EP0099793B1 - Elektrolytisches Bad auf der Basis von dreiwertigem Chrom - Google Patents

Elektrolytisches Bad auf der Basis von dreiwertigem Chrom Download PDF

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Publication number
EP0099793B1
EP0099793B1 EP83401350A EP83401350A EP0099793B1 EP 0099793 B1 EP0099793 B1 EP 0099793B1 EP 83401350 A EP83401350 A EP 83401350A EP 83401350 A EP83401350 A EP 83401350A EP 0099793 B1 EP0099793 B1 EP 0099793B1
Authority
EP
European Patent Office
Prior art keywords
chromium
trivalent chromium
bath
ions
trivalent
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
EP83401350A
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English (en)
French (fr)
Other versions
EP0099793A1 (de
Inventor
Patrick c/o René Tardy Benaben
René Tardy
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.)
Association pour la Recherche et le Developpement des Methodes et Processus Industriels
Original Assignee
Association pour la Recherche et le Developpement des Methodes et Processus Industriels
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Filing date
Publication date
Application filed by Association pour la Recherche et le Developpement des Methodes et Processus Industriels filed Critical Association pour la Recherche et le Developpement des Methodes et Processus Industriels
Publication of EP0099793A1 publication Critical patent/EP0099793A1/de
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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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium

Definitions

  • the present invention relates to an electrolysis bath based on trivalent chromium and its use for chromium plating of conductive surfaces.
  • an aqueous solution of concentrated chromic acid (hexavalent chromium) is commonly used in the presence of catalyst ions (of the sulphate or fluoride type), or alternatively an organic or semi-aqueous mi solution.
  • catalyst ions of the sulphate or fluoride type
  • organic or semi-aqueous mi solution e.g., -organic trivalent chromium.
  • the use of an electrolysis bath based on trivalent chromium is preferable because it has many advantages.
  • electrolysis bath based on trivalent chromium consisting of an aqueous solution of trivalent chromium halide
  • this bath consists of an aqueous solution of trivalent chromium halide, containing at least Cr 3 + ions.
  • H +, and halide ions and containing no complex between trivalent chromium and OH- ions or between trivalent chromium and organic molecules and it has a concentration of 0.1 to 1 gram ion per liter of trivalent chromium, a lower pH 1.5 and it is obtained by careful reduction of chromium trioxide, in a hydrohalogenated medium, using a reducing agent chosen from alcohols, hydrogen peroxide, hyposulfites, sulfur dioxide.
  • the trivalent chromium salt obtained can be used directly for a chromium plating operation, at the end of the reduction of chromium trioxide, without the essential addition of additional products, in particular complexing agent of trivalent chromium or organic solvent so that it can start the chromium plating operation, and the proper functioning of this bath is only linked to the presence of Cr 3+ ions, halide ions, water molecules and H + ions.
  • the chromium trioxide solution may possibly contain sulfuric or hydrobromic ions, but no additional additive is essential for the proper functioning of the bath.
  • the anode used for the chromium plating operation is made of a material which can resist the release of chlorine and which allows the formation of hexavalent chromium by anodic oxidation as little as possible.
  • carbon anodes which allow to obtain excellent results.
  • the use of an electrolysis bath according to the invention offers numerous advantages.
  • the bath is very simple to make and its cost price is reduced.
  • concentration of chromium in the bath being low, the losses of chromium by mechanical entrainment are limited.
  • the absence of separation of the anode and cathode compartments allows chromium plating of complex parts. Because trivalent chromium is used the problems of toxicity and effluent treatment are reduced.
  • the electrolysis bath tolerates the interruption of electric current and it can be applied to different materials.
  • This electrolysis bath makes it possible to deposit on conductive substances a deposit of decorative chromium of color identical to that obtained by chromium plating processes with hexavalent chromium, with a concentration of the solution of trivalent chromium which is between 0.1 and 1 ion-g / 1 (5.2 to 51.99 g / 1 of Cr 3+ ).
  • the bath makes it possible to deposit on conductive substances a coating of chromium with a thickness greater than several tens of microns, even exceeding one hundred microns, deposit, dense , adherent and shiny, of hardness greater than a thousand Vickers.
  • the bath according to the invention in addition to the possible addition of conductive salts, such as NaCi, KCI, NH 4 CI tolerates the products commonly used in chromium plating for improving the performance of baths.
  • Appearance of the deposit adherent, shiny, color identical to that of the chrome deposited from the hexavalent chromium baths. Appearance of the deposit: adherent, dense, slightly matt, color identical to that of the chromium deposited from the hexavalent chromium baths.
  • Appearance of the deposit adherent, rough, color identical to that of the chromium deposited from the hexavalent chromium baths.
  • the electrolysis bath makes it possible to use a potential difference of the order of 5 volts (Example 2) and the deposits obtained are always of excellent quality, even when the he average thickness of the deposit obtained is much greater than 100 ⁇ m (Example 4).

