EP2115182B1 - Bright coatings for aluminium or steel motor vehicle wheels and their production - Google Patents

Bright coatings for aluminium or steel motor vehicle wheels and their production Download PDF

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Publication number
EP2115182B1
EP2115182B1 EP08701133A EP08701133A EP2115182B1 EP 2115182 B1 EP2115182 B1 EP 2115182B1 EP 08701133 A EP08701133 A EP 08701133A EP 08701133 A EP08701133 A EP 08701133A EP 2115182 B1 EP2115182 B1 EP 2115182B1
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EP
European Patent Office
Prior art keywords
layer
aluminium
surface coating
steel
coating according
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Not-in-force
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EP08701133A
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German (de)
French (fr)
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EP2115182A1 (en
Inventor
Thomas Kränzler
Karsten Loehr
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Mercedes Benz Group AG
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Daimler AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/12764—Next to Al-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]

Definitions

  • the invention relates to durable and stain-resistant aluminum-based gloss coatings on motor vehicle wheels or motor vehicle rims and to methods for producing such gloss layers on light-metal or steel substrates.
  • high-gloss surfaces can also be achieved through the process of so-called "gloss-anodising" of the aluminum surfaces.
  • Such a method for aluminum wheels is known, for example, from Alcoa under the Dura-Bright® brand.
  • the main steps of the process include applying a chemical whitening composition to the product, deoxidizing the product surface, electrochemically generating a porous oxide on that product surface by contacting it with an electrolyte bath, containing phosphorous or phosphonic acid and applying a silicate or siloxane-based outer layer to the porous oxide.
  • the surface is dirt-repellent and scratch-resistant as possible.
  • ETC coatings Dirt-repellent coatings or so-called easy-to-clean coatings or coatings (ETC coatings) are known for the protection of high-quality components made of glass, plastic and metals and are intended to prevent contamination or facilitate cleaning. The mechanism of action varies depending on the application.
  • water-repellent coatings are used for glass surfaces. Clean glass is relatively hydrophilic and forms a contact angle of 20 ° to water. In contrast, a hydrophobic ETC coating increases the Contact angle to well over 100 ° with respect to water. This ETC coating offers a significantly reduced wettability, so that waterborne soiling can bead off or be easily washed off.
  • a chemical brightener is applied, the surface is deoxidized, then electrochemically generates a porous oxide and then applied to an outer layer based on silicate or siloxane.
  • the polysilazane is in particular a polysilazane of the formula (SiR'R '"- NR"') n , where R ', R ", R''' may be identical or different and are either hydrogen or organic or organometallic radicals.
  • the ionic reagent is preferably a salt of a carboxylic acid, especially a hydroxycarboxylic acid, or a cationic or anionic silane or an oligomer or polymer.
  • the effect of the hydrophilic layers is based on the fact that hydrophobic contaminants adhere poorly or that the surface can be washed off well with aqueous cleaning agents. It is an object of the invention to provide a process for the production of durable gloss coatings on aluminum or steel surfaces, which are not amenable to gloss anodization, and to provide gloss coatings of good resistance or dirt-repellent properties on light metal or steel wheels.
  • the object of the invention is achieved in a first aspect, by a surface coating on motor vehicle wheels of light metal casting alloys or steel, which may comprise several layers, wherein it has at least one directly applied to the wheel surface first layer of a CVD coating of aluminum or aluminum alloy, with the features of claim 1.
  • An advantage of the invention is that the visual appearance of expensive forged aluminum rims is thus possible cost-effectively even with low-cost cast aluminum rims or even on steel rims.
  • the thickness of the first layer is preferably 10 to 500 ⁇ m. Particularly preferably, the thickness of cast aluminum rims or steel rims is 30 to 100 ⁇ m.
  • the first layer of Al or Al alloy is often not durable enough.
  • the surface of the first layer therefore carries a second layer in the form of an electrochemically generated micro- or nano-porous oxide layer.
  • This coating is a coating comparable to the anodization of aluminum surfaces.
  • the metallic surface is passivated by the firmly adhering oxide layer and protected against further corrosive attack.
  • this layer forms a good primer for further organic coatings.
  • the thickness of the oxide layer must be limited so that the gloss of the surface is not lost.
  • This second layer preferably has a thickness in the range of 50 to 1000 nm.
  • the first or the second layer thus carries a third layer of a final lacquer layer, in particular a clearcoat or an easy-to-clean lacquer (ETC lacquer).
  • ETC lacquer easy-to-clean lacquer
  • the combination with an ETC coating achieves a visually high-quality surface with the highest corrosion protection and lasting shine at the same time.
  • An optional ETC coating for example with organosilicates, can effectively combat the problem of brake dust rim contamination.
  • the ETC coating can be hydrophilic or hydrophobic coatings. The optimal choice depends, among other things, on the choice of brake lining material in the vehicle brake.
  • the third layer is formed predominantly of silane, silazane, siloxane and / or silicone polymers.
  • the components form the main component of the coating.
  • Other components may in particular be the scratch-resistant filler, hydrophobic or hydrophobizing additives or catalytically active additives.
  • Silica powder, clay minerals, alumina nanopowder or SiO 2 nanofiller are particularly important as fillers.
  • As catalytically active In particular, titanium oxide is important as an additive, which acts oxidatively on the superficially deposited dirt particles by the action of UV light. Particularly favorable is the combination of hydrophilizing additives and catalytically active titanium oxide.
  • a suitable third coating is further composed of siloxane with silicate fillers.
  • the third layer comprises perhyrdosilazane polymers as the main constituent and hydrophilic (co) polymers and / or additives as additives.
  • perhyrdosilazane polymers as the main constituent
  • hydrophilic (co) polymers and / or additives as additives.
  • a combination of perhyrdosilazane polymers, hydrophilic (co) polymers and catalytically active titanium oxide proves to be a particularly effective, scratch-resistant and dirt-repellent coating or easy-to-clean lacquer on the glossy layer or the bright anodised gloss layer.
  • the surface coating of 1, 2 or 3 layers is applied to a motor vehicle wheel made of an Al casting alloy with an Si content in the range from 3 to 12% by weight.
  • the subsequent electrochemical oxidation increases the corrosion resistance of the surface and improves the surface finish for a subsequent coating.
  • a pure aluminum layer is applied in a thickness of 10 to 300 microns.
  • a cold gas process is preferably used, in particular in the deposition on light metal substrates or aluminum wheels.
  • the aluminum surfaces for deposition are brought to a temperature in the range of 280 to 350 ° C and the steel surfaces to a temperature in the range of 280 to 580 ° C.
  • the cold gas process is characterized in that the carrier gas loaded with the gaseous Al carrier substances has a lower temperature than the substrate to be coated. In particular, the carrier gas temperature is significantly below the decomposition or deposition temperature of the Al carrier substance.
  • Particularly preferred is an all-round coating of a cast aluminum rim or steel rim with an applied by a low-temperature CVD method pure aluminum layer in a layer thickness of 30 to max. 100 ⁇ m performed.
  • the second layer of alumina is preferably prepared so that the deposited layer of Al or Al alloy is anodized.
  • the anodization parameters are adjusted to form nano or microstructures of columnar alumina. Due to the interspaces of adjacent columns, the layer is constructed as such nano- or microporous.
  • a clear coat or an easy-to-clean coating is applied to the first coat, but especially to the second coat.
  • the job can be done by wet or powder coating.
  • the method is particularly suitable for coating Al cast alloy wheels for passenger cars or for steel wheels for trucks or buses.

