EP1543180B1 - Procede d'enduction par electrolyse de materiaux avec de l'aluminium, du magnesium ou des alliages d'aluminium et de magnesium - Google Patents

Procede d'enduction par electrolyse de materiaux avec de l'aluminium, du magnesium ou des alliages d'aluminium et de magnesium Download PDF

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Publication number
EP1543180B1
EP1543180B1 EP03807748A EP03807748A EP1543180B1 EP 1543180 B1 EP1543180 B1 EP 1543180B1 EP 03807748 A EP03807748 A EP 03807748A EP 03807748 A EP03807748 A EP 03807748A EP 1543180 B1 EP1543180 B1 EP 1543180B1
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EP
European Patent Office
Prior art keywords
alet
electrolyte
magnesium
aluminum
materials
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP03807748A
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German (de)
English (en)
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EP1543180A1 (fr
Inventor
Jörg HELLER
Hans De Vries
Matthias HÄRTEL
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.)
Aluminal Oberflachentechnik GmbH
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Aluminal Oberflachentechnik GmbH
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Priority to EP03807748A priority Critical patent/EP1543180B1/fr
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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals

Definitions

  • the present invention relates to a process for the electrolytic coating of materials with aluminum, magnesium or alloys of aluminum and magnesium, wherein the material is dipped into an electrolyte for pretreatment and is switched there anodically and immediately thereafter the electrolytic coating takes place in the same electrolyte.
  • the quality of the deposited aluminum, magnesium or aluminum / magnesium coating is improved.
  • the deposition of aluminum, magnesium or aluminum / magnesium alloys on materials that are made of base metals is a tried and tested means to protect these materials from corrosion. You will be provided at the same time with a decorative coating.
  • the protective metal layer is deposited here predominantly galvanically on the material. In this case, it is advantageous if the aluminum, magnesium or aluminum / magnesium layer takes place on the material without the application of metallic intermediate layers between said metal layer and the material. If intermediate layers between the material and the surface layer of aluminum, magnesium or aluminum / magnesium alloy are applied, there is a risk of contact corrosion due to the applied intermediate layer. In addition, thermal problems may occur due to the different expansion coefficients of the surface layer and the intermediate layer.
  • Electrolytes which have been well-known in the art include melt flow electrolytes such as electrolytes containing aluminum halides or aluminum alkyl complexes. All these electrolyte systems have in common that the material must be cleaned on its surface before coating. This is especially true for materials made of base metals which form an oxide layer, the problem that this oxide layer must be completely removed before the coating. If the surface of the materials is not completely cleaned, contaminants or residues of the oxide layer of the metal of which the material is made adversely affect the adhesion of the subsequently electrolytically applied metal layer. Furthermore, it is possible that at the points where impurities on the surface are present, no metal layer is applied, since the impurities are usually not electrically conductive and thus an electrolytic deposition is prevented at this point. This then inevitably leads to corrosion problems of the finished coated material at the point where the metal layer was not completely applied.
  • DE-C3-22 60 191 describes a method for the preparation of materials made of electrically conductive materials.
  • the last method step used for shaping the materials, in which a new blank surface is formed on the material is carried out in the absence of atmospheric oxygen and moisture in a suitable inert gas or inert liquid medium.
  • a disadvantage of this method is that, in particular when using inert liquid medium, which covers the surface of the material and thus can be brought into the coating electrolyte, this subsequently contaminates or hydrolyzes the electrolyte.
  • inert gas media shows in the industrial application the problem that an absolutely oxygen-free inert gas atmosphere is practically impossible to realize.
