EP1285105A1 - 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

Info

Publication number
EP1285105A1
EP1285105A1 EP01933902A EP01933902A EP1285105A1 EP 1285105 A1 EP1285105 A1 EP 1285105A1 EP 01933902 A EP01933902 A EP 01933902A EP 01933902 A EP01933902 A EP 01933902A EP 1285105 A1 EP1285105 A1 EP 1285105A1
Authority
EP
European Patent Office
Prior art keywords
metal
layer
inorganic compound
electrically conductive
conductive surface
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01933902A
Other languages
German (de)
English (en)
Other versions
EP1285105B1 (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

Links

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 in order to protect them against corrosion and / or to provide them with a primer for a subsequent organic coating.
  • the surfaces must be electrically conductive, for example represent surfaces of metals or surfaces of glass or plastics that have been made conductive by a corresponding treatment.
  • a widespread technical task is to provide metallic or non-metallic substrates with a first coating which has a corrosion-inhibiting effect and / or which is an adhesive base for a coating to be applied with organic polymers.
  • metals are pretreated before painting.
  • Various methods are available in technology for this. Examples include a layer-forming or non-layer-forming phosphating, a chromating or a chromium-free conversion treatment, for example with complex fluorides of titanium, zirconium, boron or silicon.
  • Technically easier to carry out, but less effective is a simple application of a primer layer on a metal before painting it. An example of this is the application of Menninge.
  • dry processes in which a corrosion protection or adhesive layer is deposited from a gas phase.
  • Such methods are known, for example, as PVD or CVD methods. They can be supported electrically, for example by a plasma discharge.
  • a layer produced or applied in this way can serve, on the one hand, as a corrosion-protecting adhesive base for subsequent painting.
  • the layer can also form a base for subsequent gluing.
  • metallic substrates, but also substrates made of Plastic or glass are often chemically or mechanically pretreated before bonding to improve the adhesion of the adhesive to the substrate.
  • metal or plastic parts are glued to each other, but also to each other.
  • front and rear windows of vehicles are usually glued directly into the body.
  • Further examples of the use of adhesive layers can be found in the production of rubber-metal composites.
  • the metal substrate is usually mechanically or chemically pretreated before an adhesive layer is applied for gluing with rubber.
  • the conventional wet or dry coating processes each have special disadvantages.
  • chromating processes are disadvantageous from an ecological and economic point of view due to the toxic properties of chromium and the formation of highly toxic sludges.
  • chrome-free wet processes such as phosphating are usually associated with the formation of sludges containing heavy metals, which have to be disposed of in a complex manner.
  • Another disadvantage of conventional wet coating processes is that the actual coating step often requires preparatory or post-processing additional steps. This increases the space required for the treatment line and the consumption of chemicals.
  • the phosphating used almost exclusively in automobile construction is associated with several cleaning steps, one activation step and generally a post-passivation step. In all of these steps, chemicals are consumed and waste to be disposed of.
  • An electrochemical formation of an oxide layer also takes place in the processes known as anodizing.
  • the present invention differs from this in that layers of metal compounds are deposited on a substrate, the metal of the metal compound being essentially a different metal from that which makes up the possibly metallic substrate.
  • Electrochemical support for the formation of zinc phosphate layers is not within the scope of the present invention.
  • the invention relates to the use of a layer on an electrically conductive surface, which is obtainable by a layer of at least one inorganic compound of at least one metal A with a mass per unit area of 0.01 on this surface in step a) up to 10 g / m 2 is electrochemically deposited from a solution which contains the metal A in dissolved form, the metal A being a different metal than the main component of the electrically conductive surface and the inorganic compound being less than 20% by weight Contains phosphate ions as a corrosion protection layer and / or as a primer for an organic coating.
  • the solution which contains the metal A in dissolved form is also referred to below as "electrolyte". If this represents water in which the salt of metal A is dissolved, the conductivity of this solution is generally sufficient for the purpose according to the invention If a non-aqueous solvent is used or if the conductivity of an aqueous solution is insufficient, a conductive salt such as a tetraalkylammonium halide can be added.
