WO2015039647A1 - Bain galvanique - Google Patents

Bain galvanique Download PDF

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Publication number
WO2015039647A1
WO2015039647A1 PCT/DE2014/100258 DE2014100258W WO2015039647A1 WO 2015039647 A1 WO2015039647 A1 WO 2015039647A1 DE 2014100258 W DE2014100258 W DE 2014100258W WO 2015039647 A1 WO2015039647 A1 WO 2015039647A1
Authority
WO
WIPO (PCT)
Prior art keywords
galvanic bath
nickel
molybdenum alloy
alloy according
mol
Prior art date
Application number
PCT/DE2014/100258
Other languages
German (de)
English (en)
Inventor
Frank Brode
Alexander Meyerovich
Original Assignee
Harting 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 Harting Kgaa filed Critical Harting Kgaa
Priority to EP14753005.9A priority Critical patent/EP3047051A1/fr
Priority to CN201480051791.9A priority patent/CN105579620A/zh
Priority to US14/911,442 priority patent/US20160194775A1/en
Priority to JP2016515411A priority patent/JP2016532004A/ja
Publication of WO2015039647A1 publication Critical patent/WO2015039647A1/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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • 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
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials

Definitions

  • the invention relates to a galvanic bath for the deposition of nickel-molybdenum alloys on a surface of an object.
  • nickel-molybdenum alloys for example, contact elements of connectors can be coated.
  • further layers for example composed of silver / silver alloys or gold / gold alloys or copper / copper alloys, can be applied.
  • Galvanic baths based on ammonium-nickel and ammonium-molybdenum complexes are generally classified by the experts as less stable.
  • insoluble molybdenum compounds are formed, for example MoO (OH) 3
  • Galvanic baths for the deposition of a nickel-molybdenum alloy for the deposition of a nickel-molybdenum alloy.
  • the galvanic baths also contain ammonium and / or
  • the object of the present invention is to provide a stable alloying bath which enables deposition of the nickel-molybdenum alloys having a high molybdenum content.
  • the object is achieved by a galvanic bath according to claim 1.
  • the galvanic bath according to the invention can be produced in a simple manner. It is also environmentally friendly.
  • a galvanic bath may consist of an aqueous, preferably
  • Ammonium complexes each of nickel and / or molybdenum
  • citric acid and / or the citrate can also their citric acid and / or their citrate
  • the bath contains, for example, ketoglutaric acid and / or aconitic acid and / or ⁇ -ketoglutarate and / or Ketoglutarate and / or aconitate.
  • ketoglutaric acid and / or aconitic acid and / or ⁇ -ketoglutarate and / or Ketoglutarate and / or aconitate preferably, the
  • aforementioned substances a concentration between 0, 1 and 0.6 mol / L, more preferably between 0, 1 and 0.4 mol / L in the bath.
  • Oxidation levels in the galvanic bath is present.
  • the soluble complex compounds of molybdenum can be prepared prior to their use according to the invention in that, for example, molybdenum salts in which the molybdenum in
  • the molybdenum in different oxidation states is produced by a chemical and / or electrochemical reduction of the molybdate ions. After reduction, molybdenum ions are in the
  • Salts of nickel and / or cobalt and / or iron and / or phosphorus and / or rhenium and / or palladium and / or platinum, which in combination with molybdenum salts permit different alloy compositions of the layer, are advantageously used as the electrolyte. So you can to 50% -Gew. Separate molybdenum.
  • the molybdenum content in the alloy matrix exerts a significant influence on the structure structure of a metallic coating.
  • scanning electron micrographs SEM showed that a layer with a molybdenum content of 20 to 40 Percent by weight (wt.%), Fine crystalline to amorphous structures.
  • the bath may contain organic additives such as stabilizers, wetting agents and brighteners.
