CN1768163A - 表面改性工件的制造方法 - Google Patents
表面改性工件的制造方法 Download PDFInfo
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- CN1768163A CN1768163A CNA200480008965XA CN200480008965A CN1768163A CN 1768163 A CN1768163 A CN 1768163A CN A200480008965X A CNA200480008965X A CN A200480008965XA CN 200480008965 A CN200480008965 A CN 200480008965A CN 1768163 A CN1768163 A CN 1768163A
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- described method
- salt
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- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 55
- 230000004048 modification Effects 0.000 claims abstract description 35
- 238000012986 modification Methods 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 46
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 238000005219 brazing Methods 0.000 claims description 19
- -1 zirconium organic compound Chemical class 0.000 claims description 18
- 230000004907 flux Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
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- 238000005476 soldering Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
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- 150000003863 ammonium salts Chemical group 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 5
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- 239000010703 silicon Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
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- 239000004111 Potassium silicate Substances 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000443 aerosol Substances 0.000 claims description 3
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- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
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- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 2
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- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- SKFYTVYMYJCRET-UHFFFAOYSA-J potassium;tetrafluoroalumanuide Chemical compound [F-].[F-].[F-].[F-].[Al+3].[K+] SKFYTVYMYJCRET-UHFFFAOYSA-J 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 9
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical class [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 102100030624 Proton myo-inositol cotransporter Human genes 0.000 description 1
- 101710095091 Proton myo-inositol cotransporter Proteins 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
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- 230000003750 conditioning effect Effects 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 229960002887 deanol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical class [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical class [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical class [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical class [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
- B23K35/3603—Halide salts
