EP2635724A1 - Procédé de dépôt de chrome dur à partir d'électrolytes exempts de cr(vi) - Google Patents

Procédé de dépôt de chrome dur à partir d'électrolytes exempts de cr(vi)

Info

Publication number
EP2635724A1
EP2635724A1 EP11779627.6A EP11779627A EP2635724A1 EP 2635724 A1 EP2635724 A1 EP 2635724A1 EP 11779627 A EP11779627 A EP 11779627A EP 2635724 A1 EP2635724 A1 EP 2635724A1
Authority
EP
European Patent Office
Prior art keywords
iii
chromium
takes place
solution
preparation
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.)
Granted
Application number
EP11779627.6A
Other languages
German (de)
English (en)
Other versions
EP2635724B1 (fr
Inventor
Hermann Kronberger
Günter Wolf
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.)
Cest Kompetenzzentrum fur Elektrochemische Oberflachentechnologie GmbH
Technische Universitaet Wien
Original Assignee
Cest Kompetenzzentrum fur Elektrochemische Oberflachentechnologie GmbH
Technische Universitaet Wien
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 Cest Kompetenzzentrum fur Elektrochemische Oberflachentechnologie GmbH, Technische Universitaet Wien filed Critical Cest Kompetenzzentrum fur Elektrochemische Oberflachentechnologie GmbH
Publication of EP2635724A1 publication Critical patent/EP2635724A1/fr
Application granted granted Critical
Publication of EP2635724B1 publication Critical patent/EP2635724B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • 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
    • C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used

