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EP1285105B1 - Couches formees par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive - Google Patents

Couches formees par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive Download PDF

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Publication number
EP1285105B1
EP1285105B1 EP01933902A EP01933902A EP1285105B1 EP 1285105 B1 EP1285105 B1 EP 1285105B1 EP 01933902 A EP01933902 A EP 01933902A EP 01933902 A EP01933902 A EP 01933902A EP 1285105 B1 EP1285105 B1 EP 1285105B1
Authority
EP
European Patent Office
Prior art keywords
layer
metal
conductive surface
deposited
electrically conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01933902A
Other languages
German (de)
English (en)
Other versions
EP1285105A1 (fr
Inventor
Matthias Schweinsberg
Bernd Mayer
Frank Wiechmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP03025080A priority Critical patent/EP1394292A3/fr
Publication of EP1285105A1 publication Critical patent/EP1285105A1/fr
Application granted granted Critical
Publication of EP1285105B1 publication Critical patent/EP1285105B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials

Definitions

  • the invention is in the field of coating surfaces to these to protect against corrosion and / or to provide them with a primer for a subsequent organic coating.
  • the Surfaces are electrically conductive, for example surfaces of metals or surfaces which have been made conductive by an appropriate treatment Represent glass or plastics.
  • a common technical task is metallic or not to provide metallic substrates with a first coating that has a corrosion-inhibiting effect and / or has a primer for an over it represents coating to be applied with organic polymers.
  • metals are pretreated before painting. This is what technology stands for different procedures available. Examples include one layer-forming or non-layer-forming phosphating, a chromating or a chrome-free conversion treatment, for example with complex ones Fluorides from titanium, zirconium, boron or silicon. Technically easier to carry out, but a simple application of a primer coat is less effective a metal before painting it. An example of this is the application of Redlead.
  • An alternative to the "wet" process is "dry" Procedures in which a corrosion protection or adhesive layer from a Gas phase is deposited. Such methods are for example as PVD or CVD process known. They can be electrical, for example through a Plasma discharge, be supported.
  • a layer produced or applied in this way can be used as serve as a corrosion protective primer for subsequent painting.
  • the Layer can also be a primer for subsequent gluing represent.
  • metallic substrates, but also substrates made of Plastic or glass are often chemically or mechanically pretreated to ensure the adhesion of the adhesive to the substrate improve.
  • metal or Plastic parts in each case, but also glued together. Front and Today rear windows of vehicles are usually directly in the body glued.
  • Further examples of the use of adhesive layers can be found in the production of rubber-metal composites.
  • the Metal substrates are usually mechanically or chemically pretreated before an adhesive layer is applied for gluing with rubber.
  • That thin layers of metal compounds, such as oxide layers, be generated electrochemically on an electrically conductive surface is known in the art.
  • the influence of the deposition conditions was particularly important investigated the morphology of the oxide layers. A practical application of the Layers do not emerge from this work.
  • An electrochemical formation of an oxide layer also takes place with the as Known processes take place anodizing.
  • US-A-2 081 121 describes a process for the electrolytic coating of metallic Substrates such as iron, steel, copper and brass with a thin layer of copper (I) oxide described.
  • the alkaline baths used for this contain in addition to, for example Copper sulfate is a compound that forms a soluble complex with the copper.
  • Examples of such substances are: organic acids such as lactic acid, citric acid, Glycolic acid, tartaric acid, salicylic acid also sugar, glycerin and inorganic Compounds such as pyrophosphate or borax.
  • the colored layers obtained in this way can be used as the basis for subsequent painting, varnishing or enamelling serve.
  • US-A-4 094 750 discloses the electrodeposition of metal oxides of Al, Cu, Co and Ni on titanium, magnesium, aluminum or steel substrates at current densities of 0.02 to 0.5 A / in 2 in 5 to 60 seconds using appropriate metal salts in alcoholic solution. According to the examples, metal oxide layer thicknesses in the range from 700 to 1600 A result. These layers serve as an adhesive layer for an adhesive bonding of parts.
  • the present invention relates to a method for producing an at least two-layer coating on an electrically conductive surface, characterized in that in a step a) on the electrically conductive surface a chromium-free layer of at least one X-ray crystalline inorganic compound of at least one metal A with a mass per unit area of 1.1 to 10 g / m 2 from a solution which contains the metal A in dissolved form, is deposited electrochemically, the metal A being a different metal than the main component of the electrically conductive surface and being selected from Mg. Ca. Sr.