- B23K35/3605—Fluorides
-
- 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
- C23C22/34—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 containing fluorides or complex fluorides
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
-
- 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
- C23C22/68—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 solutions with pH between 6 and 8
-
- 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
- C23C22/73—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 characterised by the process
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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Abstract
本发明提供一种工件表面的改性方法，包括将工件与至少一种改性剂相接触，以此实现表面改性。
Description
技术领域
本发明涉及一种表面被改性的、由金属和/或一种或多种合金构成的工件的制造方法，还涉及用这种方法制成的工件以及将至少两个这样的工件连接起来的方法。
背景技术
由于有机涂层体系在铝上面的附着力很低，所以几乎无法直接在铝或铝合金上面进行有机涂覆。众所周知，为了改善原始材料与有机涂层之间的附着性，可对铝或铝合金进行所谓的勃姆(Bhmit)法处理，即将工件置于热水或热蒸汽中，必要时加上氨或胺，从而在表面形成一层铝氧化膜或勃姆膜或使其增强。经过这样处理，就可进行有机涂敷。EP 1 142 663 A1对勃姆法进行了描述，在这一方法中，在温度约为100℃时使用去离子水或者在温度约为150℃时使用蒸汽，以对铝件表面进行改性。在US 3,945,899中，用温度为65到100℃的水或温度为100到180℃的蒸汽对铝件进行勃姆处理，同时，氨或胺添加物则起着对铝氧化膜的二次加强作用。
从前述的文件中还得知，可利用铬或磷溶液对铝或其合金进行表面化学处理，通过这种方式一方面提高了附着力，另一方面还降低了腐蚀敏感度。这种转换处理法也在Stolzenfels(Industrie-Lackierbetrieb，Nr.3，Seite93-98，Curt R.Vincent Verlag)中公开过，其中对在20至50℃的温度下铝工件的镀铬进行了说明。Riese-Meyer等(Aluminium 1991，Nr.12，Seite1215-1221)则描述了一种化学转换处理法，它通过磷酸盐化和铬酸钝化形成覆盖层，从而可以提高铝件的油漆附着力和防腐蚀能力。按照这个文件，铬酸钝化也是在20至30℃或30至40℃的温度下进行。
但是从能量角度看，上述方法却具有缺点。因为在现有技术条件下，需改性的工件的温度通常应为室温，也就是说钎焊或接合工艺后它要被冷却，这样，这种工件的表面改性就需要更多的搬运传送工作，耗费更多的时间。另外，在现有技术条件下，由铝或铝合金制成的需改性成型件在经过缓慢的冷却过程后会形成所谓的粗结晶现象。
发明内容
以这一技术问题为基础，本发明提供了一种克服上述缺点的方法，特别是一种低成本的、可改善铝或铝合金工件的附着力和/或防腐性能的方法。尤其是在耐腐蚀性和附着力相同或更佳的情况下，与传统的铝或铝合金工件相比，这种工件在结构上具有粗结晶程度低的特点。
本发明是通过提供一种表面被改性的、由铝和/或一种或多种铝合金构成的工件的制造方法来解决上述技术问题的。这一方法包括准备需改性的工件，工件的温度则在40至700℃之间，优选为80至550℃之间，最佳为300至550℃之间；该方法还包括在上述温度下用至少一种改性剂对工件进行处理，以获得表面改性的工件，而这至少一种改性剂的温度为-200℃至100℃，优选为最高80℃且最低0℃，最佳为20至65℃。总之，本发明是这样解决上述技术问题的：准备需改性的工件，而工件的温度相对很高，然后使工件与至少一种温度较低的改性剂接触，从而得到表面被改性的工件。
具体实施方式
与本发明有关的工件是指一个任意形成的物体，例如，可以是成型件，即具有一定形状的物体，也可以是颗粒或粉末。在优选的实施形式中，工件是热交换器或它的主要部件。
在本发明的一个优选实施形式中，需改性的工件由铝、镁、铜或一种或多种铝合金和/或镁合金和/或铜合金制成，也就是说，由铝或一种或多种合金构成，或者主要含有铝或一种或多种铝合金，例如，从工件的重量看，其重量百分率至少为50、60、70、80、90、95，尤其为99。
在本发明的第一个实施形式中，表面需改性的工件被加热，这时，需改性工件的温度为40至700℃，尤其为100至550℃，优选为150至550℃，最佳为300至550℃。在一个优选的实施形式中，可以通过以下方式实现上述情况：在工件的制作工序后，例如从钎焊区出来后、在热接合工序后或在箱式炉中加热后，将热的工件直接按照本发明进行处理，这样就充分利用了工件的现有热容。这样，就可将具有前面所述温度之一如80至550℃、尤其是300至550℃的工件，在利用其自身现有的高温条件下进行处理，即使其与至少一种表面改性剂接触，从而实现所需要的工件表面改性。
本发明中所涉及到的表面改性是一种化学转化，也就是形成一个转化层和/或形成一层勃姆膜或铝氧化膜或使其加强。在一个优选的实施形式中，本发明所要实现的表面改性还包括在铝氧化膜或勃姆膜加入缓蚀剂，和/或在必要时对已有的钎剂层实施化学—物理改性来获得转化层。
因此，一个工件在经过CAB钎焊工序后，就已经带有一个CAB钎剂层，那么就按照本发明所描述的方式对其进行处理，即将现有的CAB—钎剂层进行化学—物理改性。按照本发明的处理方式，可在现有的钎剂层中添加诸如第I、II、III或IV主族或是副族尤其是IV至VI中的金属，或/和提高氧的比例。另外，本发明的这种处理方法还提高了耐腐蚀性。
按照本发明，优选采用温度较低的改性剂，特别是温度为-200℃至100℃，优选为0到80℃，特别优选的是20至65℃，这样在处理一个温度为80至700℃、特别是达300至550℃的工件时，就可以使工件迅速冷却，这样就将抑制或减少工件内的粗结晶形成。这样所获得的工件在结构上不同于以传统方式所制作的工件。
本发明所优选的对钎剂(CAB)-覆盖的工件的处理使得铝件的钎剂层呈现出鳞片状、闭合的和圆整的具有优点的外观，与之不同的是，未经处理的铝件钎剂覆盖层的外观则带有开孔、锐边和薄片。
