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WO2006013184A1 - Revêtement de substrats à base de métaux legers ou d’alliage métallique léger - Google Patents

Revêtement de substrats à base de métaux legers ou d’alliage métallique léger Download PDF

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Publication number
WO2006013184A1
WO2006013184A1 PCT/EP2005/053676 EP2005053676W WO2006013184A1 WO 2006013184 A1 WO2006013184 A1 WO 2006013184A1 EP 2005053676 W EP2005053676 W EP 2005053676W WO 2006013184 A1 WO2006013184 A1 WO 2006013184A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
magnesium
aluminum
substrate
zinc
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.)
Ceased
Application number
PCT/EP2005/053676
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English (en)
Inventor
Jörg HELLER
Christoph Strobl
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
Original Assignee
Aluminal Oberflachentechnik GmbH
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 Oberflachentechnik GmbH filed Critical Aluminal Oberflachentechnik GmbH
Publication of WO2006013184A1 publication Critical patent/WO2006013184A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • 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
    • 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
    • C25D5/44—Aluminium

Definitions

  • the invention is directed to a method for the production of coated workpieces made of light metal or light metal alloy and to the workpieces thus produced.
  • Magnesium has a density of 1.7 g/cm 3 , thus once more being considerably lower in weight even when compared to other light metals already commonly used in construction, such as aluminum with a density of 2.7 g/cm 3 and titanium with a density of 4.5 g/cm 3 .
  • light metals are non-noble to a high degree, making them highly susceptible to corrosion.
  • most light metals form a passivation layer of the corresponding metal oxide in ambient air by reac ⁇ tion with oxygen. While the passivation layer protects from corrosion, it can nonetheless be disadvantageous to further treatment of the light metal because the nature of the surface is changed. For this reason, the passivation layer of ox- ides is frequently undesirable, and other systems must be used for corrosion protection.
  • a first well-known aspect of the prior art is to improve corrosion protection by reinforcing the natural oxide layer of light metals using anodization.
  • this is practicable only in those cases where there is no interference by the respective oxide layer.
  • Another way of protecting from corrosion is providing the light metals with metal ⁇ lic coatings, in which case metals less noble than the base material are usually employed.
  • the coatings can function as sacrificial anode on dam ⁇ aged spots, providing cathodic protection for the base material.
  • magne ⁇ sium this option applies to only a very limited extent because Mg is pronouncedly non-noble, so that no common metal is available as sacrificial an ⁇ ode.
  • Mg itself is frequently used as sac ⁇ rificial anode in steel vessels.
  • magnesium is a pronouncedly non-noble metal, be ⁇ ing considerably less noble even when compared to aluminum and zinc.
  • the electrochemical compatibility requires special attention because otherwise, there would be a risk of bimetallic corrosion between the base material and the coating material, re ⁇ sulting in corrosion of the base material. This is critical particularly with magne ⁇ sium because it has an extremely negative electric potential.
  • magnesium is attacked by bimetallic corrosion much more violently than alumi ⁇ num or zinc when in contact with virtually any common metallic construction and coating material.
  • magnesium undergoes corrosion to form alkaline corro- sion products having a pH value of more than 11. These corrosion products at ⁇ tack aluminum which dissolves from a pH value of about 9.4 on.
  • the strong alkalinity of the corrosion products represents another problem in magnesium corrosion.
  • the alkaline corrosion products of magnesium can do damage to paint films, but also to other amphoteric contact metals such as alu ⁇ minum or zinc. For this reason, the paint adhesion on magnesium component parts is difficult to handle, and the lifetime of pure aluminum coatings on magne ⁇ sium materials is extremely short.
  • DE 38 04 303 A1 suggests a method of improving the adhesion of electrodepos- ited aluminum layers on metal workpieces by applying an adhesion-promoting layer.
  • a non-aqueous electrolyte is used to apply the adhesion-promoting layer of iron, iron and nickel, nickel, cobalt, copper, and alloys of the above-mentioned metals, or tin-nickel alloys.
  • an electro-aluminum layer is applied to the intermediate layer.
  • EP 1 141 447 B1 discloses electrolytes for coating workpieces with layers of an aluminum/magnesium alloy.
  • such coating is necessary in those cases where joints with magnesium parts are to be generated, because the cor ⁇ rosion products of magnesium are alkaline, attacking the aluminum surface coat ⁇ ings.