  • a conductive salt such as a tetraalkylammonium halide
  • the electrically conductive surface can be an intrinsically conductive surface such as a metallic surface.
  • the layer can also be deposited on a surface of a material that is not electrically or only slightly conductive if the surface is made electrically conductive by suitable measures. In the case of plastics, this can be done, for example, by first chemically depositing an electrically conductive metal layer, which then forms the basis for the electrochemical deposition of a metal A compound.
  • a glass surface can be made electrically conductive, for example, by using a Dusting an electrically conductive substance powder or applying a conductive layer over the gas phase, for example as chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • the electrically conductive surface is a metal surface.
  • the inorganic compound of metal A is deposited from a solution which contains metal A in dissolved form.
  • This can be a one- or multi-component aqueous or a non-aqueous solution.
  • non-aqueous solvents with a good solubility for suitable metal compounds are liquid ammonia, dimethyl sulfoxide or organic phosphine derivatives.
  • a multi-component aqueous solution are water-alcohol mixtures.
  • the electrochemical deposition can be carried out cathodically or anodically, with cathodic deposition being more universal and therefore preferred.
  • the inorganic compound of at least one metal A can be separated from a corresponding solution by two different mechanisms.
  • the deposition can be coupled with a change in the oxidation state of metal A, a layer of a poorly soluble compound of metal A growing on the electrically conductive surface in the oxidation state which has changed compared to the solution.
  • copper (I) oxide can be deposited cathodically from an aqueous solution containing copper (II) ions.
  • Another deposition mechanism is based on the fact that the pH value shifts near the surface due to electrochemical processes on the electrically conductive surface.
  • an inorganic compound of at least one metal A can grow on the electrically conductive surface and is poorly soluble on the surface under the local pH conditions. It is not necessary for the oxidation level of metal A to change during the deposition process.
  • the pH value on the electrically conductive surface can be shifted, for example, by discharging hydrogen ions and thereby locally increasing the pH value. If this refers to an inorganic compound of at least one metal A, this means that this compound must in any case contain the metal A. However, it can also contain other metals B, C, ... These other metals can be present in the solution in addition to the metal A and can be deposited together with this.
  • these other metals can also be components of the electrically conductive surface and can be incorporated directly into this connection when the layer of an inorganic compound of at least one metal A is formed.
  • inorganic compounds which contain a further metal in addition to metal A are mixed oxides, which can belong, for example, to the structure type of spinels or perovskites. Examples include titanates and niobates.
  • the compound deposited in step a) is an oxide.
  • This can also be a mixed oxide of different metals.
  • the use according to the invention is not restricted to oxides. It also includes non-oxidic inorganic compounds such as selenides, sulfides or nitrides, which can be separated from suitable, optionally anhydrous, solvents.
  • the inorganic compound of at least one metal A is merely a binary or ternary compound. Rather, this connection can also have a more complex structure, for example by incorporating ions or molecules from the solution into the connection. Oxide hydrates or sulfates are an example of this.
  • the use according to the invention does not include a pure electroplating, since an electroplating layer is not an “inorganic compound” in the sense of this invention.
  • the condition of the layer of at least one inorganic compound of at least one metal A is rather that at least a part of the metal A in a Oxidation level> 0 is present.
  • any layer of at least one inorganic compound of at least one metal A can be used for the use according to the invention, which layer can be deposited electrochemically and which is sufficiently chemically stable to act as a corrosion protection layer. This means that the
  • Layer with or without applied paint provides better corrosion protection than the uncoated metal surface. For the sake of price and
  • the metal A is selected from Mg, Ca, Sr,
  • AI Si, Sn, Pb, Sb, Bi, Ti, Zr, V, Nb, Ta, Mo, W, Mn, Fe, Co, Ni, Zn, Cu.
  • the most important metals from this for practical purposes are AI, Si, Ti, Zr, Mo, W, Mn, Fe,
  • 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 can thus be influenced by the choice of the conditions.
  • the layer parameters mentioned depend on the concentration of the metal ions A and possibly other constituents 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 specifically changed by selecting these parameters.
