WO2005035835A2 - Pieces a usiner enduites d'un alliage aluminium-magnesium - Google Patents

Pieces a usiner enduites d'un alliage aluminium-magnesium Download PDF

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Publication number
WO2005035835A2
WO2005035835A2 PCT/EP2004/052097 EP2004052097W WO2005035835A2 WO 2005035835 A2 WO2005035835 A2 WO 2005035835A2 EP 2004052097 W EP2004052097 W EP 2004052097W WO 2005035835 A2 WO2005035835 A2 WO 2005035835A2
Authority
WO
WIPO (PCT)
Prior art keywords
coated workpiece
layer
aluminum
intermediate layer
substrate
Prior art date
Application number
PCT/EP2004/052097
Other languages
German (de)
English (en)
Other versions
WO2005035835A3 (fr
Inventor
Hans De Vries
Matthias HÄRTEL
Jörg HELLER
Original Assignee
Aluminal Oberflächentechnik Gmbh & Co. Kg
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 Aluminal Oberflächentechnik Gmbh & Co. Kg filed Critical Aluminal Oberflächentechnik Gmbh & Co. Kg
Priority to JP2006534735A priority Critical patent/JP2007509233A/ja
Priority to US10/576,284 priority patent/US20070212563A1/en
Priority to EP04766747A priority patent/EP1675974A2/fr
Publication of WO2005035835A2 publication Critical patent/WO2005035835A2/fr
Publication of WO2005035835A3 publication Critical patent/WO2005035835A3/fr

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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • 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
    • Y10T428/12181—Composite powder [e.g., coated, etc.]

