EP1302565B1 - Coating method for light metal alloy surfaces - Google Patents

Coating method for light metal alloy surfaces Download PDF

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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
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EP
European Patent Office
Prior art keywords
light metal
metal alloy
solution
treatment
acid
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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
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EP01124435A
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German (de)
French (fr)
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EP1302565A1 (en
Inventor
Wolf-Dieter Franz
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Franz Oberflaechentechnik GmbH and Co KG
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Franz Oberflaechentechnik GmbH and Co KG
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Application filed by Franz Oberflaechentechnik GmbH and Co KG filed Critical Franz Oberflaechentechnik GmbH and Co KG
Priority to EP01124435A priority Critical patent/EP1302565B1/en
Priority to DE50103781T priority patent/DE50103781D1/en
Priority to AT01124435T priority patent/ATE277207T1/en
Priority to PCT/EP2002/011291 priority patent/WO2003033777A1/en
Priority to JP2002297389A priority patent/JP2003221683A/en
Priority to KR1020020061816A priority patent/KR100553233B1/en
Priority to US10/269,265 priority patent/US20030079997A1/en
Priority to CNB021457549A priority patent/CN1213169C/en
Publication of EP1302565A1 publication Critical patent/EP1302565A1/en
Application granted granted Critical
Publication of EP1302565B1 publication Critical patent/EP1302565B1/en
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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)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (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)

Abstract

Process for coating light metal alloy surfaces comprises cleaning the surfaces; chemically metallizing using zinc; intermediate coating in a galvanic manner; and galvanically coating using tin. <??>Preferably the cleaning step comprises degreasing the surface using an alkali, and treating the surface in an acidic solution or solution of a salt of an acid with simultaneous oxidative production of a passivating layer. Treatment with the acidic solution comprises treating in a weakly acidic solution and then in a strongly acidic solution. The weakly acidic solution contains a carboxylic acid and a pyrophosphate and the strongly acidic solution contains phosphoric acid and ammonium bifluoride.

Description

Die vorliegende Erfindung bezieht sich auf ein Verfahren zum Beschichten von Leichtmetalllegierungsoberflächen. Unter Leichtmetalllegierungen sind hierbei Legierungen zu verstehen, die Al und/oder Mg in einem Anteil enthalten, der die chemischen Eigenschaften der Oberfläche wesentlich mitbestimmt.The present invention relates to a method for coating Light alloy surfaces. Among them are light alloys To understand alloys that contain Al and / or Mg in a proportion that the chemical properties of the surface significantly influenced.

Solche Leichtmetalllegierungen sind wegen ihres geringen spezifischen Gewichts für verschiedenste Anwendungen von großem Interesse, bei denen einerseits eine hohe mechanische Stabiltät erreicht werden muss und andererseits die Gesamtmasse des Bauteils eine kritische Rolle spielt. Solche Anwendungen liegen z.B. im Flugzeugbau oder, vor allem in jüngerer Zeit, bei Kraftfahrzeugen oder Gehäusen von hochwertigen Geräten. Insbesondere bei Mobiltelefonen werden Rahmenteile aus Leichtmetalllegierungen verwendet, die einerseits im Hinblick auf die Stabilität die Grundstruktur des Gesamtaufbaus bilden und andererseits den Benutzer möglichst wenig mit Gewicht belasten sollen.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. Especially with mobile phones 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.

Der Nachteil solcher Leichtmetalllegierungen besteht jedoch in ihrer Oxidationsempfindlichkeit, die immer wieder für Korrosionsprobleme sorgt und einen Bedarf an geeigneten Oberflächenbehandlungsverfahren zur Folge hat. Die Probleme mit der Konservierung solcher Leichtmetalllegierungsoberflächen haben im Übrigen auch eine wirklich dauerhafte optische Veredlung entsprechender Bauteile immer wieder behindert.The disadvantage of such light metal alloys, however, is their sensitivity to oxidation, which always causes corrosion problems and one Requires suitable surface treatment processes. The Have problems with the preservation of such light metal alloy surfaces by the way also a really permanent optical refinement corresponding Components repeatedly hindered.

Es sind die verschiedensten Verfahren versucht und auch in größerem Umfang verwendet worden. Da diese Verfahren die technischen Anforderungen entweder nur eingeschränkt erfüllen konnten oder sehr aufwendig waren oder auch wesentliche Einschränkungen im Hinblick auf die Größe oder Geometrie der zu behandelnden Teile mit sich brachten, besteht nach wie vor Bedarf an Verbesserungen bzw. Alternativen.Various methods have been tried and also used on a larger scale Service. Because these procedures only meet the technical requirements could meet to a limited extent or were very complex or essential Limitations on the size or geometry of the items to be treated Parts brought with them, there is still a need for improvements or alternatives.

