EP1302565B1 - Méthode de recouvrement des surfaces d'alliages de métaux légers - Google Patents
Méthode de recouvrement des surfaces d'alliages de métaux légers Download PDFInfo
- Publication number
- EP1302565B1 EP1302565B1 EP01124435A EP01124435A EP1302565B1 EP 1302565 B1 EP1302565 B1 EP 1302565B1 EP 01124435 A EP01124435 A EP 01124435A EP 01124435 A EP01124435 A EP 01124435A EP 1302565 B1 EP1302565 B1 EP 1302565B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- light metal
- metal alloy
- solution
- treatment
- acid
- 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.)
- Expired - Lifetime
Links
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000011282 treatment Methods 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005238 degreasing Methods 0.000 claims abstract description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims abstract description 4
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 fluoride ions Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000004922 lacquer Substances 0.000 claims description 9
- 238000001465 metallisation Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 14
- 239000003929 acidic solution Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 33
- 239000011777 magnesium Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 238000002161 passivation Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000013532 laser treatment Methods 0.000 description 2
- 229910001234 light alloy Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- DAFQZPUISLXFBF-UHFFFAOYSA-N tetraoxathiolane 5,5-dioxide Chemical compound O=S1(=O)OOOO1 DAFQZPUISLXFBF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 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 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000012791 sliding layer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
Definitions
- the present invention relates to a method for coating Light alloy surfaces.
- Light alloy surfaces are light alloys
- alloys that contain Al and / or Mg in a proportion that the chemical properties of the surface significantly influenced.
- Such light metal alloys are because of their low specific weight for various applications of great interest, in which on the one hand high mechanical stability must be achieved and on the other hand the total mass of the component plays a critical role.
- Such applications e.g. in aircraft construction or, more recently, in motor vehicles or housings of high quality devices.
- frame parts made of light metal alloys are used, on the one hand form the basic structure of the overall structure in terms of stability and on the other hand, should burden the user as little as possible with weight.
- DE 197 24 013 A shows the treatment of aluminum-magnesium alloy surfaces by degreasing, pickling with phosphoric acid and fluoride, chemical deposition a zinc layer, galvanic deposition a copper layer and galvanic Deposition of a tin bronze layer and galvanic deposition of a final black chrome top layer.
- the tin content of the tin bronze layer should preferably be at most 20% and in particular at most 9%.
- the final black chrome layer has various advantageous properties.
- the US 2,215,165 A deals with sheet metal containers for food with a anodic coating of the tinned metal containers and a paint on them.
- JP 52 068832 A deals with electrolytic Treatment of steel with phosphate solutions for anodization and a subsequent painting.
- JP 59 208098 A deals with pretreatment a metal surface before an electrophoretic coating with nickel or a tin copper alloy or other alloys in the presence of hexavalent Chrome.
- DE-A-197 23 980 shows a process for the production of chrome-plated black Injection molded parts made of magnesium alloys, in which the black chrome-plated Parts on certain surface areas with water repellent organic Fabrics, u. a. Lacquers, to be impregnated.
- EP 0 890 743 A2 shows the surface coating of a plate with Cu, Sn or a metal phosphate. Chromating is used especially for aluminum and nickel plating or copper plating is suggested, but it is also from a pure tinning. Then on this intermediate layer applied a sliding layer.
- the present invention is therefore based on the technical problem, an inexpensive one and in particular flexible coating process for light metal alloy surfaces specify.
- the method according to the invention is characterized by the galvanic containing Sn Layer that, together with the other layers mentioned, is a reliable one Sealing of the light metal alloy surface enables.
- the Sn portion in the corresponding galvanic layer is over 50% by weight.
- the passivating cleaning mentioned can contain, as a first step, an alkaline degreasing of the light metal alloy surface, whereupon the degreased surface is treated with a solution that is acidic on the one hand, contains at least the salt of an acid and thus stains the light metal alloy surface somewhat, and on the other hand has the property induce oxidative passivation.
- oxidation is generally to be understood in the sense of a valence electron transition and in particular includes the formation of oxides such as Al 2 O 3 and fluorides such as MgF 2 .
- the weakly acidic solution can, for example, be a mixture of a carboxylic acid, e.g. Citric acid, malic acid, oxalic acid or lactic acid, and one Pyrophosphate included.