Abstract

Shiny coatings for car wheels made from light metal alloys or steel comprises at least one layer of aluminum or aluminum alloy. This is applied directly to the surface of the wheel. Independent claims are included for: (A) a method for producing shiny coatings on aluminum alloy or steel surfaces comprising:(1) gas phase deposition of aluminum or aluminum alloy to from a sealed, shiny coating; and (b) electrochemical oxidation of the coating to produce a nano- to microporous second layer of aluminum oxide with a thickness of 50 - 1000 nm; and (B) car wheels made from aluminum alloys or steel with a shiny coating as described.

Description

Die Erfindung betrifft beständige und schmutzabweisende Aluminiumbasis-Glanzbeschichtungen auf Kraftfahrzeugrädern, bzw. Kraftfahrzeugfelgen und Verfahren zur Herstellung derartiger Glanzschichten auf Leichtmetall- oder Stahl-Substraten.The invention relates to durable and stain-resistant aluminum-based gloss coatings on motor vehicle wheels or motor vehicle rims and to methods for producing such gloss layers on light-metal or steel substrates.

Auf gewöhnlichen Aluminiumrädern ist üblicherweise eine Schicht aus Pulverlack, die sich auf der Felge und der Radoberfläche befindet.On ordinary aluminum wheels is usually a layer of powder coating, which is located on the rim and the wheel surface.

Der Trend bei Felgen geht neuerdings jedoch zu hochglänzenden Oberflächen die mit herkömmlichen Felgen und Lacken nicht erreicht werden können. Ein mögliches, aber teures Herstellungsverfahren ist das Verchromen der Oberflächen.The trend in rims, however, lately goes to high gloss surfaces that can not be achieved with conventional rims and paints. One possible but expensive manufacturing process is the chrome plating of the surfaces.

Im Bereich der Aluminiumräder lassen sich hochglänzende Oberflächen auch durch den Prozess des so genannten Glanzeloxierens der Aluminiumoberflächen erzielen. Ein derartiges Verfahren für Aluminiumräder ist beispielsweise von Alcoa unter der Marke Dura-Bright® bekannt.In the field of aluminum wheels, high-gloss surfaces can also be achieved through the process of so-called "gloss-anodising" of the aluminum surfaces. Such a method for aluminum wheels is known, for example, from Alcoa under the Dura-Bright® brand.