Die DE 197 24 013 A zeigt die Behandlung von Aluminium-Magnesiumlegierungsoberflächen durch Entfetten, Beizen mit Phosphorsäure und Fluorid, chemische Abscheidung einer Zink-Schicht, galvanische Abscheidung einer Kupferschicht und galvanische Abscheidung einer Zinnbronzeschicht sowie galvanische Abscheidung einer abschließenden Schwarzchrom-Deckschicht. Der Zinnanteil der Zinnbronzeschicht soll vorzugsweise höchstens 20 % und insbesondere höchstens 9 % betragen. Die abschließende Schwarzchromschicht hat verschiedene vorteilhafte Eigenschaften.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.

Die US 2,215,165 A befasst sich mit Blechbehältnissen für Nahrungsmittel mit einer anodischen Beschichtung der verzinnten Blechbehälter und einer Lackierung darauf.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.

Die JP 52 068832 A befasst sich laut Derwent Publications Abstract mit der elektrolytischen Behandlung von Stahl mit Phosphatlösungen zur Anodisierung und einem nachfolgenden Anstrich.According to Derwent Publications Abstract, JP 52 068832 A deals with electrolytic Treatment of steel with phosphate solutions for anodization and a subsequent painting.

Die JP 59 208098 A behandelt laut Derwent Publications Abstract die Vorbehandlung einer Metalloberfläche vor einer elektrophoretischen Beschichtung mit Nickel oder einer Zinnkupferlegierung oder anderen Legierungen unter Anwesenheit von sechswertigem Chrom. According to Derwent Publications Abstract, 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.

Die DE-A-197 23 980 zeigt ein Verfahren zur Herstellung schwarzverchromter Spritzgussteile aus Magnesiumlegierungen, bei dem die schwarzverchromten Teile auf bestimmten Oberflächenbereichen mit Wasser abstoßenden organischen Stoffen, u. a. Lacken, imprägniert werden.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.

Die EP 0 890 743 A2 zeigt die Oberflächenbeschichtung einer Platte mit Cu, Sn oder einem Metallphosphat. Speziell für Aluminium wird eine Chromatierung und Vernickelung oder Verkupferung vorgeschlagen, es ist jedoch auch von einer reinen Verzinnung die Rede. Auf diese Zwischenschicht wird daraufhin eine Gleitschicht aufgebracht. 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.

Der vorliegenden Erfindung liegt somit das technische Problem zugrunde, ein günstiges und insbesondere flexibles Beschichtungsverfahren für Leichtmetalllegierungsoberflächen anzugeben.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.

Erfindungsgemäß ist hierzu vorgesehen, ein Verfahren zum Beschichten von Leichtmetalllegierungsoberflächen mit den Schritten:

  • passivierende Reinigung der Leichtmetalllegierungsoberfläche,
  • chemische Metallisierung, die Zn enthält,
  • galvanische Zwischenbeschichtung,
  • galvanische Beschichtung, die über 50 Gew.-% Sn enthält, und
  • Abscheidung einer Lackschicht auf der Sn enthaltenden galvanischen Schicht.
According to the invention, there is provided a method for coating light metal alloy surfaces with the following steps:
  • passivating cleaning of the light metal alloy surface,
  • chemical metallization containing Zn
  • galvanic intermediate coating,
  • electroplated coating containing over 50% by weight of Sn, and
  • Deposition of a lacquer layer on the galvanic layer containing Sn.

Bevorzugte Ausführungsformen der Erfindung sind in den abhängigen Ansprüchen angegeben.Preferred embodiments of the invention are in the dependent claims specified.

Das erfindungsgemäße Verfahren zeichnet sich durch die Sn enthaltende galvanische Schicht aus, die zusammen mit den anderen genannten Schichten eine zuverlässige Versiegelung der Leichtmetalllegierungsoberfläche ermöglicht. Der Sn-Anteil in der entsprechenden galvanischen Schicht beträgt dabei über 50 Gew.-%.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.

Durch die zunächst erfolgende passivierende Reinigung, der dann eine chemische Metallisierung mit zumindest dem Metall Zn folgt, lässt sich eine gute Haftung der galvanischen Schicht mit Sn erreichen. Jedoch wird zur Verbesserung noch eine galvanische Zwischenschicht verwendet, die die Aufgabe hat, die zuvor chemisch erzeugte Metallschicht mit Zn vor einer Beschädigung bei einer nachfolgenden galvanischen Beschichtung mit (u.a.) Sn zu schützen. Bei der galvanischen Zwischenbeschichtung kann nämlich ein auf die Stabilität der Zn enthaltenden Metallisierung abgestimmter Prozess gewählt werden, auf dessen Schicht dann wiederum der Sn enthaltende galvanische Prozess ablaufen kann, ohne auf die Zn enthaltende Schicht Rücksicht nehmen zu müssen. Dabei kann es insbesondere sinnvoll sein, bei der galvanischen Zwischenbeschichtung einen Galvanikprozess mit einem pH-Wert im Bereich von etwa 7 bis etwa 10 zu verwenden. Die Zn enthaltende Schicht kann durch saure Prozesse einerseits und durch zu alkalische Prozesse andererseits beschädigt werden. Diese sind bei der Herstellung der Sn enthaltenden Galvanikschicht möglicherweise erwünscht oder unvermeidlich.Through the first passivating cleaning, which is then a chemical Metallization with at least the metal Zn follows, good adhesion of the achieve galvanic layer with Sn. However, there is still a galvanic one for improvement Intermediate layer used, which has the task of previously chemically generated metal layer with Zn before damage to a to protect the subsequent galvanic coating with (among other things) Sn. In the galvanic intermediate coating can namely on the stability of the Zn containing metallization can be chosen to match the process Layer then again the galvanic process containing Sn can run, without having to consider the layer containing Zn. It can it makes particular sense to have a galvanic intermediate coating Electroplating process with a pH in the range of about 7 to about 10 to use. The layer containing Zn can, on the one hand, be subjected to acidic processes and damaged on the other hand by processes that are too alkaline. These are may be desirable in the manufacture of the electroplating layer containing Sn or inevitable.