- the strongly acidic solution used below can for example, contain a mixture of phosphoric acid and ammonium bifluoride.
- the treatment in the acidic or acid salt solution can preferably be carried out in a strongly oxidizing solution Solution take place that stains simultaneously and creates the passivation layer.
- the passivation layer contains Al 2 O 3 .
- the strongly oxidizing solution are nitric acid, peroxomonosulfuric acid or potassium persulfate solution.
- the alcohol mentioned can the usual alcohols such as methanol, ethanol, propanol, butanol and higher Alcohols and their derivatives such as isopropanol. But it will come also diols, polyethers and other alcohols. Mixtures are natural also possible. Butanol and isopropanol are preferred.
- fluoride ions are preferably used to cover the surface passivate.
- the fluoride ions are in a containing the phosphoric acid Solution used, the surface also in this treatment step is connected anodically.
- This treatment step can also be used the treatment step further containing the alcohol coincides by the solution contains phosphoric acid, alcohol and fluoride ions, or thereof be carried out separately. In the latter case, the step is carried out with fluoride ions last time. He can then advantageously the or contain another alcohol.
- the fluoride ions can be used as ammonium bifluoride, as alkali fluoride, as hydrofluoric acid or in another form.
- the treatments described with fluoride ions are, on the one hand those of the two-stage acid treatments and on the other hand those with the Combination of phosphoric acid and alcohol, also useful if the Light metal alloy contains little or no Mg, but contains a proportion of Si of preferably over 0.1, in particular over 0.5 or 1 or 2% by weight and about that.
- the fluoride ion concentration can be as high as the Si concentration be coordinated.
- the treatment described with the combination of phosphoric acid and Alcohol and the fluoride ions can advantageously be combined with an alkaline Rinsing step, such as in alkalized water with a pH of about 10 or about being completed.
- the alkaline rinsing step is unfavorable for a passivation surface dominated less by MgF 2 and more by Al 2 O 3 , at least as long as the high pH values mentioned are present.
- the aqueous oxidizing agent could be a persulfate solution or a solution of peroxomonosulfuric acid (Caro's acid). The oxidation should always take place after the fluoride treatment.
- the aqueous oxidation step is problematic in any case at an acidic pH of about pH6 and below with a high Mg content, because it can damage the fluoride passivation.
- the fluoride ion fractions mentioned can lie in ranges with 0.1 or 0.3 or 0.5% by weight as the lower limit and 30 or 20 or 10% by weight as the upper limit.
- the anodic current densities in the treatment with phosphoric acid and alcohol can be between 10 or 30 or 50 A / m 2 as the lower limit and 1000 A / m 2 as the upper limit.
- Favorable temperatures are around 10-40 ° C.
- the phosphoric acid can have a share of 30-90 vol% in the solutions and 50-95 percent by weight in this volume fraction.
- the rest of the solution advantageously consists essentially of alcohol and possibly the fluoride.
- the subsequent galvanic intermediate layer could also be Cu and / or Ni contain.
- the next galvanic layer already discussed naturally contains Sn, could besides z. B. also contain Zn, Bi and / or Pb to the To improve corrosion properties.
- the method described so far leads to stable and permanent galvanic Coatings of light metal alloy surfaces. Since the process with wet chemical and galvanic process steps can be carried out, it is very flexible with regard to the usable part sizes and geometries and moreover inexpensive to carry out on a large scale. In the previously described The procedure is a metallic conductive surface that is suitable for many applications is desired.
- the lacquer contains Sn galvanic layer can also be deposited a varnish.
- the lacquer can be colored opaque or transparent and thus the achieve a wide variety of decorative effects. It can also have structures, for example Surface splashes with common painting machines can be applied by default, and the treated part one Give individual visual and haptic appearance. Most of all however, the painted surface is usually electrically insulating, depending on the application may be desired. After all, the surface is through that Lacquer layer also much better protected against corrosion.
- the paint adhesion can be significantly improved if before applying the Lacquers passivate the surface of the galvanic containing Sn Shift is performed.
- Alkaline anodic oxidation is preferred, for example in a solution containing phosphates and / or carbonates.
