steel components to a minor extent.
- sulfates from the group "aluminum III sulfate, ammonium sulfate, iron II sulfate, iron III" are to be mentioned specifically as sulfates which are contained in an aqueous solution used according to the invention and are particularly suitable for practical use. Sulfate, magnesium sulfate ".
- a sulfate from the group containing "aluminum sulfate, ammonium sulfate, iron sulfate, magnesium sulfate” provides a coating agent with optimal processing and use properties Available that can be easily provided in sufficient quantity and low cost.
- the sulfates provided in a coating agent applied according to the invention as an aqueous solution in a method of the type according to the invention are suitable for coating the surfaces of the respective tool with which the flat steel product to be formed comes into contact during the forming. So are used according to the invention Sulphates are sprayed as an aqueous solution onto the critical surfaces of the forming tool in each case, brushed or applied in another manner already known in practice for this purpose.
- the respective flat steel product is coated with the coating agent in the course of its production.
- the ease of application and the good adhesion of the sulfates used according to the invention to the surface of the flat steel product to be coated have a particularly positive effect here.
- the sulfates proposed according to the invention for use as lubricants can also be applied to the flat steel product to be formed using conventional coating systems, as are usually available for applying organic or inorganic layers to flat steel products of the type in question here.
- the respective sulfate can be applied as a coating agent to the flat steel product by dipping, spraying, coating or brushing.
- the application of the coating compositions according to the invention in the form of an aqueous solution to improve the state of friction when shaping flat steel products is particularly easy in that these sulfates wet the surface to be coated in each case and accordingly form uniform layers without requiring any special precautions.
- the coating agent present as an aqueous solution according to the invention as an aqueous solution
- the application of the sulfates contained in the coating agent is particularly simple. After a subsequent drying process, there is a dense, evenly distributed thin sulfate layer on the respective flat steel product, which ensures optimum deformation behavior during a forming process, in particular a cold forming process.
- the aqueous solution consists of two components, of which one component is water as a solvent and the other component is the respective sulfate as a tribologically active component. If distilled water is used as the solvent, this has the advantage that the function of the coating cannot be disturbed by foreign ions.
- a sufficiently thick and dense tribologically effective coating for the purposes of the invention on the surface to be coated of flat steel products or Forming tools are obtained when the content of the tribologically active sulfate component in the aqueous solution is 0.2 - 1 mol / l (based on the SO 4 2- ion concentration), with effectively effective coatings resulting in reliable operation in practice if the content of the aqueous solution in the sulfate component provided according to the invention is 0.4-0.7 mol / l (based on the SO 4 2- ion concentration).
- Mixtures of the sulfates provided as coating agents according to the invention can also be applied to the flat steel product in the manner according to the invention.
- the layer formed from the respective coating agent on the flat steel product or on the surface of the forming tool to be coated can be applied with a coating weight of 5-50 mg / m 2 .
- Optimal effects occur when the occupancy weight is 10 - 30 mg / m 2 .
- the surface in question can be cleaned alkaline before the coating agent is applied.
- the sulfates provided according to the invention to improve the tribological properties, the The coefficient of friction of the coated surface is significantly improved.
- a layer formed from the sulfates intended for use in accordance with the invention regularly reduces the coefficient of friction of the respective coated surface to 0,1 0.15.
- the Zn-based coating can be applied in a conventional manner as a pure zinc layer, as a zinc alloy layer with contents of Mg, Al or Si, for example electrolytically or by hot-dip coating on the respective steel substrate. It is also possible to coat flat steel products with Al-based coatings in the manner according to the invention in order to improve their forming behavior during cold or hot forming.
- coatings which are formed by the coating agents selected according to the invention thus achieve friction properties which certainly correspond to the friction properties of coatings which consist of conventional agents commonly used to improve tribological properties.
- a tribologically effective ammonium sulfate layer has been applied to a conventional flat steel product provided in the form of a Zn-coated sheet metal strip.
- an aqueous solution has been created in which 90 g of ammonium sulfate ((NH 4 ) 2 SO 4 ) has been dissolved in 1 l of water (dist.), So that the ammonium sulfate content of the aqueous solution is 90 g / l lay.
- the native pH of the solution obtained was 5.3.
- chemcoater which is common in industry.
- a "chemcoater” is a part of the system that is used in the steel industry to apply chemical substances to be applied as an aqueous solution to galvanized flat carbon steel.