  • organic additives such as stabilizers, wetting agents and brighteners.
  • the usual wetting agents are
  • nonionic, cationic or anionic nature can also act as brighteners, in concentrations of 0.01 to 20 g / liter.
  • the galvanic bath contains at least one
  • Brightening agents preferably in a concentration between 0.01 and 5 percent by weight (wt.%),
  • wetting agent preferably in a concentration between 0.05 and 0.5 wt .-%.
  • the usual wetting agents are nonionic, cationic or anionic in nature.
  • Conducting salts preferably in a concentration between 0.2 and 0.8 mol / L, particularly preferably in a concentration between 0.3 and 0.6 mol / L.
  • lauryl sulfate, lauryl ether sulfate or acylamidesulfonates or a mixture of the aforementioned wetting agents are used as wetting agents. These wetting agents greatly reduce the surface tension of the bath. Through these additives can optically
  • brightening agents for the nickel-containing baths are sulfonimides, sulfonamides, alkyl sulfonic acids (sulfonates), aryl sulfonic acids (sulfonates) or a
  • conductive salts of sodium and Used potassium salts are between 0.2 to 0.8 moles per liter (mol / L), but preferably between 0.3 and 0.6 mol / L.
  • the pH of the galvanic bath is between 4 and 11, more preferably between 7.5 and 9.5.
  • the pH is adjusted by addition of alkali metal hydroxide, for example NaOH. It has been found that the above-mentioned citrate in these pH ranges is particularly suitable for suppressing disproportionation.
  • the galvanic bath in a temperature range between 20 to 85 degrees Celsius (° C), in particular between 50 ° C to 75 ° C operated.
  • ketoglutaric acid and / or aconitic acid and / or ⁇ -ketoglutarates and / or ⁇ -ketoglutarates and / or aconitates the concentration of these substances preferably being in the range between 0.1 and 0.6 mol / l, particularly preferably is between 0, 1 and 0.4 mol / L.
  • the galvanic bath according to the invention is outstandingly suitable for the deposition of silver-colored nickel-molybdenum alloys on technical objects, such as abrasion-resistant and corrosion-resistant coatings of electronic components.
  • Particularly advantageous contact elements of connectors can thus be provided.
  • the galvanic bath according to the invention shows long-term stability and can be used for galvanic Deposition of nickel-molybdenum alloys can be used. Such a result could be similar to the known baths
  • Composition can not be achieved.
  • nickel (II) sulfate nickel sulfate hexahydrate or nickel chloride.
  • the nickel concentration in the bath is advantageously between 0.20 and 0.35 mol / L, more preferably between 0.22 and 0.3 mol / L.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un bain galvanique pour le dépôt d'un alliage nickel-molybdène. Ce bain galvanique est constitué d'un solution aqueuse de complexes amine et/ou de complexes ammonium-nickel et/ou de complexes ammonium- molybdène. Ledit bain galvanique contient de l'acide citrique et/ou des ions citrate et/ou des produits d'oxydation de l'acide citrique et/ou des citrates, le molybdène étant présent à diverses étapes d'oxydation, en particulier sous forme de Mo(V) et de Mo(VI), dans le bain galvanique.
PCT/DE2014/100258 2013-09-18 2014-07-15 Bain galvanique WO2015039647A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP14753005.9A EP3047051A1 (fr) 2013-09-18 2014-07-15 Bain galvanique
CN201480051791.9A CN105579620A (zh) 2013-09-18 2014-07-15 电镀浴
US14/911,442 US20160194775A1 (en) 2013-09-18 2014-07-15 Galvanic bath
JP2016515411A JP2016532004A (ja) 2013-09-18 2014-07-15 電気めっき浴

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013110263.8A DE102013110263A1 (de) 2013-09-18 2013-09-18 Galvanisches Bad
DE102013110263.8 2013-09-18

Publications (1)

Publication Number Publication Date
WO2015039647A1 true WO2015039647A1 (fr) 2015-03-26

Family

ID=51383525

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2014/100258 WO2015039647A1 (fr) 2013-09-18 2014-07-15 Bain galvanique

