EP1302565A1 - 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
- EP1302565A1 EP1302565A1 EP01124435A EP01124435A EP1302565A1 EP 1302565 A1 EP1302565 A1 EP 1302565A1 EP 01124435 A EP01124435 A EP 01124435A EP 01124435 A EP01124435 A EP 01124435A EP 1302565 A1 EP1302565 A1 EP 1302565A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- light metal
- metal alloy
- 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.)
- Granted
Links
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 239000003929 acidic solution Substances 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 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 4
- 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
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract 2
- 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
- 238000002161 passivation Methods 0.000 claims description 11
- 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
- 239000003973 paint Substances 0.000 claims description 8
- 238000001465 metallisation Methods 0.000 claims description 7
- 239000004922 lacquer Substances 0.000 claims description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- DAFQZPUISLXFBF-UHFFFAOYSA-N tetraoxathiolane 5,5-dioxide Chemical compound O=S1(=O)OOOO1 DAFQZPUISLXFBF-UHFFFAOYSA-N 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- 230000002378 acidificating effect Effects 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
- 239000002245 particle Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 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
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000013532 laser treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 238000009713 electroplating Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910001234 light alloy Inorganic materials 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy 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
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction 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
- 229910052802 copper Inorganic materials 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
- 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
- 230000006872 improvement Effects 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
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 238000004381 surface treatment Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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.
- the present invention is therefore based on the technical problem Favorable and especially flexible coating process for light metal alloy surfaces specify.
- the method according to the invention is characterized by the galvanic containing Sn Layer out together with the other layers mentioned enables a reliable sealing of the light metal alloy surface.
- the proportion of Sn should preferably be in the corresponding galvanic layer are above 40% by weight, but preferably above 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 to be understood generally in the sense of a valence electron transition and includes in particular 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 occur 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.
- cleaning is a chemical metallization made that contains Zn.
- This metallization can also the metals Contain Cu and / or Ni.
- the subsequent galvanic intermediate layer could also be Cu and / or Ni included.
- the next galvanic layer already discussed contains, of course Sn, but could also e.g. also contain Zn, Bi and / or Pb to make up the To improve corrosion properties.
- the method described so far leads to stable and permanent galvanic Coatings of light metal alloy surfaces. Because the procedure be carried out with wet chemical and galvanic process steps can, it is regarding the usable part sizes and geometries very flexible and inexpensive to carry out on a large scale. In the procedure described so far, there is a metallic one conductive surface that is desired for many applications.
- a particular attraction of the invention is that it contains Sn galvanic layer can also be deposited a varnish.
- the paint can be colored opaque or transparent be and thus achieve the most diverse decorative effects. He can too Have structures, such as surface splashes, with conventional 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.
- laser treatment can also be carried out according to the invention even in the case of unpainted coated parts to be advantageous to the already given surface conductivity partially improve.
- laser treatment can also be used when the surface treated according to the invention has other or additional insulating layers is provided, for example with sputtered oxides, nitrides and the like.
- 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 with years of use, the outer surface can with insufficient coating 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Chemically Coating (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Priority Applications (8)
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 |
AT01124435T ATE277207T1 (de) | 2001-10-11 | 2001-10-11 | Beschichtungsverfahren für leichtmetalllegierungsoberflächen |
DE50103781T DE50103781D1 (de) | 2001-10-11 | 2001-10-11 | Beschichtungsverfahren für Leichtmetalllegierungsoberflächen |
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 true EP1302565A1 (fr) | 2003-04-16 |
EP1302565B1 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) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20090405A1 (it) * | 2009-03-17 | 2010-09-18 | Nuovo Pignone Spa | Metodo di produzione di un rivestimento protettivo per un componente di una turbomacchina, il componente stesso e la relativa macchina |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2002338880A1 (en) * | 2002-10-09 | 2004-05-04 | Wolf-Dieter Franz | Method for cleaning and passivating light alloy surfaces |
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 |
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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US2215165A (en) * | 1936-06-06 | 1940-09-17 | Crosse & Blackwell Ltd | Process for treating tin-plate containers |
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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 |
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DE19724013A1 (de) * | 1997-06-06 | 1998-12-10 | Alfred R Franz Fa | Schwarzverchromte, oberflächenfehlerfreie, komplettierbare Spritzgußteile aus Magnesiumlegierungen |
DE19723975A1 (de) * | 1997-06-06 | 1998-12-10 | Alfred R Franz Fa | Kontinuierliches, rechnergesteuertes Verfahren zur Herstellung von schwarzchromatierten oberflächenfehlerfreien, komplettierbaren Spritzgußteilen aus Magnesiumlegierungen mit elektrisch leitfähigen und optimal haftfähigen Oberflächenbereichen |
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EP0978576A1 (fr) * | 1998-02-23 | 2000-02-09 | Mitsui Mining and Smelting Co., Ltd | Produit a base de magnesium resistant a la corrosion presentant le lustre d'un metal de base et son procede d'obtention |
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- 2001-10-11 AT AT01124435T patent/ATE277207T1/de active
- 2001-10-11 DE DE50103781T patent/DE50103781D1/de not_active Expired - Lifetime
- 2001-10-11 EP EP01124435A patent/EP1302565B1/fr not_active Expired - Lifetime
-
2002
- 2002-10-09 WO PCT/EP2002/011291 patent/WO2003033777A1/fr not_active Application Discontinuation
- 2002-10-10 KR KR1020020061816A patent/KR100553233B1/ko not_active IP Right Cessation
- 2002-10-10 JP JP2002297389A patent/JP2003221683A/ja active Pending
- 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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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ITMI20090405A1 (it) * | 2009-03-17 | 2010-09-18 | Nuovo Pignone Spa | Metodo di produzione di un rivestimento protettivo per un componente di una turbomacchina, il componente stesso e la relativa macchina |
EP2233534A1 (fr) * | 2009-03-17 | 2010-09-29 | Nuovo Pignone S.p.A. | Méthode de production d'un revêtement de protection pour un composant de turbomachine, le composant lui-même et la machine correspondante |
Also Published As
Publication number | Publication date |
---|---|
EP1302565B1 (fr) | 2004-09-22 |
ATE277207T1 (de) | 2004-10-15 |
KR100553233B1 (ko) | 2006-02-22 |
WO2003033777A1 (fr) | 2003-04-24 |
CN1412351A (zh) | 2003-04-23 |
KR20030030953A (ko) | 2003-04-18 |
US20030079997A1 (en) | 2003-05-01 |
JP2003221683A (ja) | 2003-08-08 |
DE50103781D1 (de) | 2004-10-28 |
CN1213169C (zh) | 2005-08-03 |
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