  • aluminum/magnesium alloys contact corrosion is avoided and long-term resistance of the coating is provided.
  • steel fas ⁇ tening elements intended to contact magnesium component parts, especially in the automobile industry, with aluminum/magnesium alloy.
  • EP 1 141 447 B1 fails to disclose any metallic intermediate layers interposed between workpiece and corrosion-reducing layer of aluminum/magnesium alloy.
  • Corrosion protection of light metals, especially of magnesium further requires considering the fact that the material magnesium is a very soft substance.
  • workpieces coated with aluminum or aluminum/magnesium layers tend to be very hard and brittle.
  • fastening means e.g. as screws
  • the latter may be exposed to increased corrosion which may lead to the destruction of said component part.
  • the technical object of the invention is therefore to provide a corrosion protection system for light metals as base materials, particularly magnesium, which system has extremely low bimetallic corrosion sensitivity, good adhesion and permanent protection of the base material for a long time even under corresponding me ⁇ chanical load.
  • step b) heat treatment of the coated substrate at a temperature between 200 and 800°C so that at least the surface layer of the substrate and the layer/layers coated in step a) undergo partial and/or complete interdiffusion.
  • the determined thicknesses of the cor ⁇ rosion protection layer are substantially greater because part of the base mate ⁇ rial is also involved in the formation of the corrosion protection layer.
  • this achieves improved adhesive strength because there is improved anchoring of the applied corrosion protection layer in the base material as a result of such heat treatment.
  • the substrate is constituted of magnesium or magne ⁇ sium alloy.
  • the magnesium alloys include alloy compositions with aluminum, wherein the aluminum content can be from greater than zero to 10 wt.-% aluminum, and wherein minor amounts of zinc, manganese, silicon, rare earths and of the elements scandium and yttrium related to the rare earths can be included.
  • the layer of step a) is applied to the substrate material from a non-aqueous elec ⁇ trolyte or from an aqueous electrolyte.
  • the method according to the invention relates to light metals and light metal al ⁇ loys.
  • Light metal is understood to be a collective term used for metallic elements of low density.
  • light metals include metals such as aluminum, scandium, yttrium and titanium.
  • light metals of technical importance also preferred within the scope of the invention - are aluminum, magnesium, zinc, titanium or alloys thereof.
  • this includes a system wherein the substrate consists of magnesium or magnesium alloy and the layer consists of aluminum, zinc or alloys thereof.
  • Another system included in the present inven ⁇ tion is a system wherein the substrate consists of aluminum or aluminum alloy and the layer consists of magnesium, zinc or alloys thereof.
  • Another preferred embodiment also includes systems consisting of three or more layers, i.e., including one or more intermediate layers.
  • this includes a system wherein the substrate consists of magnesium or magnesium alloy, the first layer (intermediate layer) consists of aluminum, zinc or alloys thereof, and the second layer (surface layer) consists of aluminum, mag ⁇ nesium, zinc or alloys thereof, the first layer and the second layer not being made of the same metal.
  • Another preferred system is a system wherein the substrate consists of alumi ⁇ num or aluminum alloy, the first layer (intermediate layer) consists of magne- sium, zinc or alloys thereof, and the second layer (surface layer) consists of alu ⁇ minum, magnesium, zinc or alloys thereof. Similarly, the metals of the first and second layers are not the same.
  • the heat treatment is preferably effected in such a way that an alloy containing metal of the surface layer of the substrate and metal or metal alloy of the applied layer will be formed at least in the boundary area between substrate and applied layer.
  • the temperature of the heat treatment ranges between 250°C and 700°C, pref ⁇ erably between 300°C and 650°C, and more preferably between 250°C and 600°C.
  • the duration of heat treatment is preferably between 1 second and 5 hours, preferably between 30 seconds and 2 hours, and most preferably between 1 mi ⁇ nute and 1 hour.
  • the layer preferably can be subjected to an additional treatment subsequent to applying the layer to the substrate material and prior to performing the heat treatment. In a preferred fashion this can be anodic oxidation, preferably anodization of the layer.
  • Each applied layer preferably has a layer thickness of from 0.1 to 100 ⁇ m.
  • the layer thickness is from 0.5 ⁇ m to 70 ⁇ m, more preferably from 1 ⁇ m to 50 ⁇ m, preferably from 2 ⁇ m to 40 ⁇ m, more preferably from 3 ⁇ m to 30 ⁇ m, more preferably from 4 ⁇ m to 28 ⁇ m and most preferably from 5 ⁇ m to 25 ⁇ m.