Definitions

  • the present invention is directed to workpieces coated with an aluminum / magnesium alloy, and to a process for their production.
  • the deposition of aluminum, magnesium or aluminum / magnesium alloys on workpieces which consist of base metal is a tried and tested means of protecting these workpieces from corrosion. At the same time, they are provided with a decorative coating.
  • the protective metal layer is mainly electrodeposited on the workpiece. The deposited metal layer significantly improves the corrosion resistance of the workpiece. It turns out, however, that the corrosion resistance of the workpiece depends on the adhesion of the protective layer applied to the workpiece. If the protective layer does not adhere sufficiently to the workpiece, the protective layer is easily removed, e.g. B. at
  • DE 31 12 919 A1 proposes to provide metal-coated iron workpieces with an adhesion-promoting intermediate layer made of cobalt, cobalt alloys or nickel-containing cobalt and to galvanically apply an aluminum layer thereon.
  • the intermediate layer serving as an adhesion promoter is applied galvanically from an aqueous medium.
  • the galvano-aluminum layer are chromated. This further improves the corrosion resistance.
  • DE 38 04 303 proposes a method for improving the adhesion of galvanic aluminum layers to metal workpieces by applying an adhesion-promoting layer.
  • a non-aqueous electrolyte is used to apply the adhesive layer made of iron, iron and nickel, nickel, cobalt, copper and alloys of the above-mentioned metals or tin-nickel alloys.
  • a galvano-aluminum layer is applied to the intermediate layer.
  • the application of the intermediate layer from a non-aqueous electrolyte is essential, since otherwise, when using an aqueous electrolyte, the metal workpiece becomes embrittled due to the hydrogen generated during the electrolysis. As a result, the often used low-alloy high-strength steels are adversely affected. Embrittlement of the workpieces is avoided by using a non-aqueous electrolyte to apply the metallic intermediate layer.
  • EP 1 141 447 B1 describes electrolytes for coating
  • Prior art layers are very hard and brittle.
  • fasteners that are provided with an aluminum / magnesium layer, such as. B. screws, used to fasten components
  • This risk is particularly so when the components are made of relatively soft or brittle materials, such as. B. made of magnesium. Due to the superficial destruction of the component, this can in turn be exposed to increased corrosion, which can lead to the destruction of the component.
  • the above-described corrosion occurs increasingly at high pH values, so that in both of the aforementioned cases of destruction of the surface layer of the fastening means or of the component, the rate of corrosion increases at high pH values.
  • the technical object of the present invention is to provide coated workpieces which have improved corrosion resistance, have in particular in the alkaline range and, in combination with other materials, show reduced corrosion, in particular if the coated workpieces are used as fastening means for fastening components.
  • a coated workpiece comprising a substrate, a metallic intermediate layer applied to the substrate and a layer applied to the intermediate layer containing an aluminum / magnesium alloy.
  • the surface of the substrate is electrically conductive. This can preferably be done by coating the substrate with graphite.
  • the substrate preferably contains a metal and / or a metal
  • the substrate can be a metallized substrate, wherein the substrate can be metallized over the entire surface or over part of the surface.
  • Preferred substrates contain plastics.
  • the substrate can furthermore be selected from the ingredients
  • the metallic intermediate layer preferably contains iron, iron and nickel, tin and nickel, nickel, cobalt, copper, chromium, molybdenum, vanadium or alloys of the above-mentioned metals.
  • the metallic intermediate layer preferably has a layer thickness of 0.1 ⁇ m to 30 ⁇ m.
  • the Layer thickness of the metallic intermediate layer 0.5 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m and most preferably 1.5 ⁇ m to 8 ⁇ m
  • the applied to the metallic intermediate layer containing an aluminum / magnesium alloy preferably contains 0.5 to 70 5 wt.% Magnesium. In a further preferred embodiment, 1 to 50% by weight, more preferably 2 to 40% by weight, in a further preferred embodiment 3 to 30% by weight, preferably 4 to 25% by weight and most preferably 5 to 20% by weight. % Magnesium contained in the aluminum / magnesium alloy.
  • the layer containing an aluminum / magnesium alloy preferably has a layer thickness of 0.1 ⁇ m to 100 ⁇ m.
  • the layer thickness is 0.5 ⁇ m to 70 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, preferably 2 ⁇ m to 40 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m, more preferably 4 ⁇ m to 28 ⁇ m and most preferred 5 ⁇ m to
  • the layer containing the aluminum / magnesium alloy is preferably the surface layer of the coated workpiece.
  • at least one layer can also be applied to the layer containing the aluminum / magnesium alloy, which is preferably a passivation 2 o.
  • the coated workpiece is preferably a rack, bulk goods or a continuous product, wherein the coated workpiece is preferably a wire, a sheet, a screw, a nut, a concrete anchor, a fastener or a machine component.
  • the coated workpiece is preferably used in the automotive industry in the transmission, engine and body area. It can be an oil pan or a transmission oil pan.