  • the pretreatment of a material in a protective gas atmosphere is described.
  • the oxide layer on the surface of the material may be removed by anodizing the material prior to depositing the aluminum layer in the electrolyte made from sodium fluoride and aluminum triethyl. Subsequently, a reversal of the current takes place, as well as a deposition of aluminum on the material.
  • the disadvantage is that the electrolyte can only be used to deposit aluminum on materials.
  • the deposition of magnesium or aluminum / magnesium layers is not possible because the presence of halide ions in the electrolyte in the anodic polarization would produce directly insoluble magnesium halide compounds which prevent deposition of magnesium or aluminum / magnesium on the material. The resulting magnesium halides would immediately prevent the flow of current in the electrolyte by blocking the electrodes.
  • DE-AS-21 22 610 describes a process for the anodic pretreatment of light metals for the electrodeposition of aluminum.
  • the components are cleaned by treating the light metal materials in a molten electrolyte, the materials being subjected to anodic loading.
  • the light metal materials cleaned in this way are humidified, so that they are still contaminated with the molten electrolyte, and immersed in an aluminizing cell. In this case, it can not be ruled out that atmospheric oxygen still reaches the pretreated material and oxidizes it again on the surface. Further, contamination of the aluminizing electrolyte by the surface-treating electrolyte, which is a molten electrolyte, takes place.
  • the material in the molten electrolyte which serves for the surface treatment by anodic oxidation of the material, also for the electrodeposition of aluminum on the Beryllium or aluminum material is used.
  • the melt electrolyte described in DE-AS-21 22 610 is only suitable for pretreating beryllium or aluminum materials in order subsequently to coat them with aluminum in the same melt electrolyte.
  • the molten electrolyte is not suitable for electroplating aluminum, magnesium or aluminum / magnesium layers on other materials.
  • DE-A1-198 55 666 describes an electrolyte suitable for depositing aluminum / magnesium alloy layers.
  • the disclosed aluminum-organic electrolyte contains K [AlEt 4 ] or Na [Et 3 Al-H-AlEt 3 ], as well as Na [AlEt 4 ], as well as trialkylaluminum.
  • the electrolyte can be present as a toluene solution.
  • the electrolytic deposition of aluminum / magnesium alloy layers from the described electrolyte is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an aluminum / magnesium alloy anode. In the described method, the electrolyte composition is adjusted by pre-electrolysis so that the deposited layer has the desired aluminum / magnesium ratio.
  • Mg [AlEt 4 ] 2 can also be added to the electrolyte.
  • DE-A1-198 55 666 thus teaches that the ratio of aluminum and magnesium in the deposited aluminum / magnesium layer is very much dependent on the concentration ratio of magnesium and aluminum in the electrolyte.
  • great care must be taken in the pretreatment of the materials to be coated, as contamination of the surface of the material by oxidation or other influences leads to reduced quality of the electrodeposited metal layer.
  • the technical object of the present invention is to provide a method in which aluminum, magnesium or aluminum / magnesium layers can be applied to materials, wherein the quality of the metal coating is increased by an improved pretreatment of the material.
  • a method is provided be, in which the materials to be coated are reliably and inexpensively freed from adhering oxide layers or other impurities, after the pretreatment of the materials, a renewed contamination or oxidation of the materials to be prevented.
  • the technical object of the present invention is achieved by a process for the electrolytic coating of materials with aluminum, magnesium or alloys of aluminum and magnesium, wherein the material is immersed in the electrolyte for pretreatment, is anodically switched there and immediately thereafter the electrolytic coating in the same Electrolytes takes place, wherein the electrolyte bath organoaluminum compounds of the general formula M [(R 1 ) 3 Al- (H-Al (R 2 ) 2 ) n -R 3 ] (I) and Al (R 4 ) 3 (II) as the electrolyte and n is 0 or 1, M is sodium or potassium and R 1 , R 2 , R 3 , R 4 may be the same or different, wherein R 1 , R 2 , R 3 , R 4 are C 1 - to C 4 alkyl group and is used as a solvent for the electrolyte, a halogen-free, aprotic solvent.