  • step b) at least one layer of a cathodically or anodically depositable electrodeposition paint or a powder paint is applied to the layer deposited in step a).
  • the solution containing metal A in dissolved form is also referred to below as "Electrolyte” called.
  • a conductive salt such as a tetraalkylammonium halide.
  • the Ions of the conductive salt are not or only to a minor extent in the Layer installed, but increase the electrical conductivity of the electrolyte.
  • the electrically conductive surface can be intrinsic act conductive surface such as a metallic surface.
  • layer can also be on a surface of an electrically little or not conductive material are deposited if the Surface is made electrically conductive.
  • plastics for example done by first electrically chemical deposits conductive metal layer, which then forms the basis for the electrochemical Deposition of a compound of metal A.
  • a glass surface can be made electrically conductive, for example, by using them with a Powdered an electrically conductive substance or a conductive layer through the gas phase, for example as a chemical Vapor Deposition (CVD). It is for the use according to the invention however preferred that the electrically conductive surface be a metal surface represents.
  • the inorganic compound of metal A is separated from a solution that contains the metal A in dissolved form. It can be a one- or multi-component aqueous or a non-aqueous solution act.
  • non-aqueous solvents with a good one Solvent for suitable metal compounds are liquid ammonia, Dimethyl sulfoxide or organic phosphine derivatives.
  • one multicomponent aqueous solution are water-alcohol mixtures.
  • the electrochemical deposition can be carried out cathodically or anodically, a cathodic deposition can be used more universally and is therefore preferred is.
  • the deposition of the inorganic compound of at least one metal A from a corresponding solution can be done according to 2 different mechanisms respectively.
  • the deposition can be coupled with a change in the Oxidation level of metal A, with a on the electrically conductive surface Layer of a poorly soluble compound of metal A in the opposite of the Solution changed oxidation level grows up.
  • Another separation mechanism is based on the fact that the pH value through electrochemical processes on the electrically conductive surface shifts near the surface.
  • the electrical conductive surface an inorganic compound of at least one metal A grow up that are hard on the surface under local pH conditions is soluble. It is not necessary that the oxidation state of the metal A changes during the deposition process.
  • a shift in pH can take place on the electrically conductive surface, for example, in that Hydrogen ions are discharged and the pH value rises locally as a result.
  • the inorganic compound of at least one metal This means that this connection is definitely the metal A must contain. However, it can also contain other metals B, C, ... This other metals can be present in the solution in addition to metal A. and be deposited with it. These other metals can however, also be components of the electrically conductive surface and at Formation of the layer of an inorganic compound of at least one metal A. can be built directly into this connection.
  • inorganic Compounds that contain another metal in addition to metal A Mixed oxides, for example the structure type of the spinels or the Perovskite can belong. Examples include titanates and niobates.
  • the in step a) deposited compound is an oxide.
  • This can also be a mixed oxide different metals.
  • the use according to the invention is not limited to oxides. It also includes non-oxide inorganic Compounds such as, for example, selenides, sulfides or nitrides suitable, possibly anhydrous, solvents can be separated.
  • the inorganic Connection of at least one metal A is only binary or ternary Represents connection. Rather, this connection can also be set up in a more complex manner be, for example, ions or molecules from the solution into the compound can also be installed. Oxide hydrates or sulfates are an example of this.
  • the use according to the invention does not include a pure galvanization, since a plating layer is not an "inorganic compound" in the sense of this Represents invention.
  • To the layer of at least one inorganic Connection of at least one metal A is rather the condition that at least part of the metal A is in an oxidation state> 0.
  • any layer can be used for the use according to the invention at least one inorganic compound of at least one metal A are used, which can be deposited electrochemically and which are sufficient is chemically stable to act as a corrosion protection layer.
  • the Layer with or without applied varnish better corrosion protection delivers as the uncoated metal surface.
  • the metal A selected from Mg, Ca, Sr, Ba, Si, Sn, Pb, Sb, Bi, Ti, Zr, Nb, Ta, Mn, Fe, Co, Ni, Zn, Cu.
  • the for The most important metal for practical purposes are Si, Ti, Zr, Mn, Fe, Co, Ni, Zn and Cu.
  • the electrochemical deposition can be potentiostatic or galvanostatic.