Die erwähnte passivierende Reinigung kann als ersten Schritt eine alkalische Entfettung der Leichtmetalllegierungsoberfläche enthalten, woraufhin die entfettete Oberfläche mit einer Lösung behandelt wird, die einerseits sauer ist, zumindest das Salz einer Säure enthält, und damit die Leichtmetalllegierungsoberfläche etwas beizt, und andererseits die Eigenschaft hat, eine oxidative Passivierung herbeizuführen. Der Begriff der Oxidation ist dabei allgemein im Sinne eines Valenzelektronenübergangs zu verstehen und beinhaltet insbesondere die Bildung von Oxiden wie Al2O3 und von Fluoriden wie MgF2.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. The term 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 .

Bei einem wesentlichen Mg-Anteil, vorzugsweise bei einem Mg-Anteil von mindestens 50 Gew.-%, insbesondere mindestens 80 Gew.-%, bietet sich an, die bereits erwähnte Behandlung in der sauren bzw. Säuresalz-Lösung in zwei Stufen durchzuführen. Zum einen wird zunächst eine Behandlung in einer relativ schwach sauren Lösung mit einem pH-Wert in der Größenordnung von 3-5, vorzugsweise um 4, vorgenommen. Zum anderen wird danach eine weitere saure Lösung verwendet, die jedoch mit einem pH-Wert in der Größenordnung von 0,5-2, vorzugsweise um 1, sehr viel saurer ist und zum anderen Fluoridionen enthält. Diese Fluoridionen bilden während der Beizung der Oberfläche gleichzeitig eine Passivierungsschicht, die MgF2 enthält. With a substantial Mg content, preferably with a Mg content of at least 50% by weight, in particular at least 80% by weight, it is advisable to carry out the above-mentioned treatment in the acid or acid salt solution in two stages. On the one hand, treatment is first carried out in a relatively weakly acidic solution with a pH in the order of 3-5, preferably around 4. On the other hand, another acidic solution is used thereafter, which, however, is much more acidic with a pH of the order of 0.5-2, preferably around 1, and on the other hand contains fluoride ions. These fluoride ions simultaneously form a passivation layer which contains MgF 2 during the pickling of the surface.

Die schwach saure Lösung kann beispielsweise eine Mischung einer Carbonsäure, z.B. Zitronensäure, Apfelsäure, Oxalsäure oder Milchsäure, und einem Pyrophosphat enthalten. Die stark saure, nachfolgend verwendete Lösung kann beispielsweise eine Mischung von Phosphorsäure und Ammoniumbifluorid enthalten.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.

Wenn die Leichtmetalllegierung andererseits einen erheblichen Al-Anteil aufweist, insbesondere einen Al-Anteil von mind. 60 Gew.-%, insbesondere mindestens 80 Gew.-%, so kann die Behandlung in der sauren bzw. Säuresalz-Lösung vorzugsweise in einer stark oxidierenden Lösung erfolgen, die gleichzeitig beizt und die Passivierungsschicht erzeugt. Dabei enthält die Passivierungsschicht Al2O3. Günstige Beispiele für die stark oxidierende Lösung sind Salpetersäure, Peroxomonoschwefelsäure oder Kaliumpersulfatlösung.If, on the other hand, the light metal alloy has a considerable Al content, in particular an Al content of at least 60% by weight, in particular at least 80% by weight, 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 . Favorable examples of the strongly oxidizing solution are nitric acid, peroxomonosulfuric acid or potassium persulfate solution.