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)

Claims (2)

1. Elektrolytisches Bad auf der Basis von dreiwertigem Chrom, gebildet aus einer wässerigen Lösung von Chromhalogenid, dadurch gekennzeichnet, dass das Bad aus einer wässerigen Lösung von dreiwertigem Chrom besteht, die wenigstens Cr3+, H+ und Halogenidionen enthält, nicht aber Komplexverbindungen zwischen dreiwertigem Chrom und organischen Molekülen, und dass es eine Konzentration von 0,1 bis 1 lonengramm pro Liter des dreiwertigen Chroms und einen pH-Wert unter 1,5 aufweist und durch schonende Reduktion von Chromtrioxyd in einem Hydrohalogenmilieu und durch ein Reduktionsmittel erhalten wird, das aus einer Alkohole, Wasserstoffperoxyd, Hyposulfite und schwefelige Anhydride enthaltenden Gruppe ausgewählt ist.
2. Anwendung des elektrolytischen Bades nach Anspruch 1, zur Beschichtung leitender Substanzen mit einem dichten und haftenden Überzug aus metallischem Chrom ohne die Notwendigkeit, die Zusammensetzung des Bades während der Beschichtung zu wechseln, gekennzeichnet durch folgende Bedingungen:
Dichte des Anodenstroms über 10 A/dm2,
pH-Wert unter 1,5, vorzugsweise in der Nähe von 1,
keine Trennung des Anodenbeckens vom Kathodenbecken in der benutzten elektrolytischen Zelle und
Aufrechterhaltung der Chromkonzentration zwischen 0,1 bis 1 lonengramm pro Liter.
EP83401350A 1982-06-30 1983-06-30 Elektrolytisches Bad auf der Basis von dreiwertigem Chrom Expired EP0099793B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8211488 1982-06-30
FR8211488A FR2529581A1 (fr) 1982-06-30 1982-06-30 Bain d'electrolyse a base de chrome trivalent

Publications (2)

Publication Number Publication Date
EP0099793A1 EP0099793A1 (de) 1984-02-01
EP0099793B1 true EP0099793B1 (de) 1987-04-01

Family

ID=9275557

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83401350A Expired EP0099793B1 (de) 1982-06-30 1983-06-30 Elektrolytisches Bad auf der Basis von dreiwertigem Chrom

Country Status (4)

Country Link
US (1) US4612091A (de)
EP (1) EP0099793B1 (de)
DE (1) DE3370661D1 (de)
FR (1) FR2529581A1 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
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US5413646A (en) * 1991-02-08 1995-05-09 Blount, Inc. Heat-treatable chromium
US5294326A (en) * 1991-12-30 1994-03-15 Elf Atochem North America, Inc. Functional plating from solutions containing trivalent chromium ion
JP3188361B2 (ja) * 1994-06-27 2001-07-16 ペルメレック電極株式会社 クロムめっき方法
FR2726289B1 (fr) * 1994-10-28 1997-03-28 Floquet Monopole Procede d'electrodeposition d'un revetement de chrome comportant des inclusions solides et bain mis en oeuvre dans ce procede
US6004448A (en) * 1995-06-06 1999-12-21 Atotech Usa, Inc. Deposition of chromium oxides from a trivalent chromium solution containing a complexing agent for a buffer
US6248228B1 (en) 1999-03-19 2001-06-19 Technic, Inc. And Specialty Chemical System, Inc. Metal alloy halide electroplating baths
DE10354760A1 (de) * 2003-11-21 2005-06-23 Enthone Inc., West Haven Verfahren zur Abscheidung von Nickel und Chrom(VI)freien metallischen Mattschichten
US7052592B2 (en) * 2004-06-24 2006-05-30 Gueguine Yedigarian Chromium plating method
CN101410556B (zh) * 2006-03-31 2010-12-29 爱托特奇德国股份有限公司 结晶态功能性铬镀层
CA2700147C (en) 2007-10-02 2015-12-29 Atotech Deutschland Gmbh Crystalline chromium alloy deposit
US9758884B2 (en) * 2012-02-16 2017-09-12 Stacey Hingley Color control of trivalent chromium deposits
CN104775139A (zh) * 2015-04-21 2015-07-15 柳州凡一科技有限公司 一种插秧机船板电镀方法

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GB301478A (en) * 1927-12-01 1929-02-21 Langbein Pfanhauser Werke Ag Process for the electrolytic deposition of chromium
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US1797357A (en) * 1928-03-29 1931-03-24 Ternstedt Mfg Co Chromium plating
US2524803A (en) * 1947-03-26 1950-10-10 Du Pont Production of a basic chromic chloride
US2928723A (en) * 1956-08-23 1960-03-15 Diamond Alkali Co Process for making basic chromic chlorides
US3414492A (en) * 1965-12-14 1968-12-03 Corillium Corp Chromium plating process
US3419481A (en) * 1966-04-08 1968-12-31 Diamond Shamrock Corp Electrolyte and process for electroplating black chromium and article thereby produced
US3442777A (en) * 1966-06-20 1969-05-06 Corillium Corp Chromium plating process
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SU475346A1 (ru) * 1972-10-23 1975-06-30 Институт Органического Катализа И Электрохимии Ан Казахской Сср Способ получени хлорида хрома
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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Gmelins Handbuch der Anorganischen Chemie, Vol. 52, A1(1962), Seiten 480-482 *

Also Published As

Publication number Publication date
FR2529581A1 (fr) 1984-01-06
DE3370661D1 (en) 1987-05-07
EP0099793A1 (de) 1984-02-01
US4612091A (en) 1986-09-16

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