Aus der DE 699 12 966 ist ein Verfahren zur Oberflächenbehandlung von Aluminium-Raderzeugnissen bekannt. Die Hauptschritte des Verfahrens umfassen das Aufbringen einer Zusammensetzung zum chemischen Aufhellen auf das Produkt, das Desoxidieren der Produktoberfläche, das elektrochemische Erzeugen eines porösen Oxids auf dieser Produktoberfläche durch Kontaktieren mit einem Elektrolytbad, das Phosphor- oder Phosphonsäure enthält und das Aufbringen einer äußeren Schicht auf Silicat- oder Siloxan-Basis auf das poröse Oxid.From the DE 699 12 966 a method for the surface treatment of aluminum wheel products is known. The main steps of the process include applying a chemical whitening composition to the product, deoxidizing the product surface, electrochemically generating a porous oxide on that product surface by contacting it with an electrolyte bath, containing phosphorous or phosphonic acid and applying a silicate or siloxane-based outer layer to the porous oxide.

Die elektrochemische Anodisation zur Herstellung der Oxidschicht ist allerdings stark an bestimmte Legierungszusammensetzungen gebunden. Nur wenige Legierungen bilden bei dieser Behandlung überhaupt eine hoch gleichmäßige, gut haftende und glänzende Oberflächenbeschichtung aus. Im Bereich der Aluminiumräder führt ein derartiges Verfahren nur bei relativ reinen Knet-Aluminium-Legierungen, die für hochpreisige geschmiedete Felgen verwendet werden, zu akzeptablen Ergebnissen. Kostengünstige Aluminium-Gusslegierungen für kostengünstige Aluminiumräder, die sich gegenüber den Knetlegierungen durch vergleichsweise hohe Si-Anteile von über 1 Gew.% bis zu 12 Gew.% auszeichnen, bilden bei der elektrochemischen Anodisation beispielsweise fleckige bräunliche und matte Oberflächen aus. Die Behandlung der noch preisgünstigeren Stahlfelgen durch Glanzeloxieren scheidet grundsätzlich aus.The electrochemical anodization for the production of the oxide layer, however, is strongly linked to certain alloy compositions. Only a few alloys form a highly uniform, well-adhering and glossy surface coating in this treatment. In the field of aluminum wheels, such a process leads only to relatively clean kneading-aluminum alloys, which are used for high-priced forged rims, to acceptable results. Cost-effective aluminum casting alloys for low-cost aluminum wheels, which are distinguished from the wrought alloys by comparatively high Si contents of more than 1% by weight up to 12% by weight, form for example spotty brownish and matte surfaces during electrochemical anodization. The treatment of the even cheaper steel wheels by gloss anodizing is basically eliminated.

Für die Herstellung eines dauerhaften Glanzes auf dem Leichtmetall- oder Stahlsubstrat, insbesondere dem Kraftfahrzeugrad, ist es erforderlich, dass die Oberfläche schmutzabweisend und möglichst kratzfest ist.For the production of a permanent gloss on the light metal or steel substrate, in particular the motor vehicle wheel, it is necessary that the surface is dirt-repellent and scratch-resistant as possible.

Schmutzabweisende Beschichtungen oder so genannte Easy-to-Clean-Beschichtungen oder -Lacke (ETC-Beschichtungen) sind zum Schutz hochwertiger Bauteile aus Glas, Kunststoff und Metallen bekannt und sollen die Verschmutzung verhindern oder die Reinigung erleichtern. Der Wirkmechanismus ist je nach Anwendungsfall unterschiedlich.Dirt-repellent coatings or so-called easy-to-clean coatings or coatings (ETC coatings) are known for the protection of high-quality components made of glass, plastic and metals and are intended to prevent contamination or facilitate cleaning. The mechanism of action varies depending on the application.