  • the galvanostatic deposition is technically easier to carry out and is therefore preferred.
  • the layer formation preferably takes place in that the inorganic compound on the electrically conductive surface at a potential compared to a standard hydrogen electrode between ⁇ 0.1 and ⁇ 300 V or a current density in the range of ⁇ 0.1 to ⁇ 10000 mA per cm 2 electrically conductive surface is deposited. It is preferred to work at potentials between ⁇ 0.1 and ⁇ 100 V or at a current density in the range from ⁇ 0.5 to ⁇ 100 mA per cm 2 .
  • the signs in front of voltage and current density express that the deposition can be cathodic or anodic. Cathodic deposition, ie a negative potential compared to the standard hydrogen electrode, is preferred.
  • the morphology, the chemical composition and the crystal structure of the deposited Layer depend on the deposition conditions and thus by choice of Conditions can be affected.
  • the above mentioned Layer parameters from the concentration of the metal ions A and possibly further Components in the solution, the flow rate of the solution relative to the electrically conductive surface, the set potential and / or the set current density.
  • the layer properties can thus be chosen specifically change this parameter.
  • the deposition is carried out here under such conditions that the inorganic compound deposits in X-ray crystalline form.
  • X-ray crystalline means that the inorganic compound in a sharp X-ray diffraction experiment X-ray reflexes delivers.
  • the resulting highly structured surface is particularly favorable as a primer for an organic coating.
  • Electrolytes relative to the metallic conductive surface can form layers accelerate and influence the morphology of the layer. For example this is done by stirring the electrolyte or in the Pumped around electrolysis vessel. Furthermore, the electrolyte can be blown through a Gases, especially air, are mixed and moved.
  • a cathodically or anodically depositable electrodeposition paint can be applied.
  • the layer is deposited between the layers inorganic compound and the application of electrocoat preferably rinsed with water. This can be done by dipping or spraying respectively. It can be advantageous, at least in the last rinsing step rinse low-salt or deionized water.
  • a chemical Post-passivation of the inorganic layer before the electrical one Dip painting, as is usually the case with phosphating, for example is not necessary in the method according to the invention.
  • a powder coating can also be used in sub-step b) be applied.
  • the inorganic layer on the electrical conductive surface can no longer be electrically conductive to the extent that for Subsequent electrocoating is required.
  • a powder paint is preferably applied to molded objects that are not strong exposed to corrosive loads. Examples of this are items such as Household appliances or electronic devices used in enclosed spaces be kept.
  • the advantages of the invention lies in the fact that thickness, composition and inner and outer structure of the inorganic layer by the choice of Deposition parameters are easier to control than with purely chemical ones Process management. Less will be needed to apply the layer Process stages are required than for phosphating and they generally fall less sludge than with a purely chemical layer formation. Compared The deposition process from the gas phase is electrochemical Separation faster and with less equipment and Energy consumption connected. Furthermore, it is not necessary as the Vapor deposition to provide volatile starting compounds.
  • Another advantage of electrochemical layer formation is that Layer growth over the electrical resistance on the metallic conductive Surface is controllable. Unless the growing layer has a higher one has electrical resistance than the electrically conductive surface - what in the The rule is the case - so the layer growth slows down when the electrical resistance becomes too high due to the layer formation. As long as it is there are still unoccupied areas of the metallic conductive surface or the layer is so thin that a current still flows at the set voltage the layer growth at these points. Is the metallic conductive surface almost completely covered with a layer of such a thickness that the electrical resistance increases significantly, the process of layer formation can be ended. With galvanostatically controlled layer growth it shows up the almost complete layer formation in that the terminal voltage rises sharply. The process can then automatically run at a preselected value the terminal voltage can be interrupted.
  • Electrolyte 0.4 M CuSO 4 + 3 M lactic acid, pH 10, 60 ° C, with 400 revolutions per minute stirring
  • the layers formed are closed after a treatment time of approx. 50 s and consist of fine ( ⁇ 1 ⁇ m) crystals of Cu 2 O:
  • the layer properties are very easy to control even without interfering with the electrolyte composition.
  • Corrosion tests (10 cycles VDA alternating climate test, cathodic dip painting) show a significant improvement in corrosion protection through the coating depending on the applied layer thickness: Process time (seconds) Alternating climate test: infiltration U / 2 (mm) 10 4.8 30 4.5 60 3.9 120 3.6 300 2.6

