WO2009046328A1 - Dépôt galvanique de couches de métal sur des surfaces en magnésium ou en alliage de magnésium - Google Patents

Dépôt galvanique de couches de métal sur des surfaces en magnésium ou en alliage de magnésium Download PDF

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Publication number
WO2009046328A1
WO2009046328A1 PCT/US2008/078792 US2008078792W WO2009046328A1 WO 2009046328 A1 WO2009046328 A1 WO 2009046328A1 US 2008078792 W US2008078792 W US 2008078792W WO 2009046328 A1 WO2009046328 A1 WO 2009046328A1
Authority
WO
WIPO (PCT)
Prior art keywords
magnesium
zincate
etchant
magnesium alloy
bonding
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/US2008/078792
Other languages
English (en)
Inventor
Christoph Werner
Andreas MÖBIUS
Karl-Heiinz Wandner
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.)
MacDermid Enthone Inc
Original Assignee
Enthone Inc
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 Enthone Inc filed Critical Enthone Inc
Publication of WO2009046328A1 publication Critical patent/WO2009046328A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • 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
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C25D3/40—Electroplating: Baths therefor from solutions of copper from cyanide baths, e.g. with Cu+

Definitions

  • the present invention relates to a method for the galvanic deposition of metal layers on magnesium or magnesium alloy surfaces.
  • magnesium has been increasingly used in the automotive industry, in commercial aircraft construction and in the electronics industry. Especially in the production of high-quality products magnesium or magnesium alloys are used in order to save weight. Compared to other light alloys, magnesium or magnesium alloys have the advantage that they offer excellent casting properties, so that both injection- molded parts and die-cast parts having very good production qualities can be produced from corresponding magnesium alloys or from magnesium. Particularly the production of construction parts by means of a magnesium injection molding process seems to be of high interest also in future times, especially in the field of the automotive industry. During injection molding of magnesium or magnesium alloys the same are not heated until their complete melting but only to approx 100° below the melting point. A thixotropic state of the magnesium will be achieved thereby, in which state it can be correspondingly injection- molded.
  • the substrates which have been produced by means of corresponding casting processes must be subject as a rule to a surface finishing treatment.
  • the same may serve to corrosion protection of the magnesium or the magnesium alloy surface on one side and on the other side to the production of corresponding glossy or dull decorative surfaces by means of a deposition of metal layers on the surface.
  • Magnesium alloys which are frequently employed in the industry are such of the type AZ31 to AZ91, wherein AZ symbolize aluminum and zinc that have been added as alloy elements, and the subsequent numerals identify the size of the fraction of these alloy elements in the magnesium.
  • the invention is directed to a process for the galvanic coating of a magnesium or magnesium alloy surface with a metal-based layer, the process comprising a) an alkaline cleaning process, b) an alkaline deposition process for depositing the metal-based layer after the alkaline cleaning process, and no intermediate processes between (a) and (b) which involve exposure of the surface to an acidic solution.
  • the present invention is therefore based on the object of providing a process for the galvanic coating of magnesium or magnesium alloys, which process achieves a satisfying coating result for a great number of different magnesium alloys while avoiding the formation of pores as the same is known in prior art.
  • This object is solved by a process for the galvanic coating of magnesium or magnesium alloy surfaces, characterized in that during the entire coating process and until the complete coverage with a metal layer of the metal to be deposited, the surfaces to be coated are contacted exclusively with process solutions and washing solutions which have a pH value > pH7, preferably > pH 8.
  • the cleaning of the substrate to be coated can be performed with the aid of hot degreasing.
  • the substrate to be cleaned is treated with a suitable degreasing agent at a temperature of about 70 - 80 0 C for a duration of 10 minutes.
  • a suitable degreasing agent at a temperature of about 70 - 80 0 C for a duration of 10 minutes.
  • the selection of the degreasing agents to be used being made in dependence of the contaminations present on the substrates or substrate surfaces to be treated.
  • the degreasing agents that are to be employed are alkaline degreasing agents.
  • Kavitec modulus or of eductor nozzles may be provided in accordance with the invention.
  • Kavitec systems are high-pressure water nozzles which support the cleaning-off by cavitation effects.
  • a treatment of the substrate surface with an alkaline, cyanide-free pre-bonding etchant is performed.
  • a pre-bonding etchant is a zincate etchant, which in addition to sodium pyrophosphate (Na 4 P 2 O ?
  • zinc sulfate sodium carbonate
  • sodium fluoride includes suitable wetting agents for reducing the surface tension of the zincate etchant.
  • the zincate etchant which has been described and which is to be used in accordance with the invention has a pH value adjusted with sodium carbonate to within the range of pH 9 to 11, in preferred embodiments between 9.7 and 10.3, and in certain embodiments between 9.9 and 10.1
  • the substrate surface to be treated of the magnesium or magnesium alloy substrate to be coated is contacted with the zincate etchant at a temperature between 60 and 80 0 C, preferably between 65 and 75°C.
  • the exposing time is between 5 and 15 minutes, preferably between 9 and 11 minutes.
  • Zincate etchant 100 - 300 g/1 sodium pyrophosphate x 10 H 2 O
  • the composition of the zincate etchant is
  • a wetting agent known as Nonpitter 62 A or a wetting agent known as EnPREP TTM WA may be preferably used as a wetting agent.
  • a wetting agent known as EnPREP TTM WA may be preferably used as a wetting agent.
  • also combinations of different wetting agents may be employed.
  • a pre-bonding zincate layer is formed on the magnesium or magnesium alloy surface to be coated.
  • the thickness of the zincate layer is not narrowly critical and is most influenced by the nature of the substrates. In many embodiments it is a continuous layer having a thickness of on the order of less about 1 micron.
  • a cyanidic glossy copper electrolyte for example an electrolyte of the type CUPRALYTE 1545 from Enthone Inc., at a temperature between 40 and 55°C.
  • a current density between 0.5 and 2.0 A/dm 2 is set.
  • a current density is to be provided here which is lower for the use of plate or billet anodes than for the use of copper pieces in corresponding anode baskets.
  • the voltage to be applied lies within a range of 2.0 to 12.0 Volts, depending on the anodes which are used and on the substrates or substrate surfaces which are to be coated.
  • the cyanidic copper electrolyte which is used in the herein described embodiment of the process according to the invention exhibits a photometrically determined pH value within a range of pH 11.0 and pH 12.0.
  • the copper concentration in the copper electrolyte which is to be employed according to the invention is between 20 g/1 and 50 g/1.
  • the free potassium cyanide concentration in the cyanidic copper electrolyte which is to be employed here is between 20 g/1 and 35 g/1.
  • the electrolyte includes potassium carbonate of maximally 120 g/1.
  • the density of an electrolyte as described above is approximately 1.15 g/cm 3 .
  • copper layers can be deposited at a deposition speed in the order of approximately 0.4 ⁇ m/min at a set current density of 1 A/dm 2 on the substrate surfaces of the magnesium or magnesium alloy substrates which have been pre-treated in the above-described way.
  • the deposited copper layers are strongly adhering and show a uniform gloss.
  • additional metal layers can be applied to the so deposited copper layers, and this subsequent deposition of metal layers may take place both in acidic and alkaline coating electrolytes, provided that the underlying magnesium or magnesium alloy layer is completely covered with a corresponding copper layer.