Country Status (6)

Country Link
US (1) US20160194775A1 (fr)
EP (1) EP3047051A1 (fr)
JP (1) JP2016532004A (fr)
CN (1) CN105579620A (fr)
DE (1) DE102013110263A1 (fr)
WO (1) WO2015039647A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA029776B1 (ru) * 2016-12-08 2018-05-31 Белорусский Государственный Университет (Бгу) Способ получения композиционного защитного покрытия на основе металла
CN113430557B (zh) * 2021-06-09 2023-01-13 有研工程技术研究院有限公司 多功能幂层电极材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3032485A (en) * 1958-10-01 1962-05-01 Ncr Co Electrolytic bath for use in electrodeposition of ferromagnetic compositions
US3947331A (en) * 1970-11-30 1976-03-30 Agence Nationale De Valorisation De La Recherche (Anvar) Methods for forming an electrolytic deposit containing molybdenum on a support and the products obtained thereby
GB2033429A (en) * 1978-10-06 1980-05-21 Statni Vyzkumny Ustav Material Electrolyte for Cathodic Deposition of Alloys of Nickel with Molybdenum
JPH04124293A (ja) 1990-09-13 1992-04-24 C Uyemura & Co Ltd ニッケル―モリブデン合金めっき浴及びめっき方法
JP2005082856A (ja) 2003-09-08 2005-03-31 Osaka Prefecture ニッケル−モリブデン合金めっき液とそのめっき皮膜及びめっき物品
JP2006161151A (ja) * 2004-11-12 2006-06-22 Toyo Kohan Co Ltd 鉄族金属とＭｏ及び／又はＷからなる合金の電気めっき方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0171685B1 (ko) * 1994-02-26 1999-02-18 문성수 팔라듐 2원 또는 3원 합금 도금 조성물, 이를 이용한 도금방법 및 도금체
JP3985904B2 (ja) * 2004-09-13 2007-10-03 株式会社黄金メッキ工場 ニッケル−タングステン合金めっき液及びニッケル−タングステン合金めっき皮膜の形成方法
CN102409374A (zh) * 2011-11-28 2012-04-11 上海应用技术学院 一种镍-钼镀层的制备方法
CN102787329A (zh) * 2012-08-31 2012-11-21 重庆大学 一种高效Ni-Mo-P/Ni析氢电极制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3032485A (en) * 1958-10-01 1962-05-01 Ncr Co Electrolytic bath for use in electrodeposition of ferromagnetic compositions
DE1216647B (de) 1958-10-01 1966-05-12 Ncr Co Bad zum galvanischen Abscheiden eines ferromagnetischen UEberzugs
US3947331A (en) * 1970-11-30 1976-03-30 Agence Nationale De Valorisation De La Recherche (Anvar) Methods for forming an electrolytic deposit containing molybdenum on a support and the products obtained thereby
GB2033429A (en) * 1978-10-06 1980-05-21 Statni Vyzkumny Ustav Material Electrolyte for Cathodic Deposition of Alloys of Nickel with Molybdenum
JPH04124293A (ja) 1990-09-13 1992-04-24 C Uyemura & Co Ltd ニッケル―モリブデン合金めっき浴及びめっき方法
JP2005082856A (ja) 2003-09-08 2005-03-31 Osaka Prefecture ニッケル−モリブデン合金めっき液とそのめっき皮膜及びめっき物品
JP2006161151A (ja) * 2004-11-12 2006-06-22 Toyo Kohan Co Ltd 鉄族金属とＭｏ及び／又はＷからなる合金の電気めっき方法

Also Published As

Publication number Publication date
DE102013110263A1 (de) 2015-03-19
US20160194775A1 (en) 2016-07-07
CN105579620A (zh) 2016-05-11
EP3047051A1 (fr) 2016-07-27
JP2016532004A (ja) 2016-10-13

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