Für Glasoberflächen werden beispielsweise Wasser abweisende Beschichtungen angewendet. Sauberes Glas ist relativ hydrophil und bildet gegen Wasser einen Kontaktwinkel um 20°. Eine hydrophobe ETC-Beschichtung erhöht dagegen den Kontaktwinkel auf weit über 100° gegenüber Wasser. Diese ETC-Beschichtung bietet eine deutlich herabgesetzte Benetzbarkeit, so dass wässrige Verschmutzungen abperlen oder sich leicht abwaschen lassen.
Aus der US 6440290 B1 ist ein Verfahren zum Reinigen und Oberflächenbehandeln von Aluminium-Raderzeugnissen zur Verbesserung ihres Glanzes bekannt. Hierzu wird ein chemischer Aufheller aufgebracht, die Oberfläche Desoxidiert, darauf elektrochemisch ein poröses Oxids erzeugt und hierauf eine äußere Schicht auf Silicat- oder Siloxan-Basis aufgebracht.
In der US 5,029,149 werden Dekorationsgegenstände für Uhren und Schmuck offenbart, welche eine doppelte Beschichtung aus Reinaluminium und Aluminiumoxid aufweisen.
Aus der WO2005 085 374 A1 sind besonders kratzfeste Beschichtungen für Leichtmetallfelgen bekannt, die auf der Basis von Perhydrosilazanen bestehen. Kratzfeste und zugleich schmutzabweisende Schichten sind beispielsweise aus der WO 02088269 A1 oder der DE 10 2004 001 288 A1 bekannt. Letzteres Dokument beschreibt hydrophile Beschichtungen für Oberflächen, enthaltend ein oder mehrere Polysilazane und ein ionisches Reagens oder Mischungen von ionischen Reagenzien. Das Polysilazan ist insbesondere ein Polysilazan der Formel (SiR'R'"-NR"')n, wobei R', R", R''' gleich oder unterschiedlich sein können und es sich entweder um Wasserstoff oder organische oder metallorganische Reste handelt. In einer bevorzugten Ausführungsform ist das Polysilazan ein Perhydropolysilazan (R'=R"=R"'=H). Das ionische Reagens ist vorzugsweise ein Salz einer Carbonsäure, insbesondere einer Hydroxycarbonsäure, oder ein kationisches oder anionisches Silan oder ein Oligomer oder Polymer. Hierdurch werden hydrophile Beschichtungen gebildet. Die Wirkung der hydrophilen Schichten beruht darauf, dass hydrophobe Verschmutzungen schlecht haften, beziehungsweise dass sich mit wässrigen Reinigungsmitteln die Oberfläche gut abwaschen lässt.
Es in Aufgabe der Erfindung, ein Verfahren zur Herstellung beständiger Glanzbeschichtungen auf Aluminium- oder Stahloberflächen, welche einer Glanzanodisation nicht zugänglich sind, aufzuzeigen sowie Glanzbeschichtungen guter Beständigkeit oder schmutzabweisender Eigenschaften auf Leichtmetall- oder Stahlrädern bereit zu stellen.For glass surfaces, for example, water-repellent coatings are used. Clean glass is relatively hydrophilic and forms a contact angle of 20 ° to water. In contrast, a hydrophobic ETC coating increases the Contact angle to well over 100 ° with respect to water. This ETC coating offers a significantly reduced wettability, so that waterborne soiling can bead off or be easily washed off.
From the US 6440290 B1 For example, a method for cleaning and surface treating aluminum wheel products to improve their gloss is known. For this purpose, a chemical brightener is applied, the surface is deoxidized, then electrochemically generates a porous oxide and then applied to an outer layer based on silicate or siloxane.
In the US 5,029,149 decorative items for watches and jewelry are disclosed, which have a double coating of pure aluminum and aluminum oxide.
From the WO2005 085 374 A1 Particularly scratch-resistant coatings are known for alloy wheels, which are based on perhydrosilazanes. Scratch-resistant and dirt-repellent layers are for example from the WO 02088269 A1 or the DE 10 2004 001 288 A1 known. The latter document describes hydrophilic coatings for surfaces containing one or more polysilazanes and an ionic reagent or mixtures of ionic reagents. The polysilazane is in particular a polysilazane of the formula (SiR'R '"- NR"') n , where R ', R ", R''' may be identical or different and are either hydrogen or organic or organometallic radicals. In a preferred embodiment, the polysilazane is a perhydropolysilazane (R '= R "= R"' = H) The ionic reagent is preferably a salt of a carboxylic acid, especially a hydroxycarboxylic acid, or a cationic or anionic silane or an oligomer or polymer The effect of the hydrophilic layers is based on the fact that hydrophobic contaminants adhere poorly or that the surface can be washed off well with aqueous cleaning agents.
It is an object of the invention to provide a process for the production of durable gloss coatings on aluminum or steel surfaces, which are not amenable to gloss anodization, and to provide gloss coatings of good resistance or dirt-repellent properties on light metal or steel wheels.

Die Aufgabe der Erfindung wird in einem ersten Aspekt gelöst, durch eine Oberflächenbeschichtung auf Kraftfahrzeugrädern aus Leichtmetall-Gusslegierungen oder Stahl, welche mehrere Schichten umfassen kann, wobei sie zumindest eine unmittelbar auf die Radoberfläche aufgebrachte erste Schicht einer CVD-Beschichtung aus Aluminium oder Aluminiumlegierung aufweist, mit den Merkmalen des Anspruchs 1.The object of the invention is achieved in a first aspect, by a surface coating on motor vehicle wheels of light metal casting alloys or steel, which may comprise several layers, wherein it has at least one directly applied to the wheel surface first layer of a CVD coating of aluminum or aluminum alloy, with the features of claim 1.

In einem weiteren Aspekt wird die Erfindung gelöst durch ein Verfahren zur Herstellung einer beständigen Glanzbeschichtung auf Aluminium- oder Stahloberflächen umfassend die Schritte

  • Gasphasenabscheidung von Aluminium oder Al-Legierung zur Bildung einer dichten ersten Schicht
  • elektrochemische Oxidation der Oberfläche der ersten Schicht und Bildung einer nano- bis mikroporösen zweiten Schicht aus Aluminiumoxid in einer Dicke im Bereich von 50 bis 1000 nm, mit den Merkmalen des Anspruchs 11.
In a further aspect, the invention is achieved by a process for producing a durable glossy coating on aluminum or steel surfaces comprising the steps
  • Vapor deposition of aluminum or Al alloy to form a dense first layer
  • electrochemical oxidation of the surface of the first layer and formation of a nano- to microporous second layer of alumina in a thickness in the range of 50 to 1000 nm, having the features of claim 11.