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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

La présente invention concerne un procédé de revêtement galvanique de surfaces en magnésium ou en alliage de magnésium. Pour le dépôt de différentes couches de métal sur des surfaces en magnésium ou en alliage de magnésium, le procédé selon l'invention propose de mettre en contact les surfaces à recouvrir exclusivement avec des solutions de traitement et des solutions de lavage ayant une valeur de pH value ≥ 7 jusqu'à ce qu'une première couche de métal ait été déposée sur lesdites surfaces. Il a été démontré que des couches de métal pouvaient être déposées sur une pluralité de surfaces en magnésium ou en alliage de magnésium avec une excellente résistance d'adhésion et avec un bon résultat de dépôt, si le contact entre les surfaces à recouvrir et les solutions de traitement qui possèdent une valeur de pH < 7 était évité.
PCT/US2008/078792 2007-10-05 2008-10-03 Dépôt galvanique de couches de métal sur des surfaces en magnésium ou en alliage de magnésium Ceased WO2009046328A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200710048043 DE102007048043A1 (de) 2007-10-05 2007-10-05 Galvanische Abscheidung von Metallschichten auf Magnesium- oder Magnesiumlegierungsoberflächen
DE102007048043.3 2007-10-05

Publications (1)

Publication Number Publication Date
WO2009046328A1 true WO2009046328A1 (fr) 2009-04-09

Family

ID=40113008

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/078792 Ceased WO2009046328A1 (fr) 2007-10-05 2008-10-03 Dépôt galvanique de couches de métal sur des surfaces en magnésium ou en alliage de magnésium

Country Status (3)

Country Link
EP (1) EP2045364A2 (fr)
DE (1) DE102007048043A1 (fr)
WO (1) WO2009046328A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105543919A (zh) * 2015-12-18 2016-05-04 沈阳理工大学 镁合金表面通过物理气相沉积形成电镀用导电涂层的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010062357B4 (de) 2010-12-02 2013-08-14 Innovent E.V. Vorrichtung und Verfahren zur Herstellung eines mit zumindest einer Korrosionsschutzschicht beschichteten magnesiumhaltigen Substrats
DE102018216317A1 (de) * 2018-09-25 2020-03-26 Thyssenkrupp Ag Verfahren zur Modifikation von feuerverzinkten Oberflächen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4351713A (en) * 1979-08-22 1982-09-28 Thomas Steel Strip Corp. Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates
US5503682A (en) * 1991-11-06 1996-04-02 Henkel Kommanditgesellschaft Auf Aktien Process for degreasing and cleaning metal surfaces
US6068938A (en) * 1997-04-15 2000-05-30 Kabushiki Kaisha Kobe Seiko Sho Magnesium based alloys article and a method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4351713A (en) * 1979-08-22 1982-09-28 Thomas Steel Strip Corp. Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates
US5503682A (en) * 1991-11-06 1996-04-02 Henkel Kommanditgesellschaft Auf Aktien Process for degreasing and cleaning metal surfaces
US6068938A (en) * 1997-04-15 2000-05-30 Kabushiki Kaisha Kobe Seiko Sho Magnesium based alloys article and a method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105543919A (zh) * 2015-12-18 2016-05-04 沈阳理工大学 镁合金表面通过物理气相沉积形成电镀用导电涂层的方法

Also Published As

Publication number Publication date
EP2045364A2 (fr) 2009-04-08
DE102007048043A1 (de) 2009-04-23

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