  • the deposition is carried out here preferably under conditions such that the inorganic compound is deposited in X-ray crystalline form.
  • X-ray crystalline means that the inorganic compound gives sharp X-ray reflections in an X-ray diffraction experiment.
  • the resulting highly structured surface is particularly favorable as an adhesive base for an organic coating.
  • Mixing the electrolyte and / or a relative movement of the electrolyte relative to the metallically conductive surface can accelerate the layer formation and influence the morphology of the layer. For example, this can be done by stirring the electrolyte or by pumping it around in the electrolysis vessel. Furthermore, the electrolyte can be mixed and moved by blowing in a gas, in particular air.
  • the invention relates to a method for producing an at least two-layer coating on an electrically conductive surface, characterized in that in step a) on the electrically conductive surface a layer of at least one inorganic compound of at least one metal A with a mass per unit area from 0.01 to 10 g / m 2 is electrochemically deposited from a solution containing the metal A in dissolved form, the metal A being a metal other than the main component of the electrically conductive surface and the inorganic compound being less than 20 wt .-% Contains phosphate ions, and in a subsequent step b) at least one layer of an organic polymer is applied to the layer deposited in step a).
  • an at least two-layer coating means that, as described above, a layer of at least one inorganic compound of at least one metal A is applied to the electrically conductive surface and in turn at least one layer of an organic polymer.
  • an inorganic compound can be applied to the layer several different layers of organic polymers can also be applied, for example, this is known from automotive engineering, where, according to the prior art, at least 3 different layers of organic polymers are generally applied to the phosphate layer serving as an inorganic corrosion protection and adhesive layer Layers of an electrocoat, a filler and a topcoat.
  • a layer whose formation, properties and composition has been described above can be selected as the layer of at least one inorganic compound of at least one metal A.
  • a cathodically or anodically depositable electrodeposition paint can be applied.
  • the inorganic compound is preferably rinsed with water between the deposition of the layer of the inorganic compound and the application of the electrocoating material.
  • This can be done by dipping or spraying. It can be advantageous, at least in the last rinsing step rinse low or deionized water.
  • the process according to the invention is carried out as a belt process.
  • an organic polymer layer is applied by immersion or spraying or by application rollers.
  • a belt process implicitly requires a non-rigid substrate, so that this process variant is preferably carried out on strips of metal.
  • the method is preferably carried out continuously. The electrochemical layer formation in sub-step a) and the application of the organic polymer layer in sub-step b) thus take place with the belt running.
  • the application of an organic polymer layer to a running belt is known in the prior art as the “coil coating method”.
  • the coating systems used for this are also suitable for the method according to the invention.
  • the organic polymer layer can have different thicknesses and different functions. For example, they are only a few ⁇ m thick and serve as a shaping aid and / or as a primer for subsequent painting.
  • the composition and layer thickness of the primer are preferably set such that electrical resistance welding is still possible.
  • Such organic primer layers on a chemically produced inorganic layer on a metal surface, depending on their function and composition are known in the art under various trade names, for example Durasteel R un d Granocoat R.
  • the layer thickness in the above-described primer layers is in the range of below 10 ⁇ m and is, for example, 6 to 9 ⁇ m
  • a thicker organic lacquer layer can also be used directly in the coil coating process applied, which will not be painted over later.
  • the layer thicknesses are then in the range from 50 to 200 ⁇ m.
  • a powder coating can be applied as organic polymer in sub-step b).
  • the inorganic layer on the electrically conductive surface no longer has to be electrically conductive to the extent that is required for a subsequent electrocoating.
  • a powder coating is preferably applied to molded objects that are not exposed to strong corrosive loads. Examples of this are items such as household appliances or electronic devices that are kept in closed rooms.
  • the organic layer applied in sub-step b) can also be an adhesive layer.
  • the inorganic layer of at least one metal A then serves as an adhesive layer between the adhesive and the metallic conductive base.