  • Another object of the present invention is to provide a method for producing a coated workpiece, comprising the steps of: a) applying a metallic intermediate layer to a substrate and b) applying a layer containing an aluminum / magnesium alloy to the metallic intermediate layer ,
  • the metallic intermediate layer is deposited from an aqueous solution or a non-aqueous solution.
  • the metallic intermediate layer is chemically deposited.
  • the metallic intermediate layer can be electrodeposited from an aqueous electrolyte.
  • electrolytes are solutions of the metal salts of iron, cobalt, nickel, copper or tin. These can be in the form of halides, sulfates, sulfonates or fluoroborates.
  • the electrolytes can contain further additives, such as, for example. B. complexing substances.
  • step a) it is also possible in step a) to electrodeposit the metallic intermediate layer from a non-aqueous electrolyte.
  • Possible electrolytes contain compounds of molybdenum or vanadium or all other aforementioned metals, which the intermediate layer can contain.
  • the metals are preferably in the form of halides which can be complexed or reacted with ether, in particular diethyl ether and / or acetylacetonate (acac), to give corresponding metal acetylacetonates.
  • the layer containing an aluminum / magnesium alloy is preferably deposited from an anhydrous electrolyte.
  • the layer containing an aluminum / magnesium alloy is electrodeposited from a water-free electrolyte in step b).
  • Any electrolyte which is known to the person skilled in the art can be used as the electrolyte.
  • the electrolyte contains organoaluminum compounds of the general formulas (I) and (II)
  • n 0 or 1
  • M is sodium or potassium and R 1 , R 2 , R 3 , R 4 may be the same or different, where R 1 , R 2 , R 3 , R 4 is a Ci to C Al- are alkyl group and a halogen-free, aprotic solvent is used as the solvent for the electrolyte.
  • a mixture of the complexes K [AIEt 4 ], Na [AlEtJ and AIEt 3 can be used as the electrolyte.
  • the molar ratio of the complexes to AIEt 3 is preferably 1: 0.5 to 1: 3 and more preferably 1: 2.
  • the electrolytic deposition of the layer containing an aluminum / magnesium alloy on the workpiece is carried out using a soluble aluminum and a likewise soluble magnesium anode or using an anode made of an aluminum / magnesium alloy.
  • the electrolytic coating is preferably carried out at a temperature of 80 to 105 ° C.
  • a temperature of the electroplating bath of 91 to 100 ° C. is preferred
  • a layer that conducts the electrical current is applied to the substrate before the metallic intermediate layer is applied in step a).
  • the layer which conducts the electrical current can be applied to the substrate by any method which is known to the person skilled in the art.
  • the layer that conducts the electrical current is preferably applied to the substrate by metallization.
  • a sheet of size 100 x 25 x 1 mm made of St37 steel is provided with a nickel intermediate layer with a thickness of approx. 1 ⁇ m.
  • the nickel layer is electrodeposited from an aqueous nickel sulfamate electrolyte.
  • a layer of an aluminum / magnesium alloy with a magnesium content of 20% by weight and a layer thickness of 12 ⁇ m is subsequently deposited on the nickel layer by electrodeposition from a non-aqueous electrolyte.
  • the coated sheet is bent lengthwise through an angle of 180 °, the applied metal layers remaining intact in the area of the bending edge.
  • a sheet of size 100 x 25 x 1 mm made of St37 steel is provided with a layer of an aluminum / magnesium alloy with a magnesium content of 20% by weight and a layer thickness of 12 ⁇ m by electrodeposition from a non-aqueous electrolyte.
  • the sheet coated in this way is bent lengthwise through an angle of 180 °, parts of the coating tearing open at the bending edge and flaking off in the form of the finest needles.
  • Five M6 x 55 screws are provided with an aluminum / magnesium alloy with a magnesium content of 15% by weight and a layer thickness of 16 ⁇ m by electrodeposition from a non-aqueous electrolyte.
  • Five additional M6 x 55 screws are covered with a nickel layer with a layer thickness of approx. 1 ⁇ m.
  • the nickel layer is electrodeposited from an aqueous nickel sulfamate electrolyte.
  • An aluminum / magnesium alloy with a magnesium content of 15% by weight and a layer thickness of 16 ⁇ m is subsequently applied to the nickel layer by electrodeposition from a non-aqueous electrolyte.
  • M5 x 5 screws are electroplated in a drum with an aluminum / magnesium alloy with a magnesium content of 10% by weight and an average layer thickness of 14 ⁇ m from a non-aqueous electrolyte.
  • Additional screws are provided with an intermediate nickel layer with a layer thickness of approx. 1-2 ⁇ m nickel.
  • the nickel layer is electroplated from an aqueous nickel sulfamate electrolyte.
  • a layer of an aluminum / magnesium alloy with a magnesium content of 10% by weight and an average layer thickness of 15 ⁇ m from a non-aqueous electrolyte is applied galvanically to the nickel layer in a drum.
  • the metallic intermediate layer causes a significant improvement in the corrosion resistance.
  • Coated workpieces comprising a substrate, a metallic intermediate layer applied to the substrate and a layer containing an aluminum / magnesium alloy applied to the intermediate layer show a superior property profile which the prior art workpieces do not have.