Eine andere Möglichkeit für die passivierende Reinigung besteht in einer Behandlung (oder enthält eine Behandlung) in einer Lösung, die einerseits Phosphorsäure und andererseits einen Alkohol enthält. Bei dieser Behandlung soll die Oberfläche anodisch gepolt sein. Hierzu wird verwiesen auf die Voranmeldung "Verfahren zum Reinigen und Passivieren von Leichtmetalllegierungsoberflächen" vom 20.06.01 mit dem Aktenzeichen 01 114 981.2 derselben Anmelderin. Der Offenbarungsgehalt dieser Voranmeldung wird hiermit in Bezug genommen. Mit diesem Reinigungsschritt lässt sich eine sehr wirksame Entfettung der Oberfläche mit einer Anätzung kombinieren, wobei der anodische Betrieb einen sehr flexiblen Optimierungsparameter (anodische Stromdichte, Spannung oder dergleichen) zur Verfügung stellt. Der erwähnte Alkohol können die üblichen Alkohole wie Methanol, Ethanol, Propanol, Butanol und höherwertige Alkohole sowie deren Derivate wie etwa Isopropanol sein. Es kommen aber auch Diole, Polyether und andere Alkohole in Betracht. Mischungen sind natürlich auch möglich. Bevorzugt sind Butanol und Isopropanol.Another option for passivating cleaning is treatment (or contains a treatment) in a solution containing phosphoric acid and on the other hand contains an alcohol. This treatment is said to the surface is anodically poled. Please refer to the pre-registration "Process for cleaning and passivating light metal alloy surfaces" dated 06/20/01 with the file number 01 114 981.2 from the same applicant. The disclosure content of this prior application is hereby incorporated by reference taken. With this cleaning step a very effective degreasing can be done combine the surface with an etch, the anodic operation a very flexible optimization parameter (anodic current density, Voltage or the like) provides. 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.

Bei den bereits zuvor erwähnten Legierungen mit wesentlichem Mg-Anteil werden wiederum vorzugsweise Fluoridionen verwendet, um die Oberfläche zu passivieren. Die Fluoridionen werden dabei in einer die Phosphorsäure enthaltenden Lösung eingesetzt, wobei auch bei diesem Behandlungsschritt die Oberfläche anodisch geschaltet ist. Dieser Behandlungsschritt kann im übrigen mit dem ferner den Alkohol enthaltenden Behandlungsschritt zusammenfallen, indem die Lösung Phosphorsäure, Alkohol und Fluoridionen enthält, oder davon getrennt durchgeführt werden. Im letztgenannten Fall erfolgt der Schritt mit Fluoridionen zeitlich zuletzt. Er kann dann dennoch vorteilhafterweise den oder einen anderen Alkohol enthalten.In the alloys mentioned above with a significant Mg content in turn, 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.

Die Fluoridionen können als Ammoniumbifluorid, als Alkalifluorid, als Flusssäure oder in anderer Form vorliegen.The fluoride ions can be used as ammonium bifluoride, as alkali fluoride, as hydrofluoric acid or in another form.

Übrigens sind die beschriebenen Behandlungen mit Fluoridionen, nämlich einerseits die der zweistufig sauren Behandlungen und andererseits die mit der Kombination aus Phosphorsäure und Alkohol, auch dann sinnvoll, wenn die Leichtmetalllegierung zwar kein oder wenig Mg enthält, jedoch einen Si-Anteil von vorzugsweise über 0,1, insbesondere über 0,5 oder 1 oder 2 Gew.-% und darüber. Die Fluoridionenkonzentration kann dabei auf die Höhe der Si-Konzentration abgestimmt werden.Incidentally, 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.

Die beschriebene Behandlung mit der Kombination aus Phosphorsäure und Alkohol und den Fluoridionen kann vorteilhafterweise mit einem alkalischen Spülschritt, etwa in alkalisiertem Wasser mit einem pH-Wert von etwa 10 oder darüber, abgeschlossen werden.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.

Allerdings ist der alkalische Spülschritt bei einer weniger von MgF2 und vielmehr von Al2O3 dominierten Passivierungsoberfläche ungünstig, jedenfalls solange die genannten hohen pH-Werte vorliegen. Man wird dann eher einen zu Al2O3 oxidierenden Schritt in einem wässrigen Oxidationsmittel verwenden. Wegen eines Si-Anteils kann jedoch die Verwendung von Fluoridionen davor trotzdem sinnvoll sein. Das wässrige Oxidationsmittel könnte eine Persulfatlösung oder eine Lösung von Peroxomonoschwefelsäure (Carosche Säure) sein. Die Oxidation sollte dabei immer nach der Fluoridbehandlung erfolgen. Andererseits ist der wässrige Oxidationsschritt jedenfalls bei saurem pH-Wert von etwa pH6 und darunter bei hohem Mg-Anteil problematisch, weil er die Fluoridpassivierung beschädigen kann. However, 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. One will then rather use an Al 2 O 3 oxidizing step in an aqueous oxidizing agent. However, because of the Si content, the use of fluoride ions beforehand can still be useful. 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. On the other hand, 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.

Die genannten Fluoridionenanteile können in Bereichen mit 0,1 oder 0,3 oder 0,5 Gew.-% als Untergrenze und 30 oder 20 oder 10 Gew.-% als Obergrenze liegen. Die anodischen Stromdichten bei der Behandlung mit Phosphorsäure und Alkohol können zwischen 10 oder 30 oder 50 A/m2 als Untergrenze und 1000 A/m2 als Obergrenze liegen. Günstige Temperaturen liegen bei 10-40°C. Die Phosphorsäure kann an den Lösungen einen Anteil von 30-90 Vol% haben und in diesem Volumenanteil 50-95 gewichtsprozentig sein. Vorteilhafterweise besteht die Lösung im Rest im Wesentlichen aus Alkohol und ggf. dem Fluorid.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.