- such coaters are used to apply water-soluble media, which serve to pretreat the respective flat steel product for a subsequent coating or film coating or to improve the corrosion protection.
- Various treatment chemicals can be applied to the flat steel product to be coated using rollers.
- the flat steel product covered with the coating then passes through an oven in which the coating is dried.
- a tribologically effective iron (II) sulfate layer has been applied to a conventional flat steel product, also in the form of a Zn coating of thin sheet metal strip.
- a tribologically effective aluminum sulfate layer has been applied to a conventional flat steel product, also in the form of a Zn coating of thin sheet metal strip.
- the aqueous solution was applied to the previously alkaline-cleaned flat steel product at room temperature by means of the coater already described above.
- the application parameters are also shown in Table 1.
- the specification "Setting the dipping and application roller” denotes the amount by which the between the dipping and application roller existing nip is smaller than the thickness of the processed steel flat product.
- PMT also means the so-called "peak metal temperature”.
- the tribologically active layers which consist of the sulfates proposed according to the invention for use, thus achieve the same effect as the conventional coatings, for example consisting of ZnSO 4 .
- Table 1 attempt Operation of the coater Peripheral speeds Setting the dipping and application roller Thickness of the flat steel product Gap width between dipping and application roller Edition weight Drying oven PMT Applicator roller Dipping roller Transport roller temperature Dwell time [m / min] [m / min] [m / min] [ ⁇ m] [mm] [ ⁇ m] [mg / m 2 ] [° C] [s] [° C] 1 Reverse 30th 10th 25th -400 1 0.9 30th 100 100 71 2nd Reverse 25th 10th 23 -500 1 0.9 30th 100 100 71 3rd Mitlaufia 30th 10th 40 -400 1 0.9 30th 100 35 71
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
- Chemical Treatment Of Metals (AREA)
- Mounting, Exchange, And Manufacturing Of Dies (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Claims (13)
- Utilisation d'une solution aqueuse, qui consiste en deux composants, l'un des composants étant de l'eau en tant que solvant, et l'autre composant un sulfate, choisi à partir du groupe « sulfate d'aluminium, sulfate d'ammonium, sulfate de fer, sulfate de magnésium », comme moyen de revêtement pour la valorisation du comportement tribologique d'un produit plat en acier, lors du formage dans une machine de formage.
- Utilisation selon la revendication 1, caractérisée en ce que le sulfate est choisi à partir du groupe «sulfate d'aluminium III, sulfate d'ammonium, sulfate de fer II, sulfate de fer III, sulfate de magnésium».
- Utilisation selon l'une des revendications précédentes, caractérisée en ce que la couche obtenue avec le moyen de revêtement est soluble à l'eau.
- Procédé de fabrication d'un élément de construction en acier par formage d'un produit plat en acier dans une machine de formage, lequel comprend les étapes suivantes:- Mise à disposition du produit plat en acier- réalisation d'une couche active au niveau tribologique sur au moins l'une des surfaces du produit plat en acier, qui se touchent lors du formage, ou de la machine de formage utilisée, par revêtement avec un moyen de revêtement, qui est appliqué en tant que solution aqueuse, qui consiste en deux composants, l'un des composants étant de l'eau en tant que solvant, et l'autre composant étant un sulfate, choisi à partir du groupe « sulfate d'aluminium, sulfate d'ammonium, sulfate de fer, sulfate de magnésium »,- mise en place du produit plat en acier dans l'outil de formage,- formage du produit plat en acier déposé dans la machine de formage pour l'obtention d'un élément de construction.
- Procédé selon la revendication 4, caractérisé en ce que le sulfate est choisi à partir du groupe « sulfate d'aluminium III, sulfate d'ammonium, sulfate de fer II, sulfate de fer III, sulfate de magnésium ».
- Procédé selon l'une des revendications 4 ou 5, caractérisé en ce que le formage est effectué en tant que formage à froid.
- Procédé selon l'une des revendications 4 à 6, caractérisé en ce que la couche active au niveau tribologique est générée sur le produit plat en acier.
- Procédé selon l'une des revendications 4 à 7, caractérisé en ce que le solvant est de l'eau distillée.
- Procédé selon l'une des revendications 4 à 8, caractérisé en ce que la teneur en composant actif au niveau tribologique de la solution aqueuse est de 0,2 mol/l (par rapport à la concentration en ions SO4 2).