  • the inorganic layer can therefore act as an adhesive layer between one of the substrates metal, plastic or glass and an adhesive, it being possible for the adhesive to bond the same or different substrates to one another. Examples can be found in the construction of vehicles, airplanes or household appliances, where metals are glued to one another or with plastic or glass. Bonding plastic with plastic is also an option. In particular, glass panes can be glued into vehicle bodies in this way.
  • a special embodiment consists in applying an adhesive in sub-step b), with which a vulcanized or non-vulcanized rubber part is connected to a metal part.
  • the component that is created in this way is generally referred to as a “rubber-metal composite”.
  • the general procedure is to connect an unvulcanized rubber part with an adhesive to the metallic substrate via the inorganic layer serving as an adhesive layer and then by increasing the temperature , often with simultaneous exercise of pressure, vulcanized.
  • the invention relates to a metal component, the surface of which bears an at least two-layer coating which can be obtained in one of the ways described above.
  • This can be, for example, vehicles or vehicle parts, household appliances, housings for electronic devices, furniture or architectural parts.
  • Preferred materials for the metal components are iron, zinc, aluminum, magnesium and alloys which consist of more than 50 atom% of one of these elements. Metals and alloys can be selected that are currently common for the metal components mentioned.
  • the metal component described above carries the inorganic compound of at least one metal A in X-ray crystalline form.
  • X-ray crystalline means that the inorganic compound gives sharp X-ray reflections in an X-ray diffraction experiment.
  • the advantages of the use according to the invention and of the method according to the invention are in particular that the thickness, composition and inner and outer structure of the inorganic layer can be controlled more easily by the choice of the deposition parameters than in the case of purely chemical process control. Fewer process steps are required to apply the layer than with phosphating and there are generally fewer sludges than with purely chemical layer formation. Compared to deposition processes from the gas phase, electrochemical deposition is faster and requires less equipment and less energy. Furthermore, it is not necessary, like the vapor deposition, to provide volatile starting compounds. Another advantage of electrochemical layer formation is that the layer growth can be controlled via the electrical resistance on the metallically conductive surface.
  • the layer growth slows down if the electrical resistance becomes too high due to the layer formation. As long as there are still unoccupied places on the metallic conductive surface or the layer is so thin that a current still flows at the set voltage, the layer growth takes place at these places. If the metallically conductive surface is 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, the almost complete layer formation is shown by the fact that the terminal voltage rises sharply. The process can then be stopped automatically at a preselected terminal voltage value.
  • a pilot process for corrosion protection by means of cathodic deposition of Cu 2 O was carried out on cold-rolled steel without an activation step (shortening the process chain).
  • the following process parameters were set:
  • Electrolyte 0.4 M CuSO 4 + 3 M lactic acid, pH 10, 60 ° C, with 400 revolutions per
  • the layers formed are closed after a treatment time of approx. 50 s and consist of fine ( ⁇ 1 ⁇ m) crystallites 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:

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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)
  • Paints Or Removers (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
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 true EP1285105A1 (fr) 2003-02-26
EP1285105B1 EP1285105B1 (fr) 2004-03-17

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Family Applications (2)

Application Number Title Priority Date Filing Date
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
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

Family Applications Before (1)

Application Number Title Priority Date Filing Date
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) EP1394292A3 (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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US7569132B2 (en) * 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
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US20070144914A1 (en) 2007-06-28
EP1394292A2 (fr) 2004-03-03
ES2218415T3 (es) 2004-11-16
WO2001086029A1 (fr) 2001-11-15
DE10022074A1 (de) 2001-11-08
AU2001260260A1 (en) 2001-11-20
EP1394292A3 (fr) 2004-06-16
ATE262056T1 (de) 2004-04-15
US20040099535A1 (en) 2004-05-27
US20090162563A1 (en) 2009-06-25
EP1285105B1 (fr) 2004-03-17
DE50101713D1 (de) 2004-04-22

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