Landscapes

  • 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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

L'invention concerne une pièce à usiner enduite, qui comprend un substrat, une couche intermédiaire métallique appliquée sur le substrat, ainsi qu'une couche appliquée sur cette couche intermédiaire et contenant un alliage aluminium-magnésium. L'invention concerne également un procédé pour la production d'une telle pièce à usiner.
PCT/EP2004/052097 2003-10-18 2004-09-09 Pieces a usiner enduites d'un alliage aluminium-magnesium WO2005035835A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2006534735A JP2007509233A (ja) 2003-10-18 2004-09-09 アルミニウム／マグネシウム合金で被覆された加工製品
US10/576,284 US20070212563A1 (en) 2003-10-18 2004-09-09 Workpieces Coated with an Aluminum/Magnesium Alloy
EP04766747A EP1675974A2 (fr) 2003-10-18 2004-09-09 Pieces a usiner enduites d'un alliage aluminium-magnesium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP03023454A EP1524336A1 (fr) 2003-10-18 2003-10-18 Pièces à usiner recouvertes d'un alliage aluminium-magnesium
EP03023454.6 2003-10-18

Publications (2)

Publication Number Publication Date
WO2005035835A2 true WO2005035835A2 (fr) 2005-04-21
WO2005035835A3 WO2005035835A3 (fr) 2005-06-23

Family

ID=34354482

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/052097 WO2005035835A2 (fr) 2003-10-18 2004-09-09 Pieces a usiner enduites d'un alliage aluminium-magnesium

Country Status (7)

Country Link
US (1) US20070212563A1 (fr)
EP (2) EP1524336A1 (fr)
JP (1) JP2007509233A (fr)
KR (1) KR20060097016A (fr)
CN (1) CN1871375A (fr)
RU (1) RU2353714C2 (fr)
WO (1) WO2005035835A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008051883A1 (de) 2008-10-16 2010-04-22 Nano-X Gmbh Beschichtung zum kathodischen Korrosionsschutz von Metall, Verfahren zum Herstellen der Beschichtung und Verwendung der Beschichtung.

Families Citing this family (6)

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Publication number Priority date Publication date Assignee Title
DE102007016126A1 (de) * 2007-03-29 2008-10-02 Robert Bosch Gmbh Anordnung mit mindestens einem in Berührungskontakt mit mindestens einem Kunststoffbauelement stehenden Metallteil
CN102383129A (zh) * 2010-09-03 2012-03-21 鸿富锦精密工业（深圳）有限公司 壳体及其制造方法
RU2519694C1 (ru) * 2013-05-23 2014-06-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВПО МГТУ "СТАНКИН") Способ нанесения антикоррозийных покрытий на подложку из высокотвердых сплавов
KR102471961B1 (ko) * 2017-07-12 2022-11-28 르노코리아자동차 주식회사 자동차용 이중 금속판재구조 및 이의 제조방법
DE102017126590A1 (de) * 2017-11-13 2019-05-16 Doduco Solutions Gmbh Verfahren zum Herstellen einer Bodenplatte für ein Elektronikmodul
RU2713771C1 (ru) * 2019-10-23 2020-02-07 Федеральное государственное бюджетное образовательное учреждение высшего образования "Елецкий государственный университет им. И.А. Бунина" Электролит для осаждения сплава Cr-V

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3112919A1 (de) * 1981-03-31 1982-10-07 Siemens AG, 1000 Berlin und 8000 München "metallbeschichtete eisenwerkstoffe"
US4778575A (en) * 1988-01-21 1988-10-18 The United States Of America As Represented By The United States Department Of Energy Electrodeposition of magnesium and magnesium/aluminum alloys
EP0328128A1 (fr) * 1988-02-12 1989-08-16 Studiengesellschaft Kohle mbH Procédé relatif à l'adhérence entre des matériaux métalliques et des couches d'aluminium galvaniques ainsi que l'électrolyte non aqueux utilisé dans ce but
WO2000032847A2 (fr) * 1998-12-01 2000-06-08 Studiengesellschaft Kohle Mbh Electrolyte organique d'aluminium et procede de revetement electrolytique avec de l'aluminium ou des alliages aluminium-magnesium
WO2002088434A1 (fr) * 2001-04-30 2002-11-07 Alumiplate Incorporated Formulations d'electrodeposition d'aluminium
EP1279751A1 (fr) * 2001-07-28 2003-01-29 Aluminal Oberflächtentechnik GmbH & Co. KG Appareil pour la deposition d' aluminium ou d'alliage d'aluminium à partir des electrolytes contenant des alkyles d'aluminium