  • an electrolyte is used as a mixture of the complexes K [AlEt 4 ], Na [AlEt 4 ] and AlEt 3 are used.
  • the molar ratio of the complexes to AlEt 3 is 1: 0.5 to 1: 3, with the ratio of 1: 2 being preferred.
  • a mixture of 0.8 mol of K [AlEt 4 ], 0.2 mol of Na [AlEt 4 ], 2.0 mol of AlEt 3 in 3.3 mol of toluene can be used as the electrolyte.
  • a mixture of Na [Et 3 Al-H-AlEt 3 ] and Na [AlEt 4 ] and AlEt 3 can be used as the electrolyte in the process according to the invention.
  • the molar ratio of Na [Et 3 Al-H-AlEt 3 ] to Na [AlEt 4 ] is 4: 1 to 1: 1, with a ratio of 2: 1 being preferred. It is further preferred that the molar ratio of Na [AlEt 4 ] to AlEt 3 is 1: 2.
  • the electrolyte used is a mixture of 1 mol of Na [Et 3 Al-H-AlEt 3 ], 0.5 mol of Na [AlEt 4 ] and 1 mol of AlEt 3 in 3 mol of toluene.
  • the electrolytic coating of materials with magnesium, aluminum or aluminum / magnesium alloys is preferably carried out at a temperature of 80 to 105 ° C. A temperature of the plating bath of 91 to 100 ° C is preferred.
  • the electrolytic deposition of aluminum, magnesium, or aluminum / magnesium layers on the materials is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an aluminum / magnesium alloy anode. However, it is also possible to use only one aluminum or one magnesium anode.
  • the anodic switching of the material for pretreatment can be carried out for a period of 1 to 20 minutes, with 5 to 15 minutes being preferred.
  • the anodic loading of the materials necessary for the pretreatment is carried out with a current density of 0.2 to 2 A / dm 2 , preferably 0.5 to 1.5 A / dm 2 .
  • any material can be used which is suitable for electrodeposition. It is preferred that the material consists of a metal and / or of a metal alloy and / or is a metallized, electrolyte-resistant material, which can be dissolved in the electrolyte by anodic circuit.
  • the materials to be coated are preferably rack goods, bulk goods or endless products such as wire, square plates, screws or nuts.
  • the method according to the invention is characterized in that impurities or oxide layers which adhere to the materials are safely removed. Surprisingly, no disadvantageous change of the electrolyte composition occurs here, which would prevent a high-quality deposition of aluminum, magnesium or aluminum / magnesium layers on the materials. Furthermore, the electrodeposited metal layers are firmly adhering and homogeneously applied to the material, since after cleaning a renewed contamination of the material is prevented. In addition to the quality advantages mentioned, cost optimization of the coating of molded parts with metal layers is additionally achieved by the above-mentioned method steps.
  • Phase b) The dry part was introduced into an argon or nitrogen-flooded coating cell and immediately introduced into the coating electrolyte after a pre-rinse in toluene.
  • the electrolyte used was a mixture of the complexes K [AlEt 4] , K [AlEt 4 ] and AlEt 3 dissolved in toluene.
  • the counterelectrode used was an AlMg25 alloy plate.
  • the product to be coated was first anodically poled and treated at a current density of 1 A / dm 2 for 5 minutes at an electrolyte temperature of 95 ° C. Then reversed without removing the part from the electrolyte and immediately for 45 minutes at a current density of 1 5 A / dm 2 coated.
  • An AlMg alloy layer of about 14 ⁇ m thickness was deposited.
  • the adhesion of the layer was tested by cross hatch test and heat shock test (1 h at 220 ° C and quenching in cold water). It was found that excellent adhesion of the deposited layer to the base material was present. No peeling or bubbles could be detected.
  • a treated as a comparative sample was pretreated and coated as in Example 1, but without anodic polarity in advance.
  • the layer could be peeled off in the crosshatch test as a film. In heat shock test, the layer showed bubbles.
  • a magnesium die-cast part made of an AZ-91 alloy was blasted with corundum (grain size 0-50 ⁇ m) at 2 bar pressure. The part was then immediately placed in the inert gas atmosphere of the coating cell, pre-rinsed in toluene and immersed in the electrolyte bath as described in Example 1.
  • the product to be coated was anodized for 10 minutes at a current density of 1 A / dm 2 . In this case, a layer of about 2 microns was removed on the product surface. It was then reversed and the part switched cathodically for 1 hour at 1.5 A / dm 2 .
  • An AlMg layer with 23-25% Mg content and a layer thickness of approximately 18 ⁇ m was deposited.