Definitions

  • the invention relates to a process for the electrodeposition of chromium, preferably hard chromium, on a substrate made of an electrolyte solution containing Cr (II), Cr (III) or mixtures thereof and halides.
  • Hard chrome is produced as a wear and corrosion protection according to the current state of the art in high layer thicknesses almost exclusively of chromic acid electrolyte. Depending on the deposition conditions, hardnesses between 800 and 1150 HVo . i achieved. A further increase in hardness can be achieved with conventional hard chrome only by post-treatment. Because of the carcinogenic potential of Cr (VI) compounds and the resulting limitations, such as Regulation (EC) No 1907/2006 (RE ACH Regulation), increased efforts are underway not only for products but also for manufacturing processes Cr ( VI) -free. Particularly affected are the aerospace and automotive industries and their suppliers.
  • GB 1 488 381 and GB 1 144 913 envisage the use of dimethylformamide (DMF), US 4,107,004 the use of hypophosphite.
  • DMF dimethylformamide
  • US 4,107,004 the use of hypophosphite.
  • the deposition of thin Cr layers for decorative purposes is often made of formate oxalate or maleate-based Cr (III) electrolytes with glycine as an additive.
  • US Pat. No. 4,804,446 discloses an electrolyte based on CrCl 3 with additions of boric acid (as buffer), KBr (as conducting salt) and various organic acids (formic acid, glycolic acid and citric acid) or their Na or K salts.
  • WO 2007/115030 A1 describes the chromium deposition from trivalent chromium sulfate / chloride electrolytes.
  • the published US patent application. 2008/0169199 Al describes the use of a trivalent chromium electrolyte based on sulfate and / or chloride with various bromides as additives.
  • the main disadvantages of the methods described so far compared to the deposition of hard chromium from conventional hexavalent electrolytes are usually due to a low maximum layer thickness d (usually d ⁇ 15 ⁇ ) as well as deficient layer quality or adhesion, etc.
  • Sulfate-based electrolytes frequently have the disadvantage of formation of Cr (VI) as a side reaction at the anode, which is undesirable for Cr (III) electrolytes; the disadvantage of halide-based electrolytes is the anodic reaction of the electrolyte under halogen evolution when using dimensionally stable electrodes.
  • Object of the present invention is therefore to provide a method of the type mentioned, in which these disadvantages are avoided.
  • a method is to be provided in which a chromium layer is deposited on a substrate, which has good adhesion and very high hardness and no upper limit for the achievable layer thicknesses.
  • the chrome layer should have high gloss.
  • the disadvantages of the prior art regarding the toxicity and carcinogenicity of Cr (VI) compounds should be avoided.
  • This object is achieved by a method of electrodepositing chromium, preferably hard chrome, on a substrate of an electrolyte solution containing Cr (II), Cr (III) or mixtures thereof and halides by preventing the formation of elemental halogen by using a solution anode or by complexing the elemental halogen formed during the deposition.
  • the preferred halides are iodides and bromides, although preference is given to the bromides or mixed solutions of iodide / bromide.
  • the preparation of the electrolyte solutions by dissolution of Cr metal takes place in acidic halide solutions.
  • the production of the electrolyte solutions by mixing a solution of Cr (III) halide and a Cr (II) -containing solution.
  • the preparation of the Cr (II) -containing solution is carried out discontinuously by dissolving Cr metal and admixing it with the electrolyte solution.
  • the preparation of the Cr (II) -containing solution by dissolving Cr metal and the admixing with the electrolyte solution is carried out continuously by means of a bypass.
  • the preparation of the electrolyte solutions by dissolution of Cr (III) halides and the in situ - reduction of Cr (III) to Cr (II) takes place directly on the substrate or by means of at least one auxiliary electrode.
  • the preparation of the electrolyte solutions by dissolution of Cr (III) halides and the ex situ - reduction of Cr (III) to Cr (II) by means of at least one auxiliary electrode.
  • auxiliary electrode In conventional Cr (VI) electrolytes, a too high local concentration of Cr (II) ions at the cathode is largely prevented by the high oxidation power of the high excess Cr (VI) ions.
  • an auxiliary electrode If an auxiliary electrode is used, this preferably has a (negative) hydrogen overvoltage of at least 450 mV in the range of technical current densities.
  • a sufficiently high overvoltage for hydrogen can be provided when using an auxiliary electrode, that the auxiliary electrode has a surface of Pb, Hg, amalgam or preferably of conductive (eg boron-doped) diamonds.
  • the electrolyte solutions have complexing agents for elemental halogen in order to prevent the release of toxic halogens.
  • the complexing agent is a quaternary ammonium compound or a mixture of such compounds.
  • suitable ammonium compounds are N-methyl-ethyl-pyrolidinium bromide and N-methyl-ethyl-morpholinium-bromide.
  • the complex which is formed from a reaction of the complexing agent with halogen, preferably bromine or iodine during the metal deposition, by reduction reaction to the complexing agent and halide, preferably bromide or iodide, regenerated and can be recycled in this way , This regeneration can be done for example by recombination with cathodically formed hydrogen or by dissolution of chromium metal.
  • halogen preferably bromine or iodine during the metal deposition
  • halide preferably bromide or iodide
  • the solution anode consists of chromium metal or comprises chromium alloys.
  • the embodiments will also show in detail, it has surprisingly been found to be favorable when the galvansiche deposition takes place at temperatures below 40 ° C, preferably between 20 ° C and 37 ° C. With these process conditions, it was possible to achieve qualitatively very high-quality layers.
  • hardnesses of up to 1650 HV were achieved by this process, in particular when complexing agents are used, which thus significantly exceed the hardness range of chromium from conventional Cr (VI) -B (up to about 1150 HV).
  • the process according to the invention has the advantage of virtually unlimited layer thicknesses, similar to the Cr (VI) -based processes.
  • the hardness of the deposited chromium is above 1150 HV and / or that the layer thickness of the deposited chromium is above 15 ⁇ m.
  • a piece of copper sheet with 1 cm free surface was ground (grade 600), degreased and dissolved as a substrate in a simple 2 liter reaction vessel with a Pt-coated titanium expanded metal anode in 1 liter of a freshly prepared solution of 52 g (1 mole) of chromium powder in 2.6 mol HBr, at 47 ° C for 40 min. coated at a constant current density of 110 [A.dm " ], giving a uniform, glossy layer with a layer thickness of 8 ⁇ m and a hardness of 950 HV (Vickers hardness).
  • the chromium layer obtained had a thickness of 60 ⁇ with very good layer quality and a hardness of 1400 HV.
  • Example 2
  • the formation of free halogen is avoided either by complex formation with elimination of organic, non-water-soluble halogen complexes of higher density, or by the use of solution anodes, which is possible in the case of halide solutions.
  • the invention thus relates to a process for the galvanic production of chromium layers from Cr (VI) -free electrolytes based on acid halide solutions, in particular iodide and bromide.
  • halogens preferably bromides or iodides
  • chromium solution comprising a mixture of 2- and 3-valent high-level chromium ions on Cr (II)
  • the present invention is based, for example, on tests for the deposition of Cr from CrBr 3 electrolytes, as well as from electrolytes based on Cr (II) / Cr (III) mixtures. These gave on Cu and steel substrates very good results in terms of layer quality and high layer thicknesses> 150 ⁇ .
  • the solutions used preferably consist predominantly of halides, preferably bromides or iodides.
  • the complexing agents for example, quaternary ammonium compounds, can effect the attachment of free halide to form separable organic bromine complexes.