- This alkaline anodic oxidation can be supplemented by a subsequent one cathodic treatment in a solution of hexavalent chromium ions, about in chromic acid. This creates an occupancy of the surface with trivalent chrome. From a health and environmental point of view however, the use of hexavalent chromium is problematic (however not for the product itself), which is why the painting of only with the alkaline anodic pre-treated galvanic surface preferred can be.
- the painted surface also offers the possibility of retrospectively converting partial areas back to a metallic one Attributed to surface conductivity. This can be useful, for example, to make electrical contacts to the coated component at certain points to attach, but the component should remain insulated otherwise or should have certain optical surface properties be particularly well protected against chemical and mechanical loads should.
- the invention a laser treatment is proposed for this, which is relatively easily causing the paint to flake or evaporate leads on the bombarded partial areas and this by remelting leads to metallic conductivity.
- the invention Sn portion in the surface for a particularly good electrical Conductivity and at the same time resistance of the area freed from the paint.
- a flowable metallic within hours or a few days Apply conductive substance, such as an adhesive or another hardening substance based on plastic, the metallic conductive particles contains. These could be silver particles or silver-coated particles.
- the Laser bombardment is preferably done twice to the thermal load to limit the surface, however, in an air atmosphere with a conventional Equipment.
- An Nd: YAG laser has proven itself, for example of 90 W power.
- Preferred layer thicknesses of the galvanic intermediate layer are between 5 and 10 ⁇ m.
- Preferred layer thicknesses of the galvanic containing Sn Layer are also at 5-10 microns.
- a die cast part shown in the attached figure can be made from serve the magnesium alloy AZ91. It is a frame part 1 (so-called chassis) of a mobile phone housing. This frame part 1 is to the in lines 2 drawn in the figures with other metallic or metallic coated housing parts are glued. On the one hand, it is essential that the Mg die-cast frame part 1 has a good surface durability offers high-quality appearance. Through frequent hand contact and the simultaneous exposure to salts and weak acids and moisture, as well as weather conditions and other conditions 5 with years of use, the outer surface can with insufficient tiling become unsightly. The inner surface could turn at Corrosion for particle generation and thus failure of electronic components to lead.
- a stable one Coating of the magnesium die-cast part 1 also has good electrical surface conductivity the surface areas used for the bonding 2 enable. This also applies to parts of the surface of the support domes shown 3 for a circuit board of the mobile phone, because of the necessary Earth connection also become conductive. Further details of the frame part 1 are irrelevant to the understanding of the invention.
- the frame part 1 is therefore first degreased conventionally alkaline and at pH4 in a solution treated with citric acid and pyrophosphate. thereupon passivation takes place at pH1 in a strongly acidic solution with phosphoric acid and ammonium bifluoride.
- the layer thickness is 8 ⁇ m.
- This still electrically conductive surface is now being prepared for painting with an alkaline anodic oxidation in a phosphate solution.
- On treatment with hexavalent chromium is dispensed with. Instead it will a commercial two-component paint directly onto the anodized surface applied and cured.
- the surface of the Mg die-cast part 1 has the final optical and technical quality, although it can be painted in a transparent color, so that the translucent metal gives it an attractive appearance results.
- This surface is then treated on the drawn tracks 2 and support domes 3 with a commercial Nd: YAG laser.
- This laser is Q-switched and has a power of 90W at a lamp current of around 32 A.
- the point spacing, the point size and the energy per point can be determined empirically in such a way that on the one hand there is a continuous path and on the other hand a sufficient path width.
- the web width should not be too small to optimize the electrical contact resistance to the other housing part. On the other hand, the web width should not be too large and be completely covered by the adhesive bead applied later. It is 1 mm here.
- the energy input per shot should not be set unnecessarily high in order to avoid excessive heating at greater depths.
- the energy per shot can be reduced even further by double bombardment. 15 W / mm 2 are used here per shot.
- the feed of the laser is 400 mm / s.
- a caterpillar can then be applied to the surface areas 2, 3 thus remetalized are applied from a silicone adhesive mixed with silver particles, so an electrically conductive bond with one here is not closer described other housing part can be done.