在本发明的另一个实施形式中，前面所提及的技术问题是通过一种表面被改性的、由金属和/或一种或多种合金构成的工件的制造方法解决的，它包括需改性的工件的准备和用至少一种改性剂对这个工件的处理，以得到表面改性的工件，而这至少一种改性剂的温度为80℃至550℃，优选为100℃至200℃，最佳为150℃至200℃。
在本发明的这一实施形式中，需改性的工件的温度为15至80℃，特别为40至65℃；也可以为20至60℃，特别为20至40℃，优选为20至30℃，或者为80到700℃，优选为100至700℃，特别优选为150至700℃，更优选为300至550℃。并且，本发明的这一实施形式使工件的表面改性具有优点，特别是得到一个金属氧化膜或勃姆膜，对现有金属氧化膜或勃姆膜的加强，在金属氧化膜或勃姆膜中掺加缓蚀剂，和/或对钎剂层进行化学—物理改性得到转化层。
在工件表面改性后，通常可对工件继续进行处理，如清洗或烘干。当然也可以进行另外的涂覆，例如涂敷有机涂层。这一方法也是工件如热交换器的制造方法的一个部分。在这一制造方法的框架中，本发明所规定的制造方法减少了工件的制造成本，节约了能源，特别是利用工件自身所具有的热容，减少或避免在表面处理中使用刺激性的化学剂。
几乎所有已知的化学元素、化合物、混合物或其他的组成都可以考虑作为改性剂。一种优选的改性剂是一种或多种化合物，特别是PSE(元素周期表)中一个或多个副族元素、尤其是PSE的第IV到VI副族，如钛、铪、钒、钽、钼、钨和锆的一种或多种金属盐。
在本发明的另一个实施形式中，改性剂可以是一种或多种化合物，尤其是元素周期表中第I、II、III和/或IV主族中的一个或多个元素的一种或多种金属盐，例如，铍、钡，特别是镁或钙或钠或钾的一种金属盐。
在本发明的另一个实施形式中，改性剂可以是元素周期表中第V、VI、VII和/或VIII主族中的一个或多个元素的一种或多种化合物。
在本发明的优选实施形式中，前面以盐的形式出现的金属可以同由氯化物、碳酸盐、酸式碳酸盐(Hydrogencarbonaten)、硝酸盐、硫酸盐、过氧化物和磷酸盐组成的一组中所选出的阴离子一起存在。特别是第I和II主族元素如钾、钠和钙的金属盐可以以碱的形式、即KOH、NaOH或Ca(OH)2，或硼酸盐、铝酸盐、硅酸盐或卤化物，特别是氟化物的形式存在。
在本发明的另一个优选的实施形式中，这至少一种改性剂是一种CAB(可控气氛钎焊)钎剂，其通用化学式为KxAlFy，其中x＝1到3，y＝4到6，例如六氟化铝钾(Kaliumaluminiumhexafluorid)和/或CsxAlFy。
在另一个优选的实施形式中，铵盐如氟化铵或碳酸铵、氟化钾、硅酸钠或硅酸钾、硼酸钠或硼酸钾、铝酸钠或铝酸钾，以及可交联的、特别是金属有机化合物、如锆有机化合物、钛有机化合物或硅有机化合物或过氧化氢均可作为改性剂。
在一个特别优选的实施形式中，为了对工件进行处理，使用了处于碱相的、特别是以水、优选为碱液或碱蒸汽或气雾形式出现的CAB钎剂、铵盐和/或氟化钾。
第IV到VI副族或第I、II、III或IV主族的元素中之一个元素的金属化合物可以以有机相或无机相，优选为水相、特别是以液相或气相、更加优选的是气雾或蒸汽的形式存在。用于溶液的水优选为纯水。
在另一个优选的实施形式中，用于对工件表面进行处理的改性剂为水，优选为纯水和蒸馏水。按照本发明也可以使用下列物质的溶液作为改性剂，如氨、胺，特别是伯胺、仲胺或叔胺，如一元胺、二元胺或三乙醇胺，二甲乙醇胺，氨及胺的有机酸或盐，含有机卤化物和/或有机酸等。当然也可以使用前面所述改性剂的混合物。
优选采用的溶液为含有0.1-1％的KOH和/或0.1-1％的NH4OH和/或0,1-1％的KxAlFy(x＝1到3，y＝4到6)和/或0,1-1％的Ca(NO3)2和/或0,1-1％的PSE中第IV到VI副族元素的盐的纯水。
在本发明的一个特别优选的实施形式中，一个在CAB钎焊工序中被涂覆了CAB钎剂的工件作为采用本发明方法的原始工件，在规定的条件下用一种或多种改性剂对它进行处理。特别是经过水或水溶液处理后，它的表面被改性，表面氧成分增加，同时还可根据所使用的改性剂，在表面添加第I、II、III或IV主族或第IV到VI副族中的一种或多种金属，或其它的改性剂。
在本发明的另一个优选实施形式中，使用了由金属盐、CAB钎剂、铵盐和/或氟化钾或改性剂的其它成分形成的一个组合，例如由有机和/或无机溶剂或它们的混合物形成的组合形式，来对工件表面进行处理。这一组合含有金属有机化合物，特别是硅有机化合物。特别的是，这一组合包含有机和/或无机聚合物，或者这些物质的混合物。
在一个特别优选的实施形式中，对工件表面进行处理时，使用了金属盐、CAB钎剂、铵盐和/或氟化钾或改性剂的其它成分，其浓度为10ppm至100000ppm，优选为50ppm至10000ppm。
该至少一种改性剂优选地通过以下方式与需改性的工件接触：将工件放入到改性剂中并浸泡，或者用这至少一种改性剂冲洗工件并同时将其浸泡，或者将这至少一种改性剂喷洒到工件上，特别是通过所谓的无气或超声波喷涂的方式或其它方式使它们接触。
在一个优选的实施形式中，在比气压大的压力下改性剂被喷涂到工件上。在喷涂时，除了压缩空气外，还可使用其它气体，如氧气、氮气、氟气、臭氧或蒸汽。
例如，Ca(NO3)2或Zr(NO3)4的水溶液可作为金属盐使用，其浓度为0,1％到5％，而其pH值优选在5,5和7,5到8之间。使用温度优选为40℃和60℃之间。如果添加0,005％到5％的四乙基四氟硼酸铵(Tetraethylammoniumtetrafluoroborat)，也会带来益处。
一个钎焊特别是CAB钎焊而成的热交换器优选采用这种溶液进行处理。
按照一个具有优点的实施形式，这至少一种改性剂含有生物杀灭剂。例如，在一个取暖和/或空调设备中的热交换器中，就可以通过它起到抑制细菌的作用。
按照另一个具有优点的实施形式，改性剂含有或通过本发明的方法在表面带有缓蚀剂，从而起着缓蚀作用。例如，缓蚀剂由一个金属氧化膜或勃姆膜生成。
当然，本发明还涉及用前述方法制造的表面改性工件，特别是由铝或铝合金制成的表面改性的热交换器。
在本发明的一个具有优点的进一步改型中，表面已被改性的工件在随后的工序中被涂覆上一个或多个有机或无机涂层，其特别具有抑制细菌和/或亲水或疏水的特点。这种类似油漆的涂层的涂覆既可以有中间的烘干工序，也可以无中间的烘干工序。
本发明同样还涉及按照权利要求24将两个或多个工件连接的方法。一个包含这种方法的加工工艺简便迅速，从而使制造成本降低。这尤其适用于通过材料配合连接将多个工件连接起来的方法，但如果采用其它的连接方法如机械接合，就可能需要将工件(再次)加热，从而使用本发明的方法。
本发明还涉及到一种将至少两个工件进行材料配合连接的设备，在这个设备中，用来对工件进行调温特别是加热的恒温室具有一个将表面改性剂涂覆到至少一个工件上的装置。具有优点的是，这个恒温室同时用于材料配合的连接如钎焊或熔焊，以及工件的表面改性。