Nach den bislang beschriebenen Vorbehandlungen mit einer passivierenden Reinigung wird, wie zuvor bereits aufgelistet, eine chemische Metallisierung vorgenommen, die Zn enthält. Diese Metallisierung kann daneben auch die Metalle Cu und/oder Ni enthalten.After the pretreatments described so far with passivating cleaning as previously listed, chemical metallization is carried out, which contains Zn. This metallization can also the metals Cu and / or Ni included.

Die darauf folgende galvanische Zwischenschicht könnte ebenfalls Cu und/oder Ni enthalten. Die bereits diskutierte nächste galvanische Schicht enthält natürlich Sn, könnte daneben aber z. B. auch Zn, Bi und/oder Pb enthalten, um die Korrosionseigenschaften zu verbessern.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.

Das bisher beschriebene Verfahren führt zu stabilen und dauerhaften galvanischen Beschichtungen von Leichtmetalllegierungsoberflächen. Da das Verfahren mit nasschemischen und galvanischen Prozessschritten durchgeführt werden kann, ist es hinsichtlich der verwendbaren Teilegrößen und -geometrien sehr flexibel und im Übrigen in großem Maßstab kostengünstig durchzuführen. In der bislang beschriebenen Vorgehensweise kommt dabei eine metallisch leitfähige Oberfläche zustande, die für viele Anwendungen gewünscht ist.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.

Ein besonderer Reiz der Erfindung besteht jedoch darin, dass auf die Sn enthaltende galvanische Schicht zusätzlich ein Lack abgeschieden werden kann. Damit ergeben sich weitreichende Freiheiten im Hinblick auf die optische Oberflächengestaltung. Beispielsweise kann der Lack deckend oder transparent gefärbt sein und damit die vielfältigsten Dekorationseffekte erzielen. Er kann auch Strukturen aufweisen, etwa Flächenspritzer, die mit üblichen Lackiermaschinen standardmäßig aufgebracht werden können, und dem behandelten Teil eine individuelle optische und haptische Erscheinungsform verleihen. Vor allem ist die lackierte Oberfläche jedoch in der Regel elektrisch isolierend, was anwendungsabhängig erwünscht sein kann. Schließlich ist die Oberfläche durch die Lackschicht auch deutlich besser korrosionsgeschützt.A particular attraction of the invention, however, is that it contains Sn galvanic layer can also be deposited a varnish. With it result extensive freedom with regard to the optical surface design. For example, 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.

Dabei hat es sich als sehr vorteilhaft herausgestellt, mit einem Zweikomponentenlack zu arbeiten, der im übrigen je nach Anwendung relativ frei gewählt werden kann. Einkomponentenlacke sind zwar auch möglich, jedoch im allgemeinen von schlechterer technischer Leistung.It turned out to be very advantageous with a two-component paint to work, which are relatively free to choose depending on the application can. One-component paints are also possible, but in general of poorer technical performance.

Die Lackhaftung lässt sich deutlich verbessern, wenn vor dem Aufbringen des Lacks eine Passivierung der Oberfläche der Sn enthaltenden galvanischen Schicht durchgeführt wird. Bevorzugt ist hierbei eine alkalische anodische Oxidation, beispielsweise in einer Lösung, die Phosphate und/oder Carbonate enthält.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.

Diese alkalische anodische Oxidation kann ergänzt werden durch eine nachfolgende kathodische Behandlung in einer Lösung von sechswertigen Chromionen, etwa in Chromsäure. Hierdurch entsteht eine Belegung der Oberfläche mit dreiwertigem Chrom. Aus gesundheitlichen und Umweltgesichtspunkten ist die Verwendung von sechswertigem Chrom jedoch problematisch (allerdings nicht für das Produkt selbst), weswegen die Lackierung der nur mit der alkalischen anodischen Oxidation vorbehandelten galvanischen Oberfläche bevorzugt sein kann.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.

Neben den bereits beschriebenen Vorteilen bietet die lackierte Oberfläche zusätzlich die Möglichkeit, Teilbereiche nachträglich wieder zu einer metallischen Oberflächenleitfähigkeit zurückzuführen. Dies kann beispielsweise sinnvoll sein, um an bestimmten Stellen elektrische Kontakte zu dem beschichteten Bauteil anzubringen, wobei jedoch das Bauteil im übrigen isolierend bleiben soll oder bestimmte optische Oberflächeneigenschaften aufweisen soll oder schließlich besonders gut gegen chemische und mechanische Belastung geschützt sein soll. In addition to the advantages already described, 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.