Für die Erfindung ist es wesentlich, dass die Oberfläche des Substrats beziehungsweise der Aluminiumlegierung- oder Stahloberflächen selbst keinen Glanz aufweisen müssen. Vielmehr wird auf diese Oberflächen zunächst eine dünne metallische Schicht aufgetragen, welche die glänzenden Eigenschaften aufweist. Dabei handelt es sich erfindungsgemäß um eine unmittelbar auf die Radoberfläche aufgebrachte erste Schicht aus Aluminium oder Aluminiumlegierung. Verfahrensgemäß ist vorgesehen, die erste Schicht aus glänzendem Aluminium oder Aluminiumlegierung über die Gasphase abzuscheidenden. Die erste Schicht ist insbesondere eine CVD- oder PVD-Beschichtung aus Aluminium oder Aluminiumlegierung.For the invention, it is essential that the surface of the substrate or the aluminum alloy or steel surfaces themselves need not have gloss. Rather, a thin metallic layer which has the shiny properties is first applied to these surfaces. According to the invention, this is a first layer of aluminum or aluminum alloy applied directly to the wheel surface. According to the invention, the first layer of shiny aluminum or aluminum alloy to be deposited via the gas phase. The first layer is in particular a CVD or PVD coating of aluminum or aluminum alloy.

Ein Vorteil der Erfindung ist es, dass die optische Anmutung von teuren geschmiedeten Aluminiumfelgen somit auch bei preiswerten gegossenen Aluminiumfelgen oder selbst auf Stahlfelgen kostengünstig möglich wird.An advantage of the invention is that the visual appearance of expensive forged aluminum rims is thus possible cost-effectively even with low-cost cast aluminum rims or even on steel rims.

Durch die Art der Glanzbeschichtung aus Al- oder Al-Legierung müssen an die als Substrat verwendeten Legierungen auch keine hohen Anforderungen mehr gestellt werden. Die Verwendung von Leichtmetalllegierungen, Al-Gusslegierungen oder Stahl bereitet keine Schwierigkeiten. Die gewählten Legierungen müssen einer Glanzanodisierung nicht mehr zugänglich sein, da die Al- oder Al-Legierungsschicht die Glanzwirkung entfaltet.Due to the type of gloss coating made of Al or Al alloy, no high demands must be placed on the alloys used as substrate. The use of light metal alloys, Al cast alloys or steel is not difficult. The selected alloys need no longer be accessible to a gloss anodization, since the Al or Al alloy layer unfolds the gloss effect.

Die Dicke der ersten Schicht beträgt bevorzugt 10 bis 500 µm. Besonders bevorzugt liegt die Dicke auf gegossenen Aluminiumfelgen oder Stahlfelgen bei 30 bis 100 µm.The thickness of the first layer is preferably 10 to 500 μm. Particularly preferably, the thickness of cast aluminum rims or steel rims is 30 to 100 μm.

Hinsichtlich der Wahl der Al-Legierung hat sich gezeigt, dass Reinaluminium auf Grund seiner Duktilität und seiner Passivität den meisten anderen Korrosionsschutzschichten überlegen ist und daher besonders bevorzugt Anwendung findet.With regard to the choice of the Al alloy, it has been found that pure aluminum, because of its ductility and its passivity, is superior to most other anticorrosive coatings and is therefore used with particular preference.

Für den Anwendungsfall von Kraftfahrzeugrädern, die starken Verschmutzungen, abrasiven Reinigungsvorgängen und korrosiven Medien ausgesetzt sind, ist die erste Schicht aus Al- oder Al-Legierung häufig nicht beständig genug. In weiterer Ausgestaltung der Erfindung trägt die Oberfläche der ersten Schicht daher eine zweite Schicht in Form einer elektrochemisch erzeugten mikro- oder nano-porösen Oxidschicht. Bei dieser Schicht handelt es sich um eine der Glanzanodisation von Aluminiumoberflächen vergleichbare Beschichtung. Die metallische Oberfläche wird durch die fest anhaftende Oxidschicht passiviert und gegen weiteren korrosiven Angriff geschützt. Durch geeignete Wahl der Verfahrensparameter bei der Glanzanodisation bzw. der elektrochemischen Erzeugung der nano- oder mikroporösen Oxidschicht kann eine Oberflächenstruktur erzeugt werden, die einen Lotus-Effekt, beziehungsweise einen schmutzabweisenden Effekt besitzt.For the application of automotive wheels exposed to heavy soiling, abrasive cleaning and corrosive media, the first layer of Al or Al alloy is often not durable enough. In a further embodiment of the invention, the surface of the first layer therefore carries a second layer in the form of an electrochemically generated micro- or nano-porous oxide layer. This coating is a coating comparable to the anodization of aluminum surfaces. The metallic surface is passivated by the firmly adhering oxide layer and protected against further corrosive attack. By suitable choice of the process parameters in the case of gloss anodization or electrochemical generation of the nano- or microporous oxide layer, it is possible to produce a surface structure which has a lotus effect or a dirt-repellent effect.

Darüber hinaus bildet diese Schicht einen guten Haftgrund für weitere organische Beschichtungen.In addition, this layer forms a good primer for further organic coatings.