这个涂覆表面改性剂的装置优选为喷嘴，为了实施本发明的方法，它优选地可以自我调温。同样具有优点的是，这个装置的输入管可以对表面改性剂进行调温。
此外，本发明的这种设备可以采用已知的结构，如采用真空钎焊炉或连续钎焊炉的形式。
本发明的其它具有优点的结构见从属权利要求。
Claims (27)
1.表面被改性的、由一种金属和/或一种或多种合金构成的工件的制造方法，包括需改性的工件的准备，和用至少一种改性剂对工件进行处理以获得表面改性的工件，其特征在于，准备进行改性的工件温度在40至700℃之间，优选为80至550℃之间，而这至少一种改性剂的温度最低为-200℃，尤其是最低为0℃，而最高为100℃，尤其是最高为80℃。
2.表面被改性的、由一种金属和/或一种或多种合金构成的工件的制造方法，包括需改性的工件的准备，和用至少一种改性剂对工件进行处理，以获得表面改性的工件，其特征在于，这至少一种改性剂的温度为80至550℃。
3.如权利要求2所述的方法，其特征在于，准备进行改性的工件温度为15至80℃。
4.如权利要求2所述的方法，其特征在于，准备进行改性的工件温度为40至660℃，特别为80至550℃。
5.如前面权利要求之一所述的方法，其特征在于，准备进行改性的工件温度为300至550℃。
6.如前面权利要求之一所述的方法，其特征在于，金属或合金包含铝，镁和/或铜。
7.如前面权利要求之一所述的方法，其特征在于，改性剂为盐，特别是PSE的第IV到VI副族中的一个族的一个元素的一种金属盐。
8.如前面权利要求之一所述的方法，其特征在于，改性剂为PSE的第I、II、III和/或IV主族中的一个元素的一种金属盐。
9.如前面权利要求之一所述的方法，其特征在于，改性剂为PSE的第V、VI、VII和/或VIII主族中的一个元素的一种化合物。
10.如前面权利要求之一所述的方法，其特征在于，改性剂为一种CAB钎剂，特别是六氟化铝钾。
11.如前面权利要求之一所述的方法，其特征在于，改性剂为铵盐，特别是氟化铵、氟化钾、硅酸钠或硅酸钾、硼酸钠或硼酸钾、铝酸钠或铝酸钾，和/或至少一种可交联的化合物，如金属有机化合物、特别是一种锆有机化合物或钛有机化合物和/或至少一种硅有机化合物或类似物质。
12.如前面权利要求之一所述的方法，其特征在于，金属盐以水相的形式存在，其pH值为1到14之间，优选为3到10之间，最佳为4到8之间。
13.如前面权利要求之一所述的方法，其特征在于，CAB钎剂、铵盐或氟化钾处于碱相，其pH值为碱性。
14.如前面权利要求之一所述的方法，其特征在于，改性剂为水，优选为纯水和蒸馏水，或含有氨、胺、气体或有机酸或有机盐或它们的混合物的水溶液。
15.如前面权利要求之一所述的方法，其特征在于，工件的处理以下面的方式进行，将气雾和/或蒸汽形式的至少一种改性剂与工件接触，特别是将其喷洒到工件上。
16.如前面权利要求之一所述的方法，其特征在于，工件的处理以下面的方式进行，将工件浸泡在该至少一种以水溶液形式存在的改性剂中，或用改性剂冲洗工件。
17.如前面权利要求之一所述的方法，其特征在于，盐，特别是金属盐、CAB钎剂、氟化铵、氟化钾、硅酸钠或硅酸钾、硼酸钠或硼酸钾、铝酸钠或铝酸钾，和/或至少一种可交联的化合物，如金属有机化合物、特别是一种锆有机化合物或钛有机化合物和/或至少一种硅有机化合物或类似物质以一种组合的形式用于工件的处理。
18.如权利要求17所述的方法，其特征在于，该组合由有机溶剂、无机溶剂或它们的混合物构成。
19.如前面权利要求之一所述的方法，其特征在于，盐，特别是金属盐、CAB钎剂、氟化铵、氟化钾、硅酸钠或硅酸钾、硼酸钠或硼酸钾、铝酸钠或铝酸钾，和/或金属有机化合物、特别是锆有机化合物或钛有机化合物或硅有机化合物用于工件的处理，其浓度为10ppm至100000ppm，优选为50ppm至10000ppm。
20.如前面权利要求之一所述的方法，其特征在于，需改性的工件是一个热交换器，特别是一个CAB钎焊而成的热交换器。
21.如前面权利要求之一所述的方法，其特征在于，该至少一种改性剂具有或在工件表面上产生出生物杀灭剂和/或缓蚀剂。
22.表面改性的工件，按照前面所述的方法之一制造。
23.如权利要求22所述的工件，在至少随后的一个工序中被涂覆上一个有机或无机涂层体系。
24.如权利要求23所述的工件，其特征在于，一个涂层体系具有抑制细菌和/或亲水或疏水的特性。
25.将至少两个如权利要求23或24所述的工件通过材料配合连接起来的方法，包括步骤a)准备工件，b)材料配合连接，特别是通过钎焊或熔焊将工件相互连接，c)对其中至少一个工件进行表面改性，其中，步骤b)和c)共同进行，而步骤c)则按照权利要求1到20之一进行。
26.将至少两个工件材料配合连接起来的设备，特别是为了实施权利要求25所述的方法，它具有一个恒温室和一个布置在恒温室内或恒温室上的装置，该装置用于将改性剂涂覆到至少一个工件上。
27.如权利要求26所述的设备，其特征在于，用于将改性剂涂覆到至少一个工件的装置由至少一个可调温的喷嘴构成。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2003114700 DE10314700A1 (de) | 2003-03-31 | 2003-03-31 | Verfahren zur Herstellung oberflächenmodifizierter Werkstücke |
| DE10314700.4 | 2003-03-31 |
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| CN1768163A true CN1768163A (zh) | 2006-05-03 |
| CN100478496C CN100478496C (zh) | 2009-04-15 |
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| CNB200480008965XA Expired - Lifetime CN100478496C (zh) | 2003-03-31 | 2004-03-17 | 表面改性工件的制造方法 |
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| US (2) | US7829151B2 (zh) |
| EP (2) | EP2251456B1 (zh) |
| JP (1) | JP5196784B2 (zh) |
| KR (1) | KR20050123135A (zh) |
| CN (1) | CN100478496C (zh) |
| AT (1) | ATE483833T1 (zh) |
| BR (1) | BRPI0408868A (zh) |