Erfindungsgemäß wird hierzu eine Laserbehandlung vorgeschlagen, die in relativ unproblematischer Weise zu einem Abplatzen oder Verdampfen des Lacks auf den beschossenen Teilflächen führt und diese durch ein Wiederaufschmelzen zu einer metallischen Leitfähigkeit bringt. Dabei sorgt insbesondere der erfindungsgemäße Sn-Anteil in der Oberfläche für eine besonders gute elektrische Leitfähigkeit und gleichzeitige Beständigkeit des vom Lack befreiten Bereichs.According to 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. In particular, 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.

Bevorzugt ist es weiterhin, auf die mit dem Laser beschossenen Oberflächenbereiche danach binnen Stunden oder wenigen Tagen eine fließfähige metallisch leitfähige Substanz aufzutragen, etwa einen Klebstoff oder eine andere aushärtende Substanz auf Kunststoffbasis, die metallisch leitfähige Partikel enthält. Dies könnten Silberpartikel oder silberbeschichtete Partikel sein. Der Laserbeschuss erfolgt vorzugsweise zweifach, um die thermische Belastung der Oberfläche zu begrenzen, kann jedoch unter Luftatmosphäre mit einer konventionellen Apparatur erfolgen. Bewährt hat sich ein Nd:YAG-Laser, beispielsweise von 90 W Leistung.It is furthermore preferred on the surface areas bombarded with the laser then 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.

Bevorzugte Schichtdicken der galvanischen Zwischenschicht liegen zwischen 5 und 10 µm. Bevorzugte Schichtdicken der Sn enthaltenden galvanischen Schicht liegen ebenfalls bei 5-10 µm.Preferred layer thicknesses of the galvanic intermediate layer are between 5 and 10 µm. Preferred layer thicknesses of the galvanic containing Sn Layer are also at 5-10 microns.

Als Beispiel kann ein in der beiliegenden Figur dargestelltes Druckgussteil aus der Mg-Legierung AZ91 dienen. Es handelt sich dabei um ein Rahmenteil 1 (sog. Chassis) eines Mobiltelefongehäuses. Dieses Rahmenteil 1 soll an den in den Figuren eingezeichneten Linien 2 mit anderen metallischen oder metallisch beschichteten Gehäuseteilen verklebt werden. Dabei ist zum einen wesentlich, dass das Mg-Druckgußrahmenteil 1 eine gute Oberflächendauerhaftigkeit bei hochwertigem Erscheinungsbild bietet. Durch den häufigen Handkontakt und die dadurch gegebene gleichzeitige Einwirkung von Salzen, schwachen Säuren und Feuchtigkeit, sowie durch Witterungseinflüsse und andere Gegebenheiten 5 beim jahrelangen Gebrauch, kann die Außenoberfläche bei unzureichender Beschilchtung unansehnlich werden. Die Innenoberfläche könnte wiederum bei Korrosion zur Partikelerzeugung und damit zu dem Ausfall elektronischer Bauteile führen.As an example, 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.

Bei der Verklebung ist außerdem wichtig, dass die verklebten Teile elektrisch gut leitfähig miteinander verbunden werden, um eine elektromagnetische Abschirmung des Mobiltelefons herzustellen. Insgesamt muss also eine stabile Beschichtung des Mg-Druckgußteils 1 gleichzeitig eine gute elektrische Oberflächenleitfähigkeit der für die Verklebung herangezogenen Oberflächenbereiche 2 ermöglichen. Dies gilt auch für Flächenteile der eingezeichneten Auflagedome 3 für eine Leiterplatte des Mobiltelefons, die wegen der notwendigen Masseverbindung ebenfalls leitfähig werden. Weitere Details des Rahmenteils 1 sind für das Verständnis der Erfindung ohne Belang.When gluing it is also important that the glued parts are electrical well connected to each other to form an electromagnetic shield of the mobile phone. So overall, 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.

Das Rahmenteil 1 wird daher zunächst konventionell alkalisch entfettet und bei pH4 in einer Lösung mit Zitronensäure und Pyrophosphat behandelt. Daraufhin erfolgt bei pH1 eine Passivierung in einer stark sauren Lösung mit Phosphorsäure und Ammoniumbifluorid.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.

Auf die in dieser Weise gereinigte und passivierte Oberfläche wird eine chemische Konversionsschicht aus Zn und Cu aufgebracht, auf die dann mit konventioneller Galvanik eine 7 µm starke Cu-Schicht abgeschieden werden kann.A chemical is applied to the surface cleaned and passivated in this way Conversion layer made of Zn and Cu applied to the then with conventional Electroplating a 7 µm thick Cu layer can be deposited.

Auf diese schon relativ kräftige galvanische Schicht aus Cu wird daraufhin die für die Erfindung charakteristische galvanische Schicht aus Sn und bei diesem Beispiel zusätzlich Zn abgeschieden, und zwar in diesem Fall in einem Massenverhältnis von 70 : 30 (Sn:Zn). Die Schichtdicke liegt dabei bei 8 µm. Then the already relatively strong galvanic layer made of Cu characteristic of the invention galvanic layer of Sn and this Example additionally Zn deposited, in this case in a mass ratio from 70:30 (Sn: Zn). The layer thickness is 8 µm.