Die Dicke der Oxidschicht ist so weit zu beschränken, dass der Glanz der Oberfläche nicht verloren geht. Diese zweite Schicht hat bevorzugt eine Dicke im Bereich von 50 bis 1000 nm.The thickness of the oxide layer must be limited so that the gloss of the surface is not lost. This second layer preferably has a thickness in the range of 50 to 1000 nm.

Besonders zweckmäßig ist der Schutz des beschichteten Rads bzw. der Felge mit einer abschließenden Lackschicht. In zweckmäßiger weiterer Ausgestaltung der Erfindung trägt die erste oder die zweite Schicht somit eine dritte Schicht aus einer abschließenden Lackschicht, insbesondere einem Klarlack oder einem easy-to-clean-Lack (ETC-Lack).Particularly useful is the protection of the coated wheel or rim with a final coat of paint. In an expedient further embodiment of the invention, the first or the second layer thus carries a third layer of a final lacquer layer, in particular a clearcoat or an easy-to-clean lacquer (ETC lacquer).

Durch die Kombination mit einer ETC-Beschichtung wird eine optisch hochwertige Oberfläche bei gleichzeitig höchstem Korrosionsschutz und dauerhaftem Glanz erreicht.The combination with an ETC coating achieves a visually high-quality surface with the highest corrosion protection and lasting shine at the same time.

Durch eine optionale ETC-Beschichtung beispielsweise mit Organosilikaten kann das Problem der Felgenverschmutzung durch Bremsstaub wirksam bekämpft werden.An optional ETC coating, for example with organosilicates, can effectively combat the problem of brake dust rim contamination.

Bei der ETC-Beschichtung kann es sich um hydrophile oder hydrophobe Beschichtungen handeln. Die optimale Wahl ist unter anderem von der Wahl des Bremsbelagsmaterials in der Fahrzeugbremse abhängig.The ETC coating can be hydrophilic or hydrophobic coatings. The optimal choice depends, among other things, on the choice of brake lining material in the vehicle brake.

In einer bevorzugten Ausgestaltung der Erfindung ist die dritte Schicht überwiegend aus Silan-, Silazan-, Siloxan- und/oder Silikonpolymeren gebildet.In a preferred embodiment of the invention, the third layer is formed predominantly of silane, silazane, siloxane and / or silicone polymers.

Die Komponenten bilden hierbei den Hauptbestandteil der Beschichtung. Weitere Komponenten können insbesondere die Kratzfestigkeit erhöhende Füller, hydrophobe beziehungsweise hydrophobisierende Zusatzstoffe oder katalytisch aktive Zusatzstoffe sein. Als Füller sind insbesondere Silikatpulver, Tonmineralien, Aluminiumoxid-Nanopulver oder SiO2-Nanofüller von Bedeutung. Als katalytisch aktiver Zusatzstoff ist insbesondere Titanoxid von Bedeutung, welches durch UV-Lichteinwirkung oxidierend auf die oberflächlich abgelagerten Schmutzpartikel wirkt. Besonders günstig ist die Kombination aus hydrophilisierenden Zusatzstoffen und katalytisch aktivem Titanoxid.The components form the main component of the coating. Other components may in particular be the scratch-resistant filler, hydrophobic or hydrophobizing additives or catalytically active additives. Silica powder, clay minerals, alumina nanopowder or SiO 2 nanofiller are particularly important as fillers. As catalytically active In particular, titanium oxide is important as an additive, which acts oxidatively on the superficially deposited dirt particles by the action of UV light. Particularly favorable is the combination of hydrophilizing additives and catalytically active titanium oxide.

Eine gute geeignete dritte Beschichtung ist des Weiteren aus Siloxan mit Silikat-Füllern aufgebaut.A suitable third coating is further composed of siloxane with silicate fillers.

Die dritte Schicht weist in weiterer Ausgestaltung als Hauptbestandteil Perhyrdosilazan-Polymere und als Zusatzstoffe hydrophile (Co)Polymere und/oder Zusatzstoffe auf. Eine Kombination aus Perhyrdosilazan-Polymere, hydrophilen (Co)Polymeren und katalytisch aktivem Titanoxid erweist sich auf der Glanzschicht, bzw. der glanzanodisierten Glanzschicht als besonders wirksame kratzfeste und schmutzabweisende Beschichtung oder easy-to-clean-Lack.In a further embodiment, the third layer comprises perhyrdosilazane polymers as the main constituent and hydrophilic (co) polymers and / or additives as additives. A combination of perhyrdosilazane polymers, hydrophilic (co) polymers and catalytically active titanium oxide proves to be a particularly effective, scratch-resistant and dirt-repellent coating or easy-to-clean lacquer on the glossy layer or the bright anodised gloss layer.

In bevorzugter Ausgestaltung wird die Oberflächenbeschichtung aus 1, 2 oder 3 Schichten auf ein Kraftfahrzeugrad aus einer Al-Gusslegierung mit einem Si-Anteil im Bereich von 3 bis 12 Gew.% aufgetragen.In a preferred embodiment, the surface coating of 1, 2 or 3 layers is applied to a motor vehicle wheel made of an Al casting alloy with an Si content in the range from 3 to 12% by weight.