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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)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé pour enduire par électrolyse des matériaux avec de l'aluminium, du magnésium ou des alliages d'aluminium et de magnésium. Selon ce procédé, le matériau est prétraité par immersion dans un bain électrolytique, dans lequel il est anodisé, l'enduction par électrolyse suivant immédiatement dans le même bain électrolytique.

Claims (12)

  1. Procédé d'enduction par électrolyse de matériaux avec de l'aluminium, du magnésium ou des alliages d'aluminium et de magnésium, le matériau étant trempé dans un électrolyte pour le prétraitement, y est branché anodiquement, puis directement après, l'enduction par électrolyse se produit dans le même électrolyte, le bain d'électrolyse contenant comme électrolyte des alliages alumino-organiques des formules générales (I) et (II),

            M [R1)3Al-(H-Al(R2)2)n-R3     ] (I)

            Al(R4)3     (II)

    n étant égal à 0 ou 1, M étant égal au sodium ou au potassium et R1, R2, R3, R4 pouvant être égaux ou différents, R1, R2, R3, R4 étant un groupe alkyle C1 à C4 et un solvant aprotique et exempt d'halogènes étant employé comme solvant pour l'électrolyte.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'un mélange des complexes K[AlEt4], Na[AlEt4] et AlEt3, est employé comme électrolyte.
  3. Procédé selon la revendication 2,
    caractérisé en ce que le rapport molaire des complexes à AlEt3 est de 1:0,5 à 1:3, de préférence 1:2.
  4. Procédé selon la revendication 2 ou 3,
    caractérisé en ce que 0 à 25 mol-%, de préférence 5 à 20 mol-% de Na[AlEt4], rapporté au mélange des complexes K[AlEt4] et Na [AlEt4] , est employé.
  5. Procédé selon l'une ou plusieurs des revendications 1 à 4,
    caractérisé en ce qu'un mélange de 0,8 mole K[AlEt4], de 0,2 mole Na[AlEt4], de 2 moles AlEt3 dans 3,3 moles de toluène est employé comme électrolyte.
  6. Procédé selon la revendication 1,
    caractérisé en ce qu'un mélange de Na[Et3Al-H-AlEt3] et de Na[AlEt4] et de AlEt3 est employé comme électrolyte.
  7. Procédé selon la revendication 6,
    caractérisé en ce que le rapport molaire de Na[Et3Al-H-AlEt3] à Na[AlEt4] est de 4:1 à 1:1, de préférence de 2:1.
  8. Procédé selon la revendication 6 ou 7,
    caractérisé en ce que le rapport molaire de Na[AlEt4] à AlEt3 est de 1:2.
  9. Procédé selon l'une ou plusieurs des revendications 6 à 8,
    caractérisé en ce qu'un mélange d'1 mole de Na[Et3Al-H-AlEt3] et d'1 mole d'AlEt3 dans 3 moles de toluène est employé comme électrolyte.
  10. Procédé selon l'une ou plusieurs des revendications 1 à 9,
    caractérisé en ce que l'enduction par électrolyse est réalisée à des températures de 80 à 105°C, de préférence de 91 à 100°C.
  11. Procédé selon l'une ou plusieurs des revendications 1 à 10,
    caractérisé en ce que le prétraitement est réalisé pour une laps de temps de 1 à 20 min., de préférence de 5 à 15 min.
  12. Procédé selon l'une ou plusieurs des revendications 1 à 11,
    caractérisé en ce que le prétraitement est réalisé à une charge anodique des matériaux avec une densité de courant de 0,2 à 2 A/dm2, de préférence de 0,5 à 1,5 A/dm2.
EP03807748A 2002-09-25 2003-07-15 Procede d'enduction par electrolyse de materiaux avec de l'aluminium, du magnesium ou des alliages d'aluminium et de magnesium Expired - Lifetime EP1543180B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03807748A EP1543180B1 (fr) 2002-09-25 2003-07-15 Procede d'enduction par electrolyse de materiaux avec de l'aluminium, du magnesium ou des alliages d'aluminium et de magnesium