  • the layer or one of the layers is electrodeposited from an aqueous electrolyte
  • solutions of the above-mentioned metals can be used as possible electrolytes. More specifically, the metals can be present as halides, sulfates, sulfonates or fluoborates.
  • the electrolytes may contain further additives such as complexing substances.
  • a layer deposited from an aqueous electrolyte or any portion of such a layer can also be deposited in an electroless fashion.
  • step a) is electrodeposited from a non-aqueous electrolyte, it is possible to use any non-aqueous electrolyte well-known to those skilled in the art.
  • organoaluminum compounds When depositing aluminum, magnesium or alloys thereof, organoaluminum compounds are preferably employed. More specifically, the electrolyte preferably includes organoaluminum compounds of general formulas (I) and (II):
  • n is equal to 0 or 1
  • M is sodium or potassium
  • R 1 , R 2 , R 3 , R 4 can be the same or different, R 1 , R 2 , R 3 , R 4 being a C 1 -C 4 alkyl group, and a halogen- free, aprotic solvent being used as solvent for the electrolyte.
  • a mixture of the complexes K[AIEt 4 ], Na[AIEt 4 ] and AIEt 3 can be employed as electrolyte.
  • the molar ratio of those complexes to AIEt 3 is preferably from 1 :0.5 to 1 :3, more preferably 1 :2.
  • Electrolytic deposition of the layer can be performed using a soluble anode in ⁇ cluding the metals to be deposited.
  • This anode either can include the above- mentioned metals intended for deposition in the form of a metal alloy, or multiple soluble anodes of the respective pure metals can be used. If a layer including an aluminum/magnesium alloy is to be deposited, it is possible to use a soluble aluminum anode and a likewise soluble magnesium anode or an anode of an aluminum/magnesium alloy.
  • Electrolytic deposition can also be effected using an insoluble anode.
  • Electrolytic coating from a non-aqueous electrolyte is preferably performed at a temperature of from 80 to 105°C. Preferred is an electroplating bath temperature of from 91 to 100°C.
  • an electroconductive layer is applied to the substrate prior to electrodepositing the layer in step a).
  • the electroconductive layer can be applied to the substrate using any method known to those skilled in the art.
  • the electroconductive layer is applied to the substrate by means of metallization.
  • step b) of the method according to the invention the temperature and/or dura ⁇ tion of the heat treatment is selected in such a way that an alloy containing metal of the surface layer of the substrate and metal and/or metal alloy of the coated layer will be formed at least in the boundary area between substrate and applied layer of step a).
  • temperature and/or duration of the heat treatment must be selected in a way so as to be adjusted to the properties of the substrate and to the specific applied layer.
  • an intermetallic phase will generally form on the surface of the coated workpiece, wherein the layer applied in step a) is con ⁇ verted either partially or completely into the intermetallic phase.
  • the coated substrate can be annealed below/along the liquidus line of the material mixture being formed.
  • the liquidus line is the melting temperature of the resulting material mixture as a function of the specific composition.
  • the initial proportion of aluminum in the surface layer will be 100%.
  • a magne ⁇ sium/aluminum alloy is formed which has a specific melting point.
  • the heat treatment of the coated substrate can be carried out in such a way that a liquid phase will form on the surface of the coated substrate. This is achieved by performing the treatment at a temperature which is higher than the melting temperature of the surface layer being formed.
  • Heat treatment can be effected under a protective gas atmosphere.
  • a protective gas that would not undergo reaction with the coated material.
  • the protective gas is a noble gas such as argon.
  • heat treatment it is not necessary that heat treatment be performed in a protective gas atmosphere.
  • heat treatment can also be effected in air.
  • the layer is subjected to further treatment in a preferred embodiment.
  • Any treatment procedure known to those skilled in the art can be used.
  • the treatment can be anodic oxidation, preferably anodization of the layer.
  • Such treatment is recommendable in those cases where a layer in ⁇ cluding aluminum has been applied in step a).
  • the coated workpiece employed in the method of the present invention is pref ⁇ erably a rack article, bulk material, continuous product or molded article.
  • the coated workpiece is preferably a wire, a band, a screw, a nut, a concrete an ⁇ chorage, a machine component part, an engine, an engine part, or a turbine blade.
  • the workpieces produced according to the method of the invention have a strongly adhering corrosion protection layer which has very low tendency to un ⁇ dergo bimetallic corrosion and is permanently stable.