- This other part of the case is also metallic or metallic coated and is glued so that it makes electrical contact with the adhesive. In this way receives electrical contact with the adhesive. In this way, a total a tight and electrically shielded housing can be produced.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
- Chemically Coating (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Claims (19)
- Procédé de revêtement de surfaces en alliages de métaux légers (1) avec les étapes suivantes :nettoyage passivant de la surface en alliage de métaux légers (1) ;métallisation chimique qui contient du Zn ;revêtement galvanique intermédiaire ;revêtement galvanique qui contient plus de 50% en poids de Sn etenlèvement d'une couche de vernis de la couche galvanique contenant du Sn.
- Procédé selon la revendication 1, dans lequel le nettoyage passivant comprend les étapes suivantes :dégraissage alcalin de la surface en alliage de métaux légers (1) ettraitement de la surface en alliage de métaux légers (1) dans une solution acide ou dans la solution d'un sel d'acide avec réalisation oxydante simultanée d'une couche de passivation.
- Procédé selon la revendication 2, dans lequel l'alliage de métaux légers (1) contient une part de Mg d'au moins 50% en poids et le traitement dans la solution acide comprend les étapes suivantes :traitement dans une solution d'acide faible ettraitement dans une solution d'acide fort, moyennant quoi la solution d'acide fort contient des ions fluorures.
- Procédé selon la revendication 3, dans lequel la solution d'acide faible contient un acide carboné et un pyrophosphate.
- Procédé selon la revendication 3 ou 4, dans lequel la solution d'acide forte contient de l'acide phosphorique et du fluorure d'ammonium.
- Procédé selon la revendication 2, dans lequel l'alliage de métaux légers contient une part d'Al d'au moins 60% en poids et le traitement dans la solution acide ou la solution de sel d'acide est réalisée dans une solution fortement oxydante.
- Procédé selon la revendication 6, dans lequel la solution fortement oxydante contient de l'acide nitrique, de l'acide péroxomonosulfurique ou une solution de persulfate.
- Procédé selon la revendication 1, dans lequel le nettoyage passivant de la surface en alliage de métaux légers (1) comprend une étape dans une solution qui contient un acide phosphorique et un alcool, dans laquelle la surface en alliages de métaux légers (1) est traitée anodiquement.
- Procédé selon la revendication 8, dans lequel l'alliage de métaux légers (1) contient une part de Mg d'au moins 50% en poids et/ou une part de Si d'au moins 0,1% en poids et le nettoyage passivant se termine par une étape de traitement dans une solution qui contient de l'acide phosphorique et des ions fluorures, dans laquelle la surface en alliages de métaux légers (1) est traitée anodiquement.
- Procédé selon la revendication 8, dans lequel l'alliage de métaux légers comprend une part d'Al d'au moins 60% en poids et le nettoyage passivant se termine par une étape de traitement dans un agent oxydant aqueux.
- Procédé selon l'une des revendications précédentes, dans lequel la métallisation chimique contient, en plus du Zn, du Cu et/ou du Ni.
- Procédé selon l'une des revendications précédentes, dans lequel le revêtement galvanique intermédiaire contient du Cu et/ou du Ni.
- Procédé selon l'une des revendications précédentes, dans lequel la couche galvanique contient, en plus du Sn, du Zn, du Bi et/ou du Pb.
- Procédé selon l'une des revendications précédentes, dans lequel le vernis est un vernis bicomposant.
- Procédé selon l'une des revendications précédentes, dans lequel, avant le revêtement à l'aide du vernis, un traitement de passivation de la couche galvanique contenant du Sn est réalisé.
- Procédé selon la revendication 15, dans lequel le traitement de passivation contient une oxydation anodique alcaline.
- Procédé selon la revendication 16, dans lequel l'oxydation anodique alcaline est réalisée dans une solution contenant des phosphates et/ou des carbonates.
- Procédé selon la revendication 15, 16 ou 17, dans lequel le traitement de passivation est un traitement cathodique dans une solution contenant des ions chromes hexavalents, réalisé le cas échéant après l'oxydation anodique alcaline.