| DE (2) | DE10314700A1 (zh) |
| ES (1) | ES2353693T3 (zh) |
| MX (1) | MXPA05010598A (zh) |
| PL (1) | PL1611266T3 (zh) |
| WO (1) | WO2004087993A2 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070822A (zh) * | 2016-11-10 | 2018-05-25 | 张永青 | 制造铝基复合物的方法、使用此方法制成的铝基复合物、以及包含铝基复合物的铝基结构 |
| CN111001923A (zh) * | 2019-11-11 | 2020-04-14 | 航天工程装备（苏州）有限公司 | 一种搅拌工具表面处理方法 |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10314700A1 (de) | 2003-03-31 | 2004-10-14 | Behr Gmbh & Co. Kg | Verfahren zur Herstellung oberflächenmodifizierter Werkstücke |
| DE102004049107A1 (de) * | 2004-10-07 | 2006-04-13 | Behr Gmbh & Co. Kg | Beschichtungsverfahren |
| DE102005035704A1 (de) * | 2005-07-27 | 2007-02-01 | Behr Gmbh & Co. Kg | Zu verlötende Oberfläche |
| WO2008017382A2 (de) * | 2006-08-07 | 2008-02-14 | Behr Gmbh & Co. Kg | Verfahren zum herstellen von bauteilen in einem mediumkreislauf, wie insbesondere eines wärmeübertragers und solche bauteile |
| DE102009013054A1 (de) | 2009-03-16 | 2010-09-23 | Behr Gmbh & Co. Kg | Wärmetauscher |
| US20150225839A1 (en) * | 2014-02-13 | 2015-08-13 | Winona PVD Coatings, LLC | Sputter coating a work piece |
| DE102018101183A1 (de) | 2017-10-17 | 2019-04-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Passives elektrisches Bauteil mit Isolierschicht |
| JP7045236B2 (ja) * | 2018-03-27 | 2022-03-31 | 三菱重工業株式会社 | 遮熱コーティング、タービン部材及びガスタービン |
| CN115302134B (zh) * | 2022-03-17 | 2024-08-06 | 山东迈拓凯尔新材料科技有限公司 | 一种用于焊接用铝箔的表面防护组合物 |
Family Cites Families (71)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH295082A (de) | 1950-12-19 | 1953-12-15 | Colgate Palmolive Peet Co | Verfahren zur Behandlung von Aluminiumtuben. |
| US2809423A (en) * | 1953-03-30 | 1957-10-15 | Gen Motors Corp | Salt flux and method for brazing aluminum parts therewith |
| NL111701C (zh) | 1958-04-14 | |||
| GB863098A (en) * | 1959-05-21 | 1961-03-15 | Pyrene Co Ltd | Improvements relating to the coating of metallic surfaces |
| GB1076678A (en) * | 1964-06-29 | 1967-07-19 | Pyrene Co Ltd | Improvements in the coating of metals |
| DE1771936A1 (de) | 1968-08-01 | 1972-01-05 | Telefunken Patent | Verfahren zum Erzeugen einer Oxydschicht |
| US3945899A (en) * | 1973-07-06 | 1976-03-23 | Kansai Paint Company, Limited | Process for coating aluminum or aluminum alloy |
| JPS5347062B2 (zh) * | 1974-01-18 | 1978-12-18 | ||
| CS218556B2 (en) | 1975-04-09 | 1983-02-25 | Alcan Res & Dev | Method of joining the aluminium components |
| US4123290A (en) | 1977-04-21 | 1978-10-31 | Diamond Shamrock Corporation | Chromium-containing coating of enhanced corrosion resistance |
| JPS6043434B2 (ja) | 1977-08-11 | 1985-09-27 | 昭和電工株式会社 | アルミニウム表面に化成皮膜を形成する方法 |
| BE864899A (fr) * | 1978-03-14 | 1978-09-14 | Centre Rech Metallurgique | Procede pour le traitement superficiel d'une bande metallique |
| JPS5544537A (en) * | 1978-09-22 | 1980-03-28 | Kawasaki Steel Corp | Chemical conversion treating method for alloying hot zinc dipped steel sheet |