Ein weiterer Aspekt der Erfindung ist ein Verfahren zur Herstellung einer beständigen Glanzbeschichtung auf Aluminiumlegierungs- oder Stahloberflächen, welches als wesentliche Schritte aufweist:

  • Die Gasphasenabscheidung von Aluminium oder Al-Legierung zur Bildung einer ersten dichten und glänzenden Schicht.
  • Die elektrochemische Oxidation der Oberfläche der ersten Schicht und Bildung einer nano- bis mikroporösen zweiten Schicht aus Aluminiumoxid in einer Dicke im Bereich von 50 bis 1000 nm.
Another aspect of the invention is a method for producing a durable glossy coating on aluminum alloy or steel surfaces, which comprises as essential steps:
  • The vapor deposition of aluminum or Al alloy to form a first dense and shiny layer.
  • Electrochemical oxidation of the surface of the first layer and formation of a nanosize to microporous second layer of alumina in a thickness in the range of 50 to 1000 nm.

Durch die Gasphasenabscheidung wird die Ausbildung einer homogenen gut haftenden Glanzbeschichtung auf unterschiedlichsten Al- oder Stahllegierungen möglich.By the vapor deposition, the formation of a homogeneous well-adhering gloss coating on a variety of Al or steel alloys is possible.

Die nachfolgende elektrochemische Oxidation erhöht die Korrosionsfestigkeit der Oberfläche und verbessert die Oberflächenbeschaffenheit für eine nachfolgende Beschichtung.The subsequent electrochemical oxidation increases the corrosion resistance of the surface and improves the surface finish for a subsequent coating.

Für die Erzeugung der Glanzbeschichtungen ist es von besonderer Bedeutung, dass gleichmäßige und fehlerfreie sowie chemisch reine Oberflächenbeschichtungen hoher Glätte erzeugt werden. CVD- und PVD-Verfahren sind hierfür besonders geeignet.For the production of the gloss coatings, it is of particular importance that uniform and error-free as well as chemically pure surface coatings of high smoothness are produced. CVD and PVD methods are particularly suitable for this.

Bevorzugt wird im Rahmen der Gasphasenabscheidung, die bevorzugt als CVD- oder PVD-Verfahren (chemical vapor deposition oder physical vapor deposition) durchgeführt wird, eine Reinaluminiumschicht in einer Dicke von 10 bis 300 µm aufgebracht.Preferably, in the context of the vapor deposition, which is preferably carried out as a CVD or PVD process (chemical vapor deposition or physical vapor deposition), a pure aluminum layer is applied in a thickness of 10 to 300 microns.

Als CVD-Prozess wird bevorzugt ein Kaltgasprozess angewendet, insbesondere bei der Abscheidung auf Leichtmetallsubstrate oder Aluminiumräder. Dabei werden die Aluminiumoberflächen zur Abscheidung auf eine Temperatur im Bereich von 280 bis 350°C und die Stahloberflächen auf eine Temperatur im Bereich von 280 bis 580°C gebracht. Der Kaltgasprozess zeichnet sich dadurch aus, dass das mit den gasförmigen Al-Trägersubstanzen beladene Trägergas eine geringere Temperatur als das zu beschichtende Substrat aufweist. Insbesondere liegt die Trägergastemperatur deutlich unterhalb der Zersetzungs- oder Abscheidetemperatur der Al-Trägersubstanz.As a CVD process, a cold gas process is preferably used, in particular in the deposition on light metal substrates or aluminum wheels. The aluminum surfaces for deposition are brought to a temperature in the range of 280 to 350 ° C and the steel surfaces to a temperature in the range of 280 to 580 ° C. The cold gas process is characterized in that the carrier gas loaded with the gaseous Al carrier substances has a lower temperature than the substrate to be coated. In particular, the carrier gas temperature is significantly below the decomposition or deposition temperature of the Al carrier substance.

Besonders bevorzugt wird eine allseitige Beschichtung einer gegossenen Aluminiumfelge oder Stahlfelge mit einer durch ein Niedertemperatur-CVD-Verfahren aufgebrachten Reinaluminiumschicht in einer Schichtdicke von 30 bis max. 100 µm durchgeführt.Particularly preferred is an all-round coating of a cast aluminum rim or steel rim with an applied by a low-temperature CVD method pure aluminum layer in a layer thickness of 30 to max. 100 μm performed.

Die Durchführung der besonders geeigneten CVD-Verfahren ist im Prinzip bereits bekannt und beispielsweise in der WO 2005 028 704 A1 beschrieben.The implementation of the particularly suitable CVD method is already known in principle and for example in the WO 2005 028 704 A1 described.

Die zweite Schicht aus Aluminiumoxid wird bevorzugt so hergestellt, dass die Glanzschicht aus abgeschiedenem Al- oder Al-Legierung anodisiert wird.The second layer of alumina is preferably prepared so that the deposited layer of Al or Al alloy is anodized.

Bevorzugt werden die Parameter der Anodisierung so eingestellt, dass sich Nano- oder Mikrostrukturen aus säulenförmigem Aluminiumoxid bilden. Aufgrund der Zwischenräume benachbarter Säulen ist die Schicht als solche nano- bzw. mikroporös aufgebaut.Preferably, the anodization parameters are adjusted to form nano or microstructures of columnar alumina. Due to the interspaces of adjacent columns, the layer is constructed as such nano- or microporous.