- Procédé selon l'une des revendications précédentes, dans lequel, des parties (2, 3) de la surface en alliage de métaux légers (1) sont irradiées à l'aide d'un laser afin d'augmenter la conductivité électrique de la surface en alliage de métaux légers.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE50103781T DE50103781D1 (de) | 2001-10-11 | 2001-10-11 | Beschichtungsverfahren für Leichtmetalllegierungsoberflächen |
AT01124435T ATE277207T1 (de) | 2001-10-11 | 2001-10-11 | Beschichtungsverfahren für leichtmetalllegierungsoberflächen |
EP01124435A EP1302565B1 (fr) | 2001-10-11 | 2001-10-11 | Méthode de recouvrement des surfaces d'alliages de métaux légers |
PCT/EP2002/011291 WO2003033777A1 (fr) | 2001-10-11 | 2002-10-09 | Procede d'enduction pour surfaces en alliage leger |
KR1020020061816A KR100553233B1 (ko) | 2001-10-11 | 2002-10-10 | 경금속 합금 표면을 위한 피복 방법 |
JP2002297389A JP2003221683A (ja) | 2001-10-11 | 2002-10-10 | 軽金属合金表面の被覆方法 |
CNB021457549A CN1213169C (zh) | 2001-10-11 | 2002-10-11 | 轻金属合金表面的覆层方法 |
US10/269,265 US20030079997A1 (en) | 2001-10-11 | 2002-10-11 | Method for coating metal surfaces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01124435A EP1302565B1 (fr) | 2001-10-11 | 2001-10-11 | Méthode de recouvrement des surfaces d'alliages de métaux légers |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1302565A1 EP1302565A1 (fr) | 2003-04-16 |
EP1302565B1 true EP1302565B1 (fr) | 2004-09-22 |
Family
ID=8178944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01124435A Expired - Lifetime EP1302565B1 (fr) | 2001-10-11 | 2001-10-11 | Méthode de recouvrement des surfaces d'alliages de métaux légers |
Country Status (8)
Country | Link |
---|---|
US (1) | US20030079997A1 (fr) |
EP (1) | EP1302565B1 (fr) |
JP (1) | JP2003221683A (fr) |
KR (1) | KR100553233B1 (fr) |
CN (1) | CN1213169C (fr) |
AT (1) | ATE277207T1 (fr) |
DE (1) | DE50103781D1 (fr) |
WO (1) | WO2003033777A1 (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004035876A1 (fr) * | 2002-10-09 | 2004-04-29 | Wolf-Dieter Franz | Procede pour nettoyer et passiver des surfaces d'alliages legers |
JP4736084B2 (ja) * | 2005-02-23 | 2011-07-27 | オーエム産業株式会社 | マグネシウム又はマグネシウム合金からなる製品の製造方法 |
US20070075406A1 (en) * | 2005-09-30 | 2007-04-05 | Yueh-Se Ho | Wafer-level method for metallizing source, gate and drain contact areas of semiconductor die |
CN101205609B (zh) * | 2006-12-18 | 2010-08-11 | 比亚迪股份有限公司 | 一种镁合金表面活化用组合物 |
IT1393140B1 (it) * | 2009-03-17 | 2012-04-11 | Nuovo Pignone Spa | Metodo di produzione di un rivestimento protettivo per un componente di una turbomacchina, il componente stesso e la relativa macchina |
CN102110866B (zh) * | 2009-12-24 | 2013-08-28 | 深南电路有限公司 | 波导槽制作工艺 |
CN103305894B (zh) * | 2012-03-09 | 2016-01-27 | 苏州汉扬精密电子有限公司 | 镁合金表面处理方法 |
EP2722930A1 (fr) * | 2012-10-16 | 2014-04-23 | Delphi Technologies, Inc. | Élément de contact avec revêtement |
CN103498156A (zh) * | 2013-09-27 | 2014-01-08 | 成都四威高科技产业园有限公司 | 碳化硅颗粒增强铝基复合材料的表面镀层工艺 |
CN104562004B (zh) * | 2015-01-28 | 2017-01-04 | 江西富意美实业有限公司 | 一种各类温度控制器铝合金感温管及其制备方法 |
DE102018203800B4 (de) * | 2018-03-13 | 2019-11-21 | Te Connectivity Germany Gmbh | Kontaktstift und Anordnung zur Verbindung von elektrischen Leitern aus Kupfer und Aluminium |
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DE19723980A1 (de) * | 1997-06-06 | 1998-12-10 | Alfred R Franz Fa | Kontinuierliches, rechnergesteuertes Verfahren zur Herstellung von schwarzverchromten, oberflächenfehlerfreien, komplettierbaren Spritzgußteilen aus Magnesiumlegierungen mit elektrisch leitfähigen und optimal haftfähigen Oberflächenbereichen |