Diese noch elektrisch leitfähige Oberfläche wird nun für die Lackierung vorbereitet mit einer alkalischen anodischen Oxidation in einer Phosphatlösung. Auf die Behandlung mit sechswertigem Chrom wird verzichtet. Stattdessen wird direkt auf die anodisierte Oberfläche ein kommerzieller Zweikomponentenlack aufgebracht und ausgehärtet.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.

Damit hat die Oberfläche des Mg-Druckgussteils 1 die endgültige optische und technische Qualität, wobei sie durchaus transparent farbig lackiert sein kann, so dass sich durch das durchscheinende Metall ein attraktives Erscheinungsbild ergibt.So that 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.

Diese Oberfläche wird daraufhin an den eingezeichneten Bahnen 2 und Auflagedomen 3 mit einem kommerziellen Nd:YAG-Laser behandelt. Dieser Laser ist gütegeschaltet und hat bei einem Lampenstrom von etwa 32 A eine Leistung von 90W. Es erfolgt ein zweifaches Nachfahren der in der Figur dargestellten Linien und Flächen, wobei genau genommen Punkt an Punkt gesetzt wird. Empirisch können der Punktabstand, die Punktgröße und die Energie pro Punkt so ermittelt werden, dass sich einerseits eine durchgehende Bahn und andererseits eine ausreichende Bahnbreite ergeben. Die Bahnbreite sollte nicht zu gering sein, um den elektrischen Übergangswiderstand zu dem anderen Gehäuseteil zu optimieren. Andererseits sollte die Bahnbreite nicht zu groß sein und vollständig von der später aufgebrachten Klebstoffraupe abgedeckt werden. Sie liegt hier bei 1 mm. Dabei sollte schließlich die eingekoppelte Energie pro Schuss nicht unnötig hoch angesetzt werden, um eine zu starke Erwärmung in größeren Tiefen zu vermeiden. Durch zweifachen Beschuss kann die Energie pro Schuss noch verkleinert werden. Pro Schuß werden hier 15 W/mm2 verwendet. Der Vorschub des Lasers beträgt dabei 400 mm/s.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. There is a double tracing of the lines and areas shown in the figure, strictly speaking point to point. 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. Finally, 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.

Auf die somit remetallisierten Oberflächenbereiche 2, 3 kann danach eine Raupe aus einem mit Silberpartikeln versetzten Silikonkleber aufgetragen werden, so dass eine elektrisch leitfähige Verklebung mit einem hier nicht näher beschriebenen anderen Gehäuseteil erfolgen kann. Dieses andere Gehäuseteil ist ebenfalls metallisch oder metallisch beschichtet und wird so verklebt, dass es einen elektrischen Kontakt zu dem Klebstoff erhält. In dieser Weise kann einen elektrischen Kontakt zu dem Klebstoff erhält. In dieser Weise kann insgesamt ein dichtes und elektrisch abgeschirmtes Gehäuse hergestellt werden.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.

Zu den weiteren Einzelheiten der Laserbehandlung wird auf die Paraltelanmeldung "Erzeugung metallisch leitfähiger Oberflächenbereiche auf beschichteten Leichtmetalllegierungen" vom gleichen Anmeldetag und der gleichen Anmelderin verwiesen. Der Offenbarungsgehalt dieser Parallelanmeldung ist hier inbegriffen.For further details of laser treatment, please go to the parallel registration "Generation of metallic conductive surface areas on coated Light metal alloys "from the same filing date and the same applicant directed. The disclosure content of this parallel application is included here.

Claims (19)