In bevorzugter weiterer Ausgestaltung wird auf die erste, insbesondere aber auf die zweite Schicht ein Klarlack oder eine easy-to-clean-Beschichtung aufgetragen.In a further preferred embodiment, a clear coat or an easy-to-clean coating is applied to the first coat, but especially to the second coat.

Der Auftrag kann im Nassverfahren oder auch als Pulverbeschichtung erfolgen.The job can be done by wet or powder coating.

Das Verfahren eignet sich insbesondere zur Beschichtung von Al-Gusslegierungsräder für Personenkraftwagen oder für Stahlräder für Lastkraftwagen oder Busse.The method is particularly suitable for coating Al cast alloy wheels for passenger cars or for steel wheels for trucks or buses.

Claims (16)

  1. Surface coating with a bright appearance on motor vehicle wheels made of casting alloys or steel, which surface coating may comprise several layers,
    characterised in that
    it comprises at least one first layer of aluminium or an aluminium alloy applied to the surface of the wheel and having a metallic lustre.
  2. Surface coating according to claim 1,
    characterised in that
    the layer of aluminium or an aluminium alloy is a CVD or PVD coating.
  3. Surface coating according to claim 1 or 2,
    characterised in that
    the surface of the first layer supports a second layer in the form of an electrochemically produced micro- or nano-porous oxide layer.
  4. Surface coating according to claim 1, 2 or 3,
    characterised in that
    the first or the second layer supports a third layer of clear lacquer or easy-to-clean lacquer.
  5. Surface coating according to claim 2,
    characterised in that
    the second layer has a thickness in the range of 50 to 1000 nm.
  6. Surface coating according to any of the preceding claims,
    characterised in that
    the third layer consists largely of silane, silazane and/or silicone polymers.
  7. Surface coating according to claim 6,
    characterised in that
    the third layer contains hydrophobic additives.
  8. Surface coating according to any of claims 1 to 6,
    characterised in that
    the third layer includes perhydrosilazane polymers, hydrophilic copolymers and/or additives as well a titanium oxide.
  9. Surface coating according to any of the preceding claims,
    characterised in that
    the motor vehicle wheel consists of an aluminium casting alloy with an Si content in the range of 3 to 12 % by weight.
  10. Surface coating according to any of the preceding claims,
    characterised in that
    the motor vehicle wheel consists of steel.
  11. Method for the production of a durable bright coating on aluminium alloy or steel surfaces of motor vehicle wheels made of casting alloys or steel, comprising the following steps:
    - vapour phase deposition of aluminium or aluminium alloy to form a first dense and bright layer directly on the wheel surface,
    - electrochemical oxidation of the surface of the first layer and formation of a nano- to micro-porous second layer of aluminium oxide with a thickness in the range of 50 to 1000 nm.
  12. Method according to claim 11,
    characterised in that
    the vapour phase deposition involves a CVD or PVD process.
  13. Method according to claim 12,
    characterised in that
    the CVD process used is a cold gas process wherein the aluminium surfaces have a temperature in the range of 280 to 350°C and the steel surfaces have a temperature in the range of 280 to 580°C.
  14. Method according to any of claims 11 to 13,
    characterised in that
    the electrochemical oxidation is carried out by anodising.
  15. Method according to any of claims 11 to 14,
    characterised in that
    a clear lacquer or easy-to-clean lacquer is applied to the first or second layer.
  16. Motor vehicle wheel made of an aluminium alloy or of steel,
    characterised in that
    it is provided with a bright coating according to any of claims 1 to 10, or in that it is coated using a method according to any of claims 11 to 15.
EP08701133A 2007-01-30 2008-01-16 Bright coatings for aluminium or steel motor vehicle wheels and their production Not-in-force EP2115182B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007004570A DE102007004570A1 (en) 2007-01-30 2007-01-30 Shiny coatings for car wheels made from light metal alloys or steel comprises at least one layer of aluminum or aluminum alloy applied directly to surface of wheel
PCT/EP2008/000291 WO2008092564A1 (en) 2007-01-30 2008-01-16 Bright coatings for aluminium or steel motor vehicle wheels and their production

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US20120308775A1 (en) * 2010-12-09 2012-12-06 You Seung M Hydrophilic surfaces and process for preparing
PT2752504T (en) * 2013-01-08 2016-08-02 Ropal Europe Ag Method for producing a corrosion resistant, glossy, metallic coated substrate, the metallic coated substrate, and its use
DE102014003508A1 (en) * 2014-03-14 2015-09-17 Airbus Defence and Space GmbH Process for the preparation and use of a polished nanostructured metallic surface with water and ice-repellent properties

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US5032568A (en) * 1989-09-01 1991-07-16 Regents Of The University Of Minnesota Deposition of superconducting thick films by spray inductively coupled plasma method
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GB9721650D0 (en) * 1997-10-13 1997-12-10 Alcan Int Ltd Coated aluminium workpiece
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US20100021757A1 (en) 2010-01-28

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