| JPS5655573A (en) | 1979-10-12 | 1981-05-16 | Nippon Steel Corp | Method and apparatus for forming oxide film rapidly on surface of tool |
| US4446057A (en) * | 1982-07-08 | 1984-05-01 | Texaco Inc. | Apparatus and method for the manufacture of gas filters |
| JPS6025503B2 (ja) * | 1982-08-06 | 1985-06-18 | 本田技研工業株式会社 | 鋼材の塗装前処理剤及び塗装前処理方法 |
| JPS59232694A (ja) * | 1983-06-15 | 1984-12-27 | Showa Alum Corp | アルミニウム製熱交換器のろう付方法 |
| US4553416A (en) * | 1983-06-20 | 1985-11-19 | Sumitomo Metal Industries, Ltd. | Dry type continuous wire drawing process |
| JPS6083771A (ja) | 1983-10-13 | 1985-05-13 | Toyota Central Res & Dev Lab Inc | アルミニウム系材料のろう付け方法 |
| GB8402191D0 (en) | 1984-01-27 | 1984-02-29 | Ici Plc | Coating process |
| JPS6133752A (ja) * | 1984-07-26 | 1986-02-17 | Toyota Central Res & Dev Lab Inc | 複合アルミニウム部材の製造方法 |
| JPH06100436B2 (ja) * | 1986-03-05 | 1994-12-12 | 三菱アルミニウム株式会社 | 熱交換器の製造方法 |
| JP2512452B2 (ja) | 1986-12-29 | 1996-07-03 | 日本パ−カライジング株式会社 | アルミニウムの親水性処理方法 |
| JPS63317297A (ja) * | 1987-06-22 | 1988-12-26 | Kanto Yakin Kogyo Kk | アルミニウム又はその合金部材の浸漬ろう付け法 |
| GB8906160D0 (en) | 1989-03-17 | 1989-05-04 | Alcan Int Ltd | Surface preparation for aluminium |
| JPH0822473B2 (ja) * | 1989-04-11 | 1996-03-06 | ヒューズ・エアクラフト・カンパニー | 金属表面を保護しはんだ付けを容易にする方法ならびにそれに使用するフィルムおよび溶液 |
| JPH0364485A (ja) * | 1989-08-01 | 1991-03-19 | Nippon Paint Co Ltd | アルミニウム又はその合金の表面処理剤及び処理浴 |
| JP2842712B2 (ja) | 1990-11-30 | 1999-01-06 | 大同ほくさん株式会社 | めつき方法 |
| US5100048A (en) * | 1991-01-25 | 1992-03-31 | Alcan International Limited | Method of brazing aluminum |
| US5350791A (en) | 1992-07-02 | 1994-09-27 | Henkel Corporation | Hydrophilicizing treatment for metal objects |
| JP3173164B2 (ja) | 1992-08-14 | 2001-06-04 | 忠弘 大見 | 表面物質の改質方法及びそのための装置 |
| KR950006282B1 (ko) | 1992-12-09 | 1995-06-13 | 삼성전기주식회사 | 알루미늄 박판(Foil)의 화성피막 형성시 산소가스 제거방법 |
| US5450666A (en) * | 1994-02-28 | 1995-09-19 | S.A. Day Mfg. Co., Inc. | Flux composition for aluminum brazing |
| JP3280804B2 (ja) * | 1994-08-15 | 2002-05-13 | 触媒化成工業株式会社 | 基材上への粒子層の形成方法、基材凹凸面の平坦化方法および粒子層付基材 |
| DE4429975C1 (de) | 1994-08-24 | 1995-12-07 | Bayer Ag | Verfahren zur Vermeidung von Lokalkorrosion bei Schweißverbindungen |
| CN1053020C (zh) | 1994-12-30 | 2000-05-31 | 邵天敏 | 一种铝及铝合金表面的涂层制备方法 |
| CN1091006C (zh) | 1995-04-12 | 2002-09-18 | 美国铝公司 | 用于涂敷金属条的方法和设备及其制品 |
| DE19515909C2 (de) * | 1995-04-29 | 2001-07-19 | Behr Gmbh & Co | Zinklöt-Verfahren zur Herstellung von hartgelöteten Wärmetauschern |
| US5532024A (en) | 1995-05-01 | 1996-07-02 | International Business Machines Corporation | Method for improving the adhesion of polymeric adhesives to nickel surfaces |
| US5496417A (en) * | 1995-06-21 | 1996-03-05 | Electro-Steam Generator Co. | Process for steam conversion coating aluminum |
| JP3159893B2 (ja) * | 1995-07-10 | 2001-04-23 | 京浜産業株式会社 | ろう付用アルミニウム合金鋳物材およびそのろう付方法 |