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US5225291A (en) * 1990-11-07 1993-07-06 Alupower, Inc. Deferred actuated battery assembly
US6203936B1 (en) * 1999-03-03 2001-03-20 Lynntech Inc. Lightweight metal bipolar plates and methods for making the same
EP1403402A1 (fr) * 2002-09-25 2004-03-31 Aluminal Oberflächtentechnik GmbH & Co. KG Procédé pour la déposition electrolytique des materiaux avec aluminium, magnesium ou les alliages d'aluminium et magnesium
EP1518945A1 (fr) * 2003-09-27 2005-03-30 Aluminal Oberflächtentechnik GmbH & Co. KG Electrolyte pour la deposition galvanique d'alliages aluminium magnesium
EP1682697A2 (fr) * 2003-11-07 2006-07-26 Aluminal Oberflächtentechnik GmbH & Co. KG Revetement de substrats

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3112919A1 (de) * 1981-03-31 1982-10-07 Siemens AG, 1000 Berlin und 8000 München "metallbeschichtete eisenwerkstoffe"
US4778575A (en) * 1988-01-21 1988-10-18 The United States Of America As Represented By The United States Department Of Energy Electrodeposition of magnesium and magnesium/aluminum alloys
EP0328128A1 (fr) * 1988-02-12 1989-08-16 Studiengesellschaft Kohle mbH Procédé relatif à l'adhérence entre des matériaux métalliques et des couches d'aluminium galvaniques ainsi que l'électrolyte non aqueux utilisé dans ce but
WO2000032847A2 (fr) * 1998-12-01 2000-06-08 Studiengesellschaft Kohle Mbh Electrolyte organique d'aluminium et procede de revetement electrolytique avec de l'aluminium ou des alliages aluminium-magnesium
WO2002088434A1 (fr) * 2001-04-30 2002-11-07 Alumiplate Incorporated Formulations d'electrodeposition d'aluminium
EP1279751A1 (fr) * 2001-07-28 2003-01-29 Aluminal Oberflächtentechnik GmbH & Co. KG Appareil pour la deposition d' aluminium ou d'alliage d'aluminium à partir des electrolytes contenant des alkyles d'aluminium

Non-Patent Citations (1)

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Title
LANDAU U ET AL: "ALUMINIUM, ALUMINIUM-MAGNESIUMLEGIERUNGEN UND WEISSE BRONZE GALVANOTECHNISCH ABGESCHIEDENE WERKSTOFFE MIT INTERESSANTEN GEBRACHSEIGENSCHAFTEN ALUMINIUM, ALUMINIUM MAGNESIUM ALLOYS AND WHITE BRONZE - ELECTRO-PLATED MATERIALS WITH INTERESTING PROPERTIES ALUMINIUM, ALLIAGES D'ALUMINIUM ET DE MAGNESIUM" ERZMETALL, RIEDERER VERLAG GMBH. STUTTGART, DE, Bd. 54, Nr. 7/8, September 2001 (2001-09), Seiten 369-380, XP001043704 ISSN: 0044-2658 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008051883A1 (de) 2008-10-16 2010-04-22 Nano-X Gmbh Beschichtung zum kathodischen Korrosionsschutz von Metall, Verfahren zum Herstellen der Beschichtung und Verwendung der Beschichtung.

Also Published As

Publication number Publication date
RU2006117025A (ru) 2007-11-27
RU2353714C2 (ru) 2009-04-27
CN1871375A (zh) 2006-11-29
EP1675974A2 (fr) 2006-07-05
US20070212563A1 (en) 2007-09-13
WO2005035835A3 (fr) 2005-06-23
KR20060097016A (ko) 2006-09-13
JP2007509233A (ja) 2007-04-12
EP1524336A1 (fr) 2005-04-20

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