  • corrosion protection for corrosion-sensitive light metals has been found, especially for aluminum al- loys and magnesium materials, with a rest potential largely adapted to the base material.
  • mag ⁇ nesium with a coating that does not represent an active anode towards the sub ⁇ strate material and, at the same time, is compatible with zinc, aluminum, as well as zinc/aluminum alloys and aluminum/magnesium alloys, neither attacking the latter, nor being attacked by the same.
  • an improvement in paintability of magnesium materials is achieved by providing them with a substrate-compatible coating which can be phosphated in the low-zinc process, including the bi- and trication processes.
  • a substrate-compatible coating which can be phosphated in the low-zinc process, including the bi- and trication processes.
  • Samples were produced at various temperatures, the material consisting of magnesium and the coating consisting of aluminum or zinc respectively.
  • the layers obtained were characterized using solid electron microscopy and subjected to quantitative analysis using an electron beam microprobe.
  • the samples were aluminized using aprotic solutions.
  • a zinc layer was applied using 20% electroless plating and 80% electroplating.
  • Example 1 The electro-aluminized magnesium system
  • An aluminum layer about 12 ⁇ m in thickness was electrodeposited on a magne ⁇ sium substrate consisting of AZ91 magnesium alloy.
  • Example 1 A Test series at 460 0 C
  • Example 1 A The samples were heated in the same way as in Example 1 A, but this time to 465°C for a period of 9 minutes. An investigation of the cooled samples showed that diffusion had taken place between magnesium material and aluminum layer. Layer growth of more than 50 ⁇ m with an aluminum content of about 35 atom % was determined, indicating an AI 2 Mg 3 intermetallic phase.
  • magnesium base material As base material, an AZ91 magnesium alloy was used, conventionally coated with a zinc layer using 20% electroless plating and 80% electroplating. The layer thickness on the sample was 12 ⁇ m.
  • the originally deposited pure zinc layer is characterized as layer A.
  • the composition thereof may contain a magnesium percent ⁇ age of up to 14 atom %. Consequently, the composition thereof may vary be ⁇ tween virtually pure zinc across the two-phase range ZJnCZMg 2 Zn 11 and up to pure Mg 2 Zn 11 .
  • Layers having the approximate composition MgZn 2 will be regarded as layer B hereinbelow.
  • a characterization as layer C applies to layers having a zinc content of about 60 atom % zinc, roughly corresponding to a composition of Mg 2 Zn 3 .
  • C This corresponds to a composition range which may include the intermetallic phases MgZn and Mg 7 Zn 3 or the high- magnesium eutectic.
  • a system having less than 8 atom % zinc, which is formed from the substrate material by zinc incorporation, with no complete formation of intermetallic phases being observed, will be characterized as layer D. Consequently, it may consist of a mixed crystal (MC), which may include a maximum of 2.4 atom % zinc, and, in addition, some percentage of low-zinc intermetallic phases.
  • MC mixed crystal
  • the table shows that diffusion of zinc into the magnesium, especially along the grain boundaries, takes place during such heat treatment.
  • the outer layer A has a lower content of pure zinc.
  • the layers B and C are formed by diffusion of zinc situated at the sur ⁇ face into the substrate, as well as by outward magnesium diffusion in the reverse direction. As a result of such mixing, there is a layer growth of about 300%.
  • Example 2A The same test series as in Example 2A was performed at a temperature of 380°C, using heating periods between 15 minutes and 90 minutes.
  • Table 2 shows the structure of the resulting layers. Table 2
  • the outer layer A is depleted in zinc from a maxi ⁇ mum of 90 atom % to 66 atom % with increasing migration time, thus being con ⁇ verted into layer B.
  • the course of porosity is approximately proportional to zinc depletion.
  • the layer decreases in thickness with increasing migration time.
  • layer B is formed from layer A by conversion.
  • the portion characterized as layer C is also depleted in zinc with time. After reaching a maximum layer thickness, this portion turns thinner again. Further enlargement thereof predominantly proceeds along the grain boundaries.
  • Layer D was invariably found to have a zinc concen- tration of less than or equal to 3 atom % and thus should be homogeneous. Fur ⁇ thermore, this layer shows a smooth transition to the zinc content of the sub ⁇ strate so that a maximum in layer thickness as a function of time can be ex ⁇ pected.
  • the layer composition is highly complex. Furthermore, it has been de ⁇ termined that the alloy layers, compared to the pure zinc layers originally pre ⁇ sent, substantially gain in volume and thickness as a result of magnesium incor ⁇ poration and the associated decrease in density.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