| US5684066A (en) * | 1995-12-04 | 1997-11-04 | H.B. Fuller Licensing & Financing, Inc. | Protective coatings having enhanced properties |
| DE19548740A1 (de) * | 1995-12-23 | 1997-06-26 | Abb Research Ltd | Verfahren zur Oberflächenbehandlung von Aluminium und Aluminiumlegierungen |
| US5820015A (en) * | 1996-04-02 | 1998-10-13 | Kaiser Aluminum & Chemical Corporation | Process for improving the fillet-forming capability of brazeable aluminum articles |
| US5762132A (en) * | 1996-04-03 | 1998-06-09 | Ford Global Technologies, Inc. | Heat exchanger and method of assembly for automotive vehicles |
| US5785770A (en) * | 1996-05-30 | 1998-07-28 | Advance Research Chemicals, Inc. | Brazing flux |
| JP3971811B2 (ja) | 1996-09-11 | 2007-09-05 | 株式会社水素エネルギー研究所 | アルミニウム又はアルミニウム−マグネシウム系合金からなる材料の表面親水化処理方法 |
| US5750197A (en) | 1997-01-09 | 1998-05-12 | The University Of Cincinnati | Method of preventing corrosion of metals using silanes |
| DE19913111A1 (de) * | 1998-03-25 | 1999-09-30 | Solvay Fluor & Derivate | Neue Flußmittel |
| US6368671B1 (en) * | 1998-06-22 | 2002-04-09 | Mccormick David R. | Treating solid, especially aluminum, surfaces |
| EP0970757B1 (en) | 1998-07-07 | 2002-10-30 | Kabushiki Kaisha Nippankenkyusho | Rust preventive coating and method for forming the same |
| DE19859735B4 (de) | 1998-12-23 | 2006-04-27 | Erbslöh Ag | Verfahren zur partiellen oder vollständigen Beschichtung der Oberflächen von Bauteilen aus Aluminium und seinen Legierungen mit Lot, Fluß- und Bindemittel zur Hartverlötung |
| US6475301B1 (en) * | 1999-07-06 | 2002-11-05 | Visteon Global Technologies, Inc. | Conversion coatings on aluminum from KF solutions |
| DE10044454A1 (de) * | 1999-12-14 | 2001-07-12 | Ford Global Tech Inc | Flußmittel für das CAB-Löten von Aluminiumwärmetauschern |
| US6497770B2 (en) | 2000-02-17 | 2002-12-24 | Toyo Aluminium Kabushiki Kaisha | Flux-containing compositions for brazing aluminum, films and brazing method thereby |
| GB2360477A (en) * | 2000-03-22 | 2001-09-26 | Gea Sprio Gills Ltd | Brazing aluminium components |
| JP2001316847A (ja) * | 2000-05-08 | 2001-11-16 | Ford Global Technol Inc | Ｋｆ溶液噴霧によるアルミニウム上の化成被覆 |
| JP3474866B2 (ja) | 2000-05-12 | 2003-12-08 | 日本ペイント株式会社 | 熱交換器の親水化処理方法および親水化処理された熱交換器 |
| JP2002146549A (ja) | 2000-11-14 | 2002-05-22 | Kobe Steel Ltd | アルミニウム製フィン材の製造方法およびこの方法により製造されたアルミニウム製フィン材 |
| WO2002061164A1 (fr) * | 2001-01-31 | 2002-08-08 | Nkk Corporation | Tole d'acier pretraite et son procede de production |
| JP2002285140A (ja) * | 2001-03-27 | 2002-10-03 | Nippon Paint Co Ltd | 親水化処理剤、親水化処理方法及び親水化処理されたアルミニウム材又はアルミニウム合金材 |
| JP4707258B2 (ja) | 2001-05-07 | 2011-06-22 | 日本ペイント株式会社 | 化成皮膜用酸性洗浄剤及び処理方法 |
| JP2003003276A (ja) | 2001-06-22 | 2003-01-08 | Suzuki Motor Corp | 表面処理装置および表面処理方法 |
| DE20121992U1 (de) | 2001-08-28 | 2003-10-23 | Behr GmbH & Co. KG, 70469 Stuttgart | Flussmittelzusammensetzungen zum Hartlöten von Teilen, insbesondere auf der Basis von Aluminium als Grundmaterial, sowie derartige Teile |