- Procédé selon l'une des revendications 4 à 9, caractérisé en ce que la couche, formée par le moyen de revêtement respectif sur le produit plat en acier ou sur la surface de l'outil de formage à revêtir, est appliquée avec un poids de 5 à 50 mg / m2.
- Procédé selon l'une des revendications 4 à 10, caractérisé en ce que le coefficient de friction du produit plat en acier, après de revêtement avec la couche active au niveau tribologique, est de 0,15 au maximum, sachant que le coefficient de friction est déterminé selon la méthode révélée dans la description.
- Procédé selon l'une des revendications 4 à 11, caractérisé en ce que le produit plat en acier est revêtu avec une couche de protection contre la corrosion et que la couche active au niveau tribologique est appliquée sur la couche de protection contre la corrosion.
- Procédé selon l'une des revendications 4 à 12, caractérisé en ce que la couche active au niveau tribologique est appliquée à une température ambiante.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14184415.9A EP2995674B1 (fr) | 2014-09-11 | 2014-09-11 | Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage |
KR1020177009712A KR102472493B1 (ko) | 2014-09-11 | 2015-08-19 | 황산염의 사용 및 성형 기계에서 성형에 의한 강 부품의 제조 방법 |
PCT/EP2015/069018 WO2016037814A1 (fr) | 2014-09-11 | 2015-08-19 | Utilisation d'un sulfate et procédé de fabrication d'une pièce en acier par formage sur une machine de formage |
US15/509,524 US10072229B2 (en) | 2014-09-11 | 2015-08-19 | Use of a sulphate, and method for producing a steel component by forming in a forming machine |
CN201580049081.7A CN106687571B (zh) | 2014-09-11 | 2015-08-19 | 硫酸盐的用途及通过在成型机中的成型制造钢构件的方法 |
JP2017513483A JP6694876B2 (ja) | 2014-09-11 | 2015-08-19 | 硫酸塩の使用、および成形機における成形により鋼部品を製造するための方法 |
CA2958500A CA2958500C (fr) | 2014-09-11 | 2015-08-19 | Utilisation d'un sulfate et procede de fabrication d'une piece en acier par formage sur une machine de formage |
Applications Claiming Priority (1)
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EP14184415.9A EP2995674B1 (fr) | 2014-09-11 | 2014-09-11 | Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage |
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EP2995674A1 EP2995674A1 (fr) | 2016-03-16 |
EP2995674B1 true EP2995674B1 (fr) | 2020-07-15 |
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EP14184415.9A Active EP2995674B1 (fr) | 2014-09-11 | 2014-09-11 | Utilisation d'un sulfate et procede pour la production d'un élément en acier par formage dans une machine de formage |
Country Status (7)
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US (1) | US10072229B2 (fr) |
EP (1) | EP2995674B1 (fr) |
JP (1) | JP6694876B2 (fr) |
KR (1) | KR102472493B1 (fr) |
CN (1) | CN106687571B (fr) |
CA (1) | CA2958500C (fr) |
WO (1) | WO2016037814A1 (fr) |
Families Citing this family (9)
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JP6629979B2 (ja) * | 2016-01-19 | 2020-01-15 | ティッセンクルップ スチール ヨーロッパ アクチェンゲゼルシャフトThyssenKrupp Steel Europe AG | Znコーティングおよびこのコーティングに堆積されたトライボロジー活性層を有する鋼製品を製造する方法、およびこの方法に従って製造された鋼製品 |
DE102016218957A1 (de) | 2016-09-30 | 2018-04-05 | Thyssenkrupp Ag | Temporäre Korrosionsschutzschicht |
DE102017208727A1 (de) * | 2017-05-23 | 2018-11-29 | Thyssenkrupp Ag | Verbesserung der Kaltumformeignung aluminiumbasierter Beschichtung durch Zulegieren von Erdalkalimetallen |
WO2019073274A1 (fr) | 2017-10-12 | 2019-04-18 | Arcelormittal | Procédé de traitement de feuille métallique et feuille métallique traitée à l'aide de ce procédé |
WO2019073273A1 (fr) | 2017-10-12 | 2019-04-18 | Arcelormittal | Procédé de traitement de feuille métallique et feuille métallique traitée avec ce procédé |