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP02021402 2002-09-25
EP02021402A EP1403402A1 (fr) 2002-09-25 2002-09-25 Procédé pour la déposition electrolytique des materiaux avec aluminium, magnesium ou les alliages d'aluminium et magnesium
EP03807748A EP1543180B1 (fr) 2002-09-25 2003-07-15 Procede d'enduction par electrolyse de materiaux avec de l'aluminium, du magnesium ou des alliages d'aluminium et de magnesium
PCT/EP2003/007632 WO2004033762A1 (fr) 2002-09-25 2003-07-15 Procede d'enduction par electrolyse de materiaux avec de l'aluminium, du magnesium ou des alliages d'aluminium et de magnesium

Publications (2)

Publication Number Publication Date
EP1543180A1 EP1543180A1 (fr) 2005-06-22
EP1543180B1 true EP1543180B1 (fr) 2006-05-31

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Application Number Title Priority Date Filing Date
EP02021402A Withdrawn EP1403402A1 (fr) 2002-09-25 2002-09-25 Procédé pour la déposition electrolytique des materiaux avec aluminium, magnesium ou les alliages d'aluminium et magnesium
EP03807748A Expired - Lifetime EP1543180B1 (fr) 2002-09-25 2003-07-15 Procede d'enduction par electrolyse de materiaux avec de l'aluminium, du magnesium ou des alliages d'aluminium et de magnesium

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP02021402A Withdrawn EP1403402A1 (fr) 2002-09-25 2002-09-25 Procédé pour la déposition electrolytique des materiaux avec aluminium, magnesium ou les alliages d'aluminium et magnesium

Country Status (7)

Country Link
US (1) US7468123B2 (fr)
EP (2) EP1403402A1 (fr)
JP (1) JP2006500476A (fr)
CN (1) CN1685087B (fr)
AU (1) AU2003250061A1 (fr)
DE (1) DE50303610D1 (fr)
WO (1) WO2004033762A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1524336A1 (fr) * 2003-10-18 2005-04-20 Aluminal Oberflächtentechnik GmbH & Co. KG Pièces à usiner recouvertes d'un alliage aluminium-magnesium
JP2016000838A (ja) * 2012-10-15 2016-01-07 住友電気工業株式会社 アルミニウム膜、アルミニウム膜形成体、及びアルミニウム膜の製造方法
CN104884666B9 (zh) 2012-12-26 2017-09-22 Posco公司 铝镁镀层钢板及其制造方法
TWI464276B (zh) * 2013-06-19 2014-12-11 China Steel Corp 陽極用鋁鎂合金片及其製造方法
CN104674219A (zh) * 2015-03-25 2015-06-03 东莞仁海科技股份有限公司 一种压铸件表面处理新工艺

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1212213B (de) * 1964-02-29 1966-03-10 Aluminium Walzwerke Singen Verfahren zur Herstellung von stab- oder drahtfoermigen Elektroden fuer Elektrolytkondensatoren
US3969195A (en) * 1971-05-07 1976-07-13 Siemens Aktiengesellschaft Methods of coating and surface finishing articles made of metals and their alloys
US4148204A (en) * 1971-05-07 1979-04-10 Siemens Aktiengesellschaft Process of mechanically shaping metal articles
DE19855666A1 (de) * 1998-12-01 2000-06-08 Studiengesellschaft Kohle Mbh Aluminiumorganische Elektrolyte und Verfahren zur elektrolytischen Beschichtung mit Aluminium oder Aluminium-Magnesium Legierungen

Also Published As

Publication number Publication date
EP1403402A1 (fr) 2004-03-31
US7468123B2 (en) 2008-12-23
JP2006500476A (ja) 2006-01-05
US20060137990A1 (en) 2006-06-29
AU2003250061A1 (en) 2004-05-04
CN1685087A (zh) 2005-10-19
WO2004033762A1 (fr) 2004-04-22
CN1685087B (zh) 2010-12-29
DE50303610D1 (de) 2006-07-06
EP1543180A1 (fr) 2005-06-22

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