EP0056590B1 - Bain galvanique pour le dépôt de revêtements de rhodium - Google Patents

Bain galvanique pour le dépôt de revêtements de rhodium Download PDF

Info

Publication number
EP0056590B1
EP0056590B1 EP82100109A EP82100109A EP0056590B1 EP 0056590 B1 EP0056590 B1 EP 0056590B1 EP 82100109 A EP82100109 A EP 82100109A EP 82100109 A EP82100109 A EP 82100109A EP 0056590 B1 EP0056590 B1 EP 0056590B1
Authority
EP
European Patent Office
Prior art keywords
rhodium
bath
acid
coatings
baths
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.)
Expired
Application number
EP82100109A
Other languages
German (de)
English (en)
Other versions
EP0056590A1 (fr
Inventor
Erika Kreuter
Werner Kuhn
Wolfgang Dipl.-Chem. Zilske
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.)
Evonik Operations GmbH
Original Assignee
Degussa 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 Degussa GmbH filed Critical Degussa GmbH
Publication of EP0056590A1 publication Critical patent/EP0056590A1/fr
Application granted granted Critical
Publication of EP0056590B1 publication Critical patent/EP0056590B1/fr
Expired 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used

Definitions

  • the invention relates to a galvanic bath for depositing veil-free, shiny rhodium coatings, which consists of rhodium sulfate or phosphate, sulfuric acid and / or phosphoric acid.
  • rhodium plating For decorative rhodium plating, especially for the coating of white gold, rhodium plating is required, which has a haze-free high gloss and a particularly light gray tone similar to the white gold color.
  • the layer thicknesses of these coatings are between 0.1 and 1 ⁇ m.
  • Baths containing rhodium phosphate or sulfate and sulfuric or phosphoric acid are mainly used to deposit galvanic rhodium layers. If layers with a thickness of more than 0.1 ⁇ m are deposited, these baths cannot be used to deposit the required haze-free, glossy coatings without additional additives. Even the light gray color of the layers is difficult to obtain reproducibly with the known baths, even if the necessary conditions are exactly met during the manufacture of the rhodium preparations.
  • Coatings from these baths also have strong internal tensions, so that numerous cracks appear in the layer even with very thin layers.
  • the corrosion protective effect of the rhodium layer is greatly reduced.
  • Rhodium baths with various additives are already known, which are said to improve the disadvantageous properties of the deposited rhodium layers.
  • Metallic additives such as thallium (CH-PS 553 255) or copper (FR-PS 1 577 593) have the disadvantage that they are highly toxic or do not give the desired light color.
  • alkali metal chlorides such as MgCl 2 or AICI 2 (DE-AS 2 329 578)
  • some chlorine can form on the anode, which makes the application considerably more difficult.
  • the constant discharge of chloride makes it difficult to achieve constant deposition conditions.
  • a rhodium bath is known (DE-PS 62 72 64), which can contain benzoic acid, phenol solution and gelatin.
  • Polybasic organic acids (DE-AS 2 242 503) and glutaric acid (DE-OS 2 242 503) are also known as additives.
  • the rhodium layers made from these baths do not show the desired white gold color.
  • rhodium baths which contain a rhodium salt, an acid and an aromatic sulfonic acid, such as phenolsulfonic acid.
  • aromatic sulfonic acid such as phenolsulfonic acid.
  • the rhodium bath additionally contains pyridine-3-sulfonic acid or naphthalene-tri-sulfonic acid.
  • a phosphonic acid e.g. B. of 1 hydroxy ethane-1,1-diphosphonic acid and / or a stable wetting agent, e.g. B. a fluorosurfactant
  • adherence of the hydrogen formed on the cathode is prevented, whereby the uniformity of color and gloss on the entire surface to be rhodium-plated is further improved.
  • the baths according to the invention advantageously contain 1-10 g / l rhodium as sulfate and / or phosphate, 20-200 g / l sulfuric, phosphoric acid or mixtures of both acids and 0.1-5 g / l pyridine-3-sulfonic acid.
  • the baths can be operated at current densities of 0.5-5 A / dm 2 and temperatures up to 60 ° C.
  • the layer is glossy and has a light reflectance of 0.716.