  1. A method of coating a light metal alloy surface (1) comprising the steps:
    a passivating cleaning of the light metal alloy surface (1),
    a chemical metallization comprising Zn,
    a galvanic intermediate coating,
    a galvanic coating comprising more than 50 weight % Sn, and
    a deposition of a lacquer layer on said galvanic layer comprising Sn.
  2. The method according to claim 1 in which said passivating cleaning comprises the steps:
    an alkaline degreasing of said light metal alloy surface (1) and
    a treatment of said light metal alloy surface (1) in an acid solution or in a solution of a salt of an acid while simultaneously producing a passivating layer in an oxidizing manner.
  3. The method according to claim 2, in which said light metal alloy (1) comprises a Mg portion of at least 50 weight % and said treatment in said acid solution comprises the steps:
    treatment in a weak acid solution and
    thereafter treatment in a strong acid solution, wherein said strong acid solution comprises fluoride ions.
  4. The method according to claim 3 in which said weak acid solution comprises a carbon acid or a pyrophosphate.
  5. The method according to claim 3 or 4 in which said strong acid solution comprises phosphoric acid and ammonium bifluoride.
  6. The method according to claim 2 in which said light metal alloy comprises an Al portion of at least 60 weight % and said treatment in said acid solution and acid salt solution, respectively, is done in a strongly oxidizing solution.
  7. The method according to claim 6 in which said strongly oxidizing solution comprises nitric acid, peroxysulfuric acid or a persulfate solution.
  8. The method according to claim 1 in which said passivating cleaning of said light metal alloy surface (1) comprises a step in a solution comprising said phosphoric acid and an alcohol, in which said light metal alloy surface (1) is anodized.
  9. The method according to claim 8 in which said light metal alloy (1) comprises an Mg-portion of at least 50 weight % and/or a Si-portion of at least 0.1 weight % and said passivating cleaning is completed by a treatment step in a solution comprising phosphoric acid and fluoride ions in which said light metal alloy surface (1) is anodized.
  10. The method according to claim 8 in which said light metal alloy comprises an Al-portion of at least 60 weight % and said passivating cleaning is completed by a treatment step in aqueous oxidizing agent.
  11. The method according to one of the preceding claims in which said chemical metallization comprises besides Zn also Cu and/or Ni.
  12. The method according to one of the preceding claims in which said galvanic intermediate coating comprises Cu and/or Ni.
  13. The method according to one of the preceding claims in which said galvanic layer comprising Sn further comprises Zn, Bi and/or Pb.
  14. The method according to one of the preceding claims in which said lacquer is a two-component lacquer.
  15. The method according to one of the preceding claims in which a passivating treatment of said galvanic layer comprising Sn is done before said lacquer coating.
  16. The method according to claim 15 in which said passivating treatment comprises an alkaline anodic oxidation.
  17. The method according to claim 16 in which said alkaline anodic oxidation is done in a solution comprising phosphates and/or carbonates.
  18. The method according to claim 15, 16 or 17 in which said passivating treatment comprises a cathodic treatment in a solution comprising hexavalent chromium ions, which is done after said alkaline anodic oxidation if any.
  19. The method according to one of the preceding claims in which parts (2, 3) of said light metal alloy surface (1) are laser-bombarded in order to increase the electrical conductivity of said light metal alloy surface.
EP01124435A 2001-10-11 2001-10-11 Coating method for light metal alloy surfaces Expired - Lifetime EP1302565B1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP01124435A EP1302565B1 (en) 2001-10-11 2001-10-11 Coating method for light metal alloy surfaces
DE50103781T DE50103781D1 (en) 2001-10-11 2001-10-11 Coating process for light metal alloy surfaces
AT01124435T ATE277207T1 (en) 2001-10-11 2001-10-11 COATING PROCESS FOR LIGHT METAL ALLOY SURFACES
PCT/EP2002/011291 WO2003033777A1 (en) 2001-10-11 2002-10-09 Coating method for light metal alloy surfaces
JP2002297389A JP2003221683A (en) 2001-10-11 2002-10-10 Coating method onto surface of light metal alloy
KR1020020061816A KR100553233B1 (en) 2001-10-11 2002-10-10 Coating process for light metal alloy surface
US10/269,265 US20030079997A1 (en) 2001-10-11 2002-10-11 Method for coating metal surfaces
CNB021457549A CN1213169C (en) 2001-10-11 2002-10-11 Light metal alloy surface coating method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01124435A EP1302565B1 (en) 2001-10-11 2001-10-11 Coating method for light metal alloy surfaces

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EP1302565B1 true EP1302565B1 (en) 2004-09-22

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AU2002338880A1 (en) * 2002-10-09 2004-05-04 Wolf-Dieter Franz Method for cleaning and passivating light alloy surfaces
JP4736084B2 (en) * 2005-02-23 2011-07-27 オーエム産業株式会社 Manufacturing method of product made of magnesium or magnesium alloy
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 (en) * 2006-12-18 2010-08-11 比亚迪股份有限公司 Composition for magnesium alloy surface activation
IT1393140B1 (en) * 2009-03-17 2012-04-11 Nuovo Pignone Spa METHOD OF PRODUCTION OF A PROTECTIVE COATING FOR A COMPONENT OF A TURBOMACCHINA, THE SAME COMPONENT AND THE RELATED MACHINE
CN102110866B (en) * 2009-12-24 2013-08-28 深南电路有限公司 Manufacturing process of waveguide slot
CN103305894B (en) * 2012-03-09 2016-01-27 苏州汉扬精密电子有限公司 Surface treatment method of Mg alloy
EP2722930A1 (en) * 2012-10-16 2014-04-23 Delphi Technologies, Inc. Coated contact element
CN103498156A (en) * 2013-09-27 2014-01-08 成都四威高科技产业园有限公司 Surface coating technology of silicon carbide particle reinforced aluminium-based composite
CN104562004B (en) * 2015-01-28 2017-01-04 江西富意美实业有限公司 A kind of all kinds of temperature controller aluminium alloy temperature-sensing pipes and preparation method thereof
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US20030079997A1 (en) 2003-05-01
JP2003221683A (en) 2003-08-08
CN1213169C (en) 2005-08-03
DE50103781D1 (en) 2004-10-28
WO2003033777A1 (en) 2003-04-24
KR100553233B1 (en) 2006-02-22
ATE277207T1 (en) 2004-10-15
CN1412351A (en) 2003-04-23
KR20030030953A (en) 2003-04-18

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