La présente invention concerne le procédé de production de pièces revêtues faites de métal léger ou d’alliage de métal, ledit procédé comprend les étapes suivantes : a) l’électrodéposition d’au moins une couche contenant au moins un métal et/ou alliage de métal sélectionné à partir d’un groupe d’aluminium, de magnésium, de zinc sur un substrat de métal léger ou d'alliage de métal léger, le substrat et la couche qui y sont appliqués ou en cas de multiples couches, deux couches adjacentes ne consistant pas au même métal ou au même alliage de métal; b) traitement à chaud de substrat revêtu à une température comprise entre 200° et 800° C de façon qu’au moins la surface de la couche du substrat et le/les couches appliquées à l'étape a) subit une interdiffusion partielle et/ou complète ; et sur les pièces revêtues produites à l’aide d’un tel procédé.
PCT/EP2005/053676 2004-08-04 2005-07-27 Revêtement de substrats à base de métaux legers ou d’alliage métallique léger Ceased WO2006013184A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04103745.8 2004-08-04
EP04103745A EP1624093A1 (fr) 2004-08-04 2004-08-04 Recouvrir des substrats en métaux legers ou en alliages de métaux légers

Publications (1)

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WO2006013184A1 true WO2006013184A1 (fr) 2006-02-09

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EP (1) EP1624093A1 (fr)
WO (1) WO2006013184A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8703234B2 (en) 2011-07-27 2014-04-22 GM Global Technology Operations LLC Cold sprayed and heat treated coating for magnesium
CN110965012A (zh) * 2019-12-20 2020-04-07 攀枝花学院 表面硬化耐蚀铝薄板及其制备方法和用途