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (4)

1. Bain électrolytique destiné à déposer des revêtements de rhodium brillants, exempts de trouble, qui est constitué de sulfate ou phosphate de rhodium, d'acide sulfurique et/ou phosphorique caractérisé en ce que le bain contient supplémentairement de l'acide pyridine-3-sulfonique ou naphthaline-tri-sulfonique.
2. Bain électrolytique suivant la revendication 1, caractérisé en ce que le bain contient 1 à 10 g/1 de rhodium sous la forme de sulfate et/ou de phosphate de rhodium, 20 à 200 g/I d'acide sulfurique et/ou phosphorique, et 0,1 à 5 g/I d'acide pyridine-3-sulfonique.
3. Bain électrolytique au rhodium suivant les revendications 1 et 2, caractérisé en ce que le bain contient supplémentairement 0,01 à 2 g/I d'un agent mouillant.
4. Bain électrolytique suivant les revendications 1 à 3, caractérisé en ce que le bain contient supplémentairement 0,5 à 10 g/I d'un acide phos- phonique.
EP82100109A 1981-01-15 1982-01-09 Bain galvanique pour le dépôt de revêtements de rhodium Expired EP0056590B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3100997 1981-01-15
DE3100997A DE3100997C2 (de) 1981-01-15 1981-01-15 Bad zum galvanischen Abscheiden von Rhodiumüberzügen

Publications (2)

Publication Number Publication Date
EP0056590A1 EP0056590A1 (fr) 1982-07-28
EP0056590B1 true EP0056590B1 (fr) 1985-04-24

Family

ID=6122621

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82100109A Expired EP0056590B1 (fr) 1981-01-15 1982-01-09 Bain galvanique pour le dépôt de revêtements de rhodium

Country Status (5)

Country Link
EP (1) EP0056590B1 (fr)
JP (1) JPS57137492A (fr)
BR (1) BR8200158A (fr)
DE (2) DE3100997C2 (fr)
HK (1) HK51088A (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001048273A1 (fr) * 1999-12-23 2001-07-05 Degussa Galvanotechnik Gmbh Bain de depot galvanique de revetements de rhodium blancs brillants et agent de blanchiment utilise
US8372744B2 (en) * 2007-04-20 2013-02-12 International Business Machines Corporation Fabricating a contact rhodium structure by electroplating and electroplating composition
DE102019109188B4 (de) * 2019-04-08 2022-08-11 Umicore Galvanotechnik Gmbh Verwendung eines Elektrolyten zur Abscheidung von anthrazit/schwarzen Rhodium/Ruthenium Legierungsschichten

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048929A1 (fr) * 1980-09-25 1982-04-07 Nippon Mining Company Limited Article revêtu de rhodium de couleur noire ou bleue, procédé pour le fabriquer et bain utilisé dans ledit procédé

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3528895A (en) * 1967-07-10 1970-09-15 Sel Rex Corp Plating low stress bright rhodium
US3671408A (en) * 1971-05-25 1972-06-20 Sel Rex Corp Rhodium-platinum plating bath and process
DD109409A1 (fr) * 1974-01-31 1974-11-05
DE2506467C2 (de) * 1975-02-07 1986-07-17 Schering AG, 1000 Berlin und 4709 Bergkamen Bad und Verfahren zur galvanischen Abscheidung von Palladium-Nickel-Legierungen
JPS5224131A (en) * 1975-08-14 1977-02-23 Dowa Mining Co Luster* thick rhodium plating method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048929A1 (fr) * 1980-09-25 1982-04-07 Nippon Mining Company Limited Article revêtu de rhodium de couleur noire ou bleue, procédé pour le fabriquer et bain utilisé dans ledit procédé

Also Published As

Publication number Publication date
DE3100997C2 (de) 1986-08-14
DE3100997A1 (de) 1982-08-05
HK51088A (en) 1988-07-15
JPH029115B2 (fr) 1990-02-28
EP0056590A1 (fr) 1982-07-28
DE3263183D1 (en) 1985-05-30
JPS57137492A (en) 1982-08-25
BR8200158A (pt) 1982-11-03

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