EP0890743A2 (fr) * | 1997-06-26 | 1999-01-13 | Taiho Kogyo Co., Ltd. | Plateau oscillant pour compresseur à plateau oscillant |
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US2871171A (en) * | 1956-05-10 | 1959-01-27 | Atkinson James Thomas Nesbitt | Method of electroplating copper on aluminum |
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US3767582A (en) * | 1970-02-02 | 1973-10-23 | Texas Instruments Inc | Etching composition preparatory to nickel plating |
US3915667A (en) * | 1973-09-20 | 1975-10-28 | Westinghouse Electric Corp | Abrasion resistant coating for aluminum base alloy and method |
FR2298619A1 (fr) * | 1975-01-22 | 1976-08-20 | Pechiney Aluminium | Procede et traitement superficiel d'un fil en aluminium a usage electrique |
JPS5268832A (en) * | 1975-12-05 | 1977-06-08 | Nippon Steel Corp | Surface treatment of tin plated steel sheet |
DE2659273C2 (de) * | 1976-12-29 | 1985-08-29 | Daimler-Benz Ag, 7000 Stuttgart | Verfahren zur kontinuierlichen Verarbeitung von Zweikomponentenlacken |
US4143210A (en) * | 1977-09-30 | 1979-03-06 | Whyco Chromium Company, Inc. | Multi-layer plating for improved corrosion resistance |
JPS59208098A (ja) * | 1983-05-12 | 1984-11-26 | Shimizu Shoji Kk | アニオン電着塗膜の密着性向上法 |
US4744872A (en) * | 1986-05-30 | 1988-05-17 | Ube Industries, Ltd. | Anodizing solution for anodic oxidation of magnesium or its alloys |
DE3808609A1 (de) * | 1988-03-15 | 1989-09-28 | Electro Chem Eng Gmbh | Verfahren zur erzeugung von korrosions- und verschleissbestaendigen schutzschichten auf magnesium und magnesiumlegierungen |
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DE19724013A1 (de) * | 1997-06-06 | 1998-12-10 | Alfred R Franz Fa | Schwarzverchromte, oberflächenfehlerfreie, komplettierbare Spritzgußteile aus Magnesiumlegierungen |
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2001
- 2001-10-11 DE DE50103781T patent/DE50103781D1/de not_active Expired - Lifetime
- 2001-10-11 EP EP01124435A patent/EP1302565B1/fr not_active Expired - Lifetime
- 2001-10-11 AT AT01124435T patent/ATE277207T1/de active
-
2002
- 2002-10-09 WO PCT/EP2002/011291 patent/WO2003033777A1/fr not_active Application Discontinuation
- 2002-10-10 JP JP2002297389A patent/JP2003221683A/ja active Pending
- 2002-10-10 KR KR1020020061816A patent/KR100553233B1/ko not_active IP Right Cessation
- 2002-10-11 CN CNB021457549A patent/CN1213169C/zh not_active Expired - Fee Related
- 2002-10-11 US US10/269,265 patent/US20030079997A1/en not_active Abandoned
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DE19723980A1 (de) * | 1997-06-06 | 1998-12-10 | Alfred R Franz Fa | Kontinuierliches, rechnergesteuertes Verfahren zur Herstellung von schwarzverchromten, oberflächenfehlerfreien, komplettierbaren Spritzgußteilen aus Magnesiumlegierungen mit elektrisch leitfähigen und optimal haftfähigen Oberflächenbereichen |
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Also Published As
Publication number | Publication date |
---|---|
DE50103781D1 (de) | 2004-10-28 |
CN1412351A (zh) | 2003-04-23 |
EP1302565A1 (fr) | 2003-04-16 |
US20030079997A1 (en) | 2003-05-01 |
WO2003033777A1 (fr) | 2003-04-24 |
KR20030030953A (ko) | 2003-04-18 |
JP2003221683A (ja) | 2003-08-08 |
CN1213169C (zh) | 2005-08-03 |
KR100553233B1 (ko) | 2006-02-22 |
ATE277207T1 (de) | 2004-10-15 |
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