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DE502005010834D1 (de) * 2005-02-03 2011-02-24 Ford Werke Gmbh Verfahren zur Herstellung einer metallischen Haftvermittlungsschicht auf einem Umgusskörper
DE102008019296A1 (de) * 2008-04-16 2009-10-22 Rolls-Royce Deutschland Ltd & Co Kg Verfahren zur Herstellung eines Feuerschutzes für aus Titan bestehende Bauteilkörper einer Fluggasturbine und Bauteilkörper aus Titan für eine Fluggasturbine
EP2312011A1 (fr) * 2009-10-15 2011-04-20 Georg Fischer Automotive AG Procédé de revêtement métallique d'une pièce de formage coulée et pièce de formage coulée fabriquée selon ce procédé
DE102009051673B3 (de) * 2009-11-03 2011-04-14 Voestalpine Stahl Gmbh Herstellung von Galvannealed-Blechen durch Wärmebehandlung elektrolytisch veredelter Bleche

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GB356443A (en) * 1930-08-20 1931-09-10 Automatic Telephone Mfg Co Ltd Improvements in or relating to electro plating of aluminium and its alloys
US2437612A (en) * 1941-08-21 1948-03-09 Osborg Hans Process for electrolytically zinc plating magnesium and magnesium base alloys
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JPS6144194A (ja) * 1984-08-09 1986-03-03 Mitsubishi Alum Co Ltd 摩擦駆動型押出材熱交換媒体製造法
CA1285857C (fr) * 1986-10-01 1991-07-09 Franz H. Vitovec Methode de traitement des surfaces en alliage d'aluminium
JPH0578888A (ja) * 1991-09-19 1993-03-30 Nippon Steel Corp 耐糸錆性に優れたアルミニウム板の製造方法
JPH05287469A (ja) * 1992-04-07 1993-11-02 Sky Alum Co Ltd 耐型かじり性、耐きず性、耐食性に優れたアルミニウム合金板の製法
JPH05320951A (ja) * 1992-05-19 1993-12-07 Nippon Steel Corp アルミニウム板の表面改質方法
JPH06179997A (ja) * 1992-12-14 1994-06-28 Nippon Steel Corp プレス成形性に優れたアルミニウム材料の製造方法
JP2000239862A (ja) * 1999-02-24 2000-09-05 Kobe Steel Ltd 耐食性に優れたＭｇ合金部材及びその製造方法
DE10257737B3 (de) * 2002-12-10 2004-02-26 Thyssenkrupp Stahl Ag Verfahren zur elektrolytischen Magnesium-Abscheidung auf verzinktem Blech
EP1533401A1 (fr) * 2003-11-14 2005-05-25 Aluminal Oberflächtentechnik GmbH & Co. KG Electroplacage de substrats suivi d'une étape de diffusion

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB356443A (en) * 1930-08-20 1931-09-10 Automatic Telephone Mfg Co Ltd Improvements in or relating to electro plating of aluminium and its alloys
DE874101C (de) * 1939-11-17 1953-04-20 Standard Steel Spring Company Verfahren zur Erhoehung des Widerstandes eines Metallgegenstandes gegen die Wirkung rissig- und bruechigmachigmachender Reagenzien und nach dem Verfahren hergestellte Metallgegenstaende
US2437612A (en) * 1941-08-21 1948-03-09 Osborg Hans Process for electrolytically zinc plating magnesium and magnesium base alloys
JPS6144194A (ja) * 1984-08-09 1986-03-03 Mitsubishi Alum Co Ltd 摩擦駆動型押出材熱交換媒体製造法
CA1285857C (fr) * 1986-10-01 1991-07-09 Franz H. Vitovec Methode de traitement des surfaces en alliage d'aluminium
JPH0578888A (ja) * 1991-09-19 1993-03-30 Nippon Steel Corp 耐糸錆性に優れたアルミニウム板の製造方法
JPH05287469A (ja) * 1992-04-07 1993-11-02 Sky Alum Co Ltd 耐型かじり性、耐きず性、耐食性に優れたアルミニウム合金板の製法
JPH05320951A (ja) * 1992-05-19 1993-12-07 Nippon Steel Corp アルミニウム板の表面改質方法
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