| BE1014525A3 (fr) * | 2001-12-04 | 2003-12-02 | Ct Rech Metallurgiques Asbl | Procede de revetement de surface metallique. |
| US7294211B2 (en) * | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
| DE10314700A1 (de) | 2003-03-31 | 2004-10-14 | Behr Gmbh & Co. Kg | Verfahren zur Herstellung oberflächenmodifizierter Werkstücke |
| CN1235702C (zh) | 2003-05-08 | 2006-01-11 | 上海交通大学 | 耐锌液腐蚀的涂层及其使用方法 |
| US6881491B2 (en) * | 2003-05-16 | 2005-04-19 | Alcoa Inc. | Protective fluoride coatings for aluminum alloy articles |
| US20050282003A1 (en) * | 2004-06-18 | 2005-12-22 | Alexander Mayzel | Coated article and process for coating article with anticorrosive finish |
| DE102009013054A1 (de) | 2009-03-16 | 2010-09-23 | Behr Gmbh & Co. Kg | Wärmetauscher |
-
2003
- 2003-03-31 DE DE2003114700 patent/DE10314700A1/de not_active Withdrawn
-
2004
- 2004-03-17 AT AT04739066T patent/ATE483833T1/de active
- 2004-03-17 US US10/551,185 patent/US7829151B2/en active Active
- 2004-03-17 BR BRPI0408868-9A patent/BRPI0408868A/pt not_active Application Discontinuation
- 2004-03-17 CN CNB200480008965XA patent/CN100478496C/zh not_active Expired - Lifetime
- 2004-03-17 EP EP10172067.0A patent/EP2251456B1/de not_active Expired - Lifetime
- 2004-03-17 KR KR1020057018725A patent/KR20050123135A/ko active Search and Examination
- 2004-03-17 ES ES04739066T patent/ES2353693T3/es not_active Expired - Lifetime
- 2004-03-17 WO PCT/EP2004/002751 patent/WO2004087993A2/de active Application Filing
- 2004-03-17 MX MXPA05010598A patent/MXPA05010598A/es active IP Right Grant
- 2004-03-17 JP JP2006504710A patent/JP5196784B2/ja not_active Expired - Fee Related
- 2004-03-17 EP EP04739066A patent/EP1611266B1/de not_active Expired - Lifetime
- 2004-03-17 PL PL04739066T patent/PL1611266T3/pl unknown
- 2004-03-17 DE DE502004011740T patent/DE502004011740D1/de not_active Expired - Lifetime
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070822A (zh) * | 2016-11-10 | 2018-05-25 | 张永青 | 制造铝基复合物的方法、使用此方法制成的铝基复合物、以及包含铝基复合物的铝基结构 |
| CN111001923A (zh) * | 2019-11-11 | 2020-04-14 | 航天工程装备（苏州）有限公司 | 一种搅拌工具表面处理方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050123135A (ko) | 2005-12-29 |
| MXPA05010598A (es) | 2005-11-23 |
| US9677166B2 (en) | 2017-06-13 |
| US20110030852A1 (en) | 2011-02-10 |
| WO2004087993A2 (de) | 2004-10-14 |
| ES2353693T3 (es) | 2011-03-04 |
| US20060118216A1 (en) | 2006-06-08 |
| JP2006522218A (ja) | 2006-09-28 |
| DE502004011740D1 (de) | 2010-11-18 |
| US7829151B2 (en) | 2010-11-09 |
| BRPI0408868A (pt) | 2006-04-11 |
| JP5196784B2 (ja) | 2013-05-15 |
| ATE483833T1 (de) | 2010-10-15 |
| EP2251456B1 (de) | 2016-11-30 |
| DE10314700A1 (de) | 2004-10-14 |
| EP1611266B1 (de) | 2010-10-06 |
| EP2251456A1 (de) | 2010-11-17 |
| WO2004087993A3 (de) | 2005-02-24 |
| CN100478496C (zh) | 2009-04-15 |
| EP1611266A2 (de) | 2006-01-04 |
| PL1611266T3 (pl) | 2011-03-31 |
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