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)
  • Electrolytic Production Of Metals (AREA)

Abstract

L'invention concerne un procédé de dépôt galvanique de chrome dur sur un substrat à partir d'une solution électrolytique contenant Cr(II), Cr(III) ou des mélanges de ces derniers et des halogénures, la formation d'halogènes élémentaires étant évitée par l'utilisation d'une anode soluble ou l'halogène élémentaire produit pendant le dépôt étant complexé.
EP11779627.6A 2010-11-04 2011-10-31 Procédé de placage de chrome dur à partir d'un électrolyte sans cr(vi) Not-in-force EP2635724B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT18172010A AT510422B1 (de) 2010-11-04 2010-11-04 Verfahren zur abscheidung von hartchrom aus cr(vi)- freien elektrolyten
PCT/EP2011/069144 WO2012059473A1 (fr) 2010-11-04 2011-10-31 Procédé de dépôt de chrome dur à partir d'électrolytes exempts de cr(vi)

Publications (2)

Publication Number Publication Date
EP2635724A1 true EP2635724A1 (fr) 2013-09-11
EP2635724B1 EP2635724B1 (fr) 2014-12-17

Family

ID=44913267

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11779627.6A Not-in-force EP2635724B1 (fr) 2010-11-04 2011-10-31 Procédé de placage de chrome dur à partir d'un électrolyte sans cr(vi)

Country Status (4)

Country Link
EP (1) EP2635724B1 (fr)
AT (1) AT510422B1 (fr)
ES (1) ES2531319T3 (fr)
WO (1) WO2012059473A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015202910A1 (de) 2015-02-18 2016-08-18 Dr.-Ing. Max Schlötter GmbH & Co KG Zinn-Nickel-Schicht mit hoher Härte
CN109056005A (zh) * 2018-09-11 2018-12-21 沈阳飞机工业（集团）有限公司 一种应用电沉积技术制备铬硼合金的方法
DE102021002197A1 (de) 2021-04-27 2022-10-27 VDEh-Betriebsforschungsinstitut Gesellschaft mit beschränkter Haftung Vorrichtung und Verfahren zum Beschichten eines Bauteils oder Halbzeugs mit einer Chromschicht
CN114525557B (zh) * 2022-03-01 2024-01-02 九牧厨卫股份有限公司 一种杀菌环保复合镀层及其制备方法和杀菌环保产品

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE330317C (de) * 1920-12-11 Ludwig Schmidt Vorrichtung zum Einschalten der Feuerschutzmittel an Kinematographen
DE575450C (de) 1930-12-14 1933-04-28 Productores De Yoto De Chile A Verfahren zur elektrolytischen Abscheidung von Chrom
DE579065C (de) 1932-07-01 1933-06-21 Productores De Yodo De Chile A Verfahren zur elektrolytischen Abscheidung von Chrom
GB1144913A (en) 1966-10-31 1969-03-12 British Non Ferrous Metals Res Electrodeposition of chromium
GB1368747A (en) * 1971-11-23 1974-10-02 British Non Ferrous Metals Res Electrodeposition of chromium
GB1482747A (en) * 1973-10-10 1977-08-10 Bnf Metals Tech Centre Chromium plating baths
US4054494A (en) * 1973-12-13 1977-10-18 Albright & Wilson Ltd. Compositions for use in chromium plating
US4107004A (en) 1975-03-26 1978-08-15 International Lead Zinc Research Organization, Inc. Trivalent chromium electroplating baths and method
GB1488381A (en) 1975-09-01 1977-10-12 Bnf Metals Tech Centre Trivalent chromium plating bath
DE3274123D1 (en) * 1982-03-05 1986-12-11 M & T Chemicals Inc Control of anode gas evolution in trivalent chromium plating bath
CA1244376A (fr) * 1983-05-12 1988-11-08 Thaddeus W. Tomaszewski Electrolyte de chrome trivalent et mode d'utilisation
US4804446A (en) 1986-09-19 1989-02-14 The United States Of America As Represented By The Secretary Of Commerce Electrodeposition of chromium from a trivalent electrolyte
DE4011201C1 (en) * 1990-04-06 1991-08-22 Lpw-Chemie Gmbh, 4040 Neuss, De Coating workpiece with chromium for improved corrosion resistance - comprises using aq. electrolyte soln. contg. chromic acid sulphate ions, and fluoro:complexes to increase deposition
ES2669050T3 (es) 2006-03-31 2018-05-23 Atotech Deutschland Gmbh Depósito de cromo cristalino
US20080169199A1 (en) 2007-01-17 2008-07-17 Chang Gung University Trivalent chromium electroplating solution and an electroplating process with the solution
WO2010069458A1 (fr) * 2008-12-17 2010-06-24 Merck Patent Gmbh Complexes d'hexahalochromate (iii)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012059473A1 *

Also Published As

Publication number Publication date
AT510422A4 (de) 2012-04-15
ES2531319T3 (es) 2015-03-12
EP2635724B1 (fr) 2014-12-17
AT510422B1 (de) 2012-04-15
WO2012059473A1 (fr) 2012-05-10

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