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Paints Or Removers (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Claims (3)

  1. Procédé de préparation d'un revêtement à au moins deux couches, sur une surface conductrice de l'électricité, caractérisé en ce que,
       dans une étape a) une couche exempte de chrome, constituée d'au moins d'un composé inorganique cristallin d'après une diffractométrie aux rayons X d'au moins un métal A ayant une masse surfacique de 1,1 à 10 g/m2, est déposée électrochimiquement sur la surface conductrice de l'électricité en partant d'une solution qui contient le métal A sous la forme dissoute, le métal A représentant un métal autre que le composant principal de la surface conductrice de l'électricité, et étant choisi parmi Mg, Ca, Sr, Ba, Si, Sn, Pb, Sb, Bi, Ti, Zr, Nb, Ta, Mn, Fe, Co, Ni, Zn, Cu, et le composé inorganique contenant moins de 20% en poids d'ions phosphate, et
       dans une étape suivante b), au moins une couche d'une peinture électrophorétique par immersion pouvant être déposée de façon cathodique ou anodique, ou une peinture en poudre est appliquée sur la couche déposée dans l'étape a).
  2. Procédé selon la revendication 1, caractérisé en ce que le composé déposé dans l'étape a) représente un oxyde.
  3. Procédé selon l'une des revendications 1 et 2 ou les deux, caractérisé en ce que le composé inorganique est déposé sur la surface conductrice de l'électricité, à un potentiel par rapport à une électrode d'hydrogène de référence, compris entre ± 0,1 et ± 300 V ou à une densité de courant dans la plage de ± 0,1 à ± 10 000 mA par cm2 de surface conductrice de l'électricité.
EP01933902A 2000-05-06 2001-04-27 Couches formees par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive Expired - Lifetime EP1285105B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03025080A EP1394292A3 (fr) 2000-05-06 2001-04-27 Couches de TiO2 formées par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10022074 2000-05-06
DE10022074A DE10022074A1 (de) 2000-05-06 2000-05-06 Elektrochemisch erzeugte Schichten zum Korrosionsschutz oder als Haftgrund
PCT/EP2001/004780 WO2001086029A1 (fr) 2000-05-06 2001-04-27 Couches formees par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP03025080A Division EP1394292A3 (fr) 2000-05-06 2001-04-27 Couches de TiO2 formées par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive

Publications (2)

Publication Number Publication Date
EP1285105A1 EP1285105A1 (fr) 2003-02-26
EP1285105B1 true EP1285105B1 (fr) 2004-03-17

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EP01933902A Expired - Lifetime EP1285105B1 (fr) 2000-05-06 2001-04-27 Couches formees par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive
EP03025080A Withdrawn EP1394292A3 (fr) 2000-05-06 2001-04-27 Couches de TiO2 formées par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive

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EP03025080A Withdrawn EP1394292A3 (fr) 2000-05-06 2001-04-27 Couches de TiO2 formées par voie electrochimique et servant de protection anticorrosion ou de peinture primaire reactive

Country Status (7)

Country Link
US (3) US20040099535A1 (fr)
EP (2) EP1285105B1 (fr)
AT (1) ATE262056T1 (fr)
AU (1) AU2001260260A1 (fr)
DE (2) DE10022074A1 (fr)
ES (1) ES2218415T3 (fr)
WO (1) WO2001086029A1 (fr)

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ATE262056T1 (de) 2004-04-15
US20040099535A1 (en) 2004-05-27
AU2001260260A1 (en) 2001-11-20
EP1394292A2 (fr) 2004-03-03
DE10022074A1 (de) 2001-11-08
EP1285105A1 (fr) 2003-02-26
US20090162563A1 (en) 2009-06-25
WO2001086029A1 (fr) 2001-11-15
DE50101713D1 (de) 2004-04-22
ES2218415T3 (es) 2004-11-16
US20070144914A1 (en) 2007-06-28
EP1394292A3 (fr) 2004-06-16

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