DE102018209737A1 (de) * | 2018-06-18 | 2019-12-19 | Thyssenkrupp Ag | Trennschicht für die Warmumformung |
EP3620502A1 (fr) * | 2018-09-10 | 2020-03-11 | Carl Bechem Gmbh | Composition destiné à la production d'une composition lubrifiante |
WO2021074672A1 (fr) | 2019-10-16 | 2021-04-22 | Arcelormittal | Procédé de traitement de feuille métallique et feuille métallique traitée à l'aide de ce procédé |
DE102019128238A1 (de) * | 2019-10-18 | 2021-04-22 | Thyssenkrupp Steel Europe Ag | Verfahren zum Herstellen eines Stahlflachprodukts und Verfahren zum Herstellen eines Bauteils daraus |
Family Cites Families (13)
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GB166949A (en) * | 1920-04-21 | 1921-07-21 | Rustproofing Syndicate Ltd | New or improved process for the prevention of black oxide of iron on ferrous metal forgings and the like |
NL95016C (fr) * | 1952-11-08 | |||
US4168241A (en) * | 1978-03-14 | 1979-09-18 | Aichi Steel Works, Limited | Lubricant and method for non-chip metal forming |
SU1204283A1 (ru) * | 1983-11-05 | 1986-01-15 | Предприятие П/Я М-5481 | Состав дл нанесени на поверхность стальных листов перед гор чей прокаткой |
US6194357B1 (en) * | 1996-06-21 | 2001-02-27 | Henkel Corporation | Waterborne lubricant for the cold plastic working of metals |
FR2783256B1 (fr) | 1998-09-15 | 2000-10-27 | Lorraine Laminage | Traitement anodique de toles d'acier zingue dans des solutions aqueuses contenant des sulfates |
DE10007625A1 (de) | 2000-02-18 | 2001-08-23 | Henkel Kgaa | Schmiermittel zur Umformung von Metallen |
DE10115696A1 (de) | 2001-03-29 | 2002-10-10 | Henkel Kgaa | Schmierstoffmischung und ihre Verwendung |
US7037384B2 (en) * | 2003-06-23 | 2006-05-02 | Bulk Chemicals, Inc. | Lubricating chemical coating for metalworking |
FR2864552B1 (fr) * | 2003-12-24 | 2006-07-21 | Usinor | Traitement de surface par hydroxysulfate |
DE102006039307B3 (de) * | 2006-08-22 | 2008-02-21 | Thyssenkrupp Steel Ag | Verfahren zum Beschichten eines 6-30 Gew.% Mn enthaltenden warm- oder kaltgewalzten Stahlbands mit einer metallischen Schutzschicht |
DE102008016348B4 (de) | 2008-03-29 | 2010-07-29 | Stefan Graichen | Hochtemperaturschmiermittel und dessen Verwendung in einem Verfahren zum Warmumformen von Metallen |
WO2013104835A1 (fr) * | 2012-01-10 | 2013-07-18 | Arcelormittal Investigación Y Desarrollo Sl | Utilisation d'une solution contenant des ions sulfates pour reduire le noircissement ou le ternissement d'une tole lors de son stockage et tole traitee par une telle solution. |
-
2014
- 2014-09-11 EP EP14184415.9A patent/EP2995674B1/fr active Active
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- 2015-08-19 CN CN201580049081.7A patent/CN106687571B/zh active Active
- 2015-08-19 KR KR1020177009712A patent/KR102472493B1/ko active IP Right Grant
- 2015-08-19 WO PCT/EP2015/069018 patent/WO2016037814A1/fr active Application Filing
- 2015-08-19 US US15/509,524 patent/US10072229B2/en not_active Expired - Fee Related
- 2015-08-19 CA CA2958500A patent/CA2958500C/fr active Active
- 2015-08-19 JP JP2017513483A patent/JP6694876B2/ja active Active
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Also Published As
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JP2017534700A (ja) | 2017-11-24 |
WO2016037814A1 (fr) | 2016-03-17 |
JP6694876B2 (ja) | 2020-05-20 |
CN106687571A (zh) | 2017-05-17 |
KR20170052670A (ko) | 2017-05-12 |
KR102472493B1 (ko) | 2022-12-01 |
CA2958500C (fr) | 2019-01-15 |
US20170260471A1 (en) | 2017-09-14 |
CA2958500A1 (fr) | 2016-03-17 |
EP2995674A1 (fr) | 2016-03-16 |
US10072229B2 (en) | 2018-09-11 |
CN106687571B (zh) | 2019-09-13 |
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