EP1798313B1 - Verfahren zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom- und Chromlegierungsschichten - Google Patents

Verfahren zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom- und Chromlegierungsschichten Download PDF

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Publication number
EP1798313B1
EP1798313B1 EP06004787.5A EP06004787A EP1798313B1 EP 1798313 B1 EP1798313 B1 EP 1798313B1 EP 06004787 A EP06004787 A EP 06004787A EP 1798313 B1 EP1798313 B1 EP 1798313B1
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EP
European Patent Office
Prior art keywords
chromium
mol
acid
depositing
layers
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.)
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Application number
EP06004787.5A
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German (de)
English (en)
French (fr)
Other versions
EP1798313A3 (de
EP1798313A2 (de
Inventor
Helmut Horsthemke
Matthias Bentele
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
MacDermid Enthone Inc
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Publication date
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Publication of EP1798313A2 publication Critical patent/EP1798313A2/de
Publication of EP1798313A3 publication Critical patent/EP1798313A3/de
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Publication of EP1798313B1 publication Critical patent/EP1798313B1/de
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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/04Electroplating: Baths therefor from solutions of chromium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/04Electroplating: Baths therefor from solutions of chromium
    • C25D3/10Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used

Definitions

  • the present patent application relates to a method for depositing a crack-free, corrosion-resistant and hard chromium or chromium alloy layer and to an electrolyte for depositing such.
  • the coating of surfaces by means of electroplating processes has for decades occupied a leading position in the field of surface refinement.
  • the reasons for coating substrate surfaces may be an improvement in surface property in terms of hardness, abrasiveness, or corrosion resistance, or may be purely aesthetic, to make the decorative appearance of substrates more pleasing.
  • the properties of the deposited chromium layers are dependent in particular on the deposition rate, the current density used and the temperature at which deposition takes place.
  • the individual parameters influence each other. So it is z. B. known at 30 ° C in a current density range between 2 and 8 A / dm 2 shiny chrome layers of sulfate-containing electrolyte, wherein at 40 ° C in comparable electrolytes at current densities of 3 to 18 A / dm 2 , and even at 50 ° C. between 6 and 28 A / dm 2 shiny layers are obtained.
  • the deposition of matt chromium layers at temperatures around 30 ° C in a range below 2 A / dm 2 is possible.
  • Hot-chromium processes known from the prior art such as, for example, ANKOR® 1141 from Enthone Inc., allow at 70 ° C. only a current efficiency of 10% with a hardness of the deposited layer of 700 HV 0.1. An increase in the current efficiency in this process leads to cracking, as well as the mechanical post-processing of these layers.
  • the object of the present invention to provide a suitable method for depositing corrosion-resistant, crack-free and hard chromium and chromium alloy layers with high current efficiency. Moreover, it is the object of the present invention to provide a corresponding chromium-containing electrolyte composition for depositing crack-free, corrosion-resistant and hard chromium and chromium alloy layers on substrates, which enables the deposition of crack-free hard chrome layers at high current yields, in particular greater than 30% and high deposition rates.
  • the object is achieved by the features of claim 1 (electrolyte composition) and the features of claim 5 (method for depositing a chromium or chromium alloy layer.
  • an electrical voltage is applied between the substrate to be coated and a counterelectrode.
  • a current density between approximately 20 A / dm 2 and approximately 150 A / dm 2 can be set.
  • the process of the invention is operated at a temperature between about 20 ° C and about 90 ° C.
  • the current efficiency achieved by the method according to the invention is 30%.
  • the deposition rate of the process according to the invention is greater than 1.3 ⁇ m / min at a current density of 50 A / dm 2 .
  • the chromium layers deposited from the electrolyte according to the invention by means of the method according to the invention are hard and have a hardness greater than 800 HV 0.1.
  • the chromium layers deposited according to the invention are extremely corrosion-resistant and have a corrosion resistance in accordance with DIN 50021 SS at 25 ⁇ m of more than 200 hours.
  • matt, gray chromium layers are deposited from the electrolyte according to the invention, which can be converted into lustrous chrome layers by means of suitable mechanical processing methods such as, for example, grinding or lapping. Even after such a mechanical corrosion-resistant, crack-free and hard chrome and chromium alloy layers with high current efficiency to provide. Moreover, it is the object of the present invention to provide a corresponding chromium-containing electrolyte composition for depositing crack-free, corrosion-resistant and hard chromium and chromium alloy layers on substrates, which enables the deposition of crack-free hard chrome layers at high current yields, in particular greater than 30% and high deposition rates.
  • the object is achieved as regards the method by a method for the deposition of chromium or chromium alloy layers on substrates, in which the deposition, the substrate with the electrolyte composition is contacted, comprising at least one mineral acid or a mineral acid salt, a chromium compound, a halogen-oxygen compound, a sulfonic acid, as well as Sulfoacetic acid and / or a salt thereof and / or a reactant from which sulfoacetic acid forms.
  • an electrical voltage is applied between the substrate to be coated and a counterelectrode.
  • a current density between approximately 20 A / dm 2 and approximately 150 A / dm 2 can be set.
  • the process of the invention is operated at a temperature between about 20 ° C and about 90 ° C.
  • the current efficiency achieved by the method according to the invention is 3 30%.
  • the deposition rate of the process according to the invention is greater than 1.3 ⁇ m / min at a current density of 50 A / dm 2 .
  • the chromium layers deposited from the electrolyte according to the invention by means of the method according to the invention are hard and have a hardness greater than 800 HV 0.1.
  • the chromium layers deposited according to the invention are extremely corrosion resistant and have a corrosion resistance according to DIN 50021 SS at 25 ⁇ m of more than 200 hours.
  • matt, gray chromium layers are deposited from the electrolyte according to the invention, which can be converted into lustrous chrome layers by means of suitable mechanical processing methods such as, for example, grinding or lapping. Even after such mechanical processing, the layers deposited according to the invention have a high corrosion resistance and hardness.
  • a chromium-containing electrolyte composition for depositing a functional chromium or chromium alloy layer on substrates comprising at least one mineral acid or a mineral acid salt, a chromium compound, a halo oxygen compound, a sulfonic acid and sulfoacetic acid and / or a salt thereof and / or a Reactants, from which sulfoacetic acid forms having.
  • Reactants may be, for example, 3-hydroxypropane-1-sulfonic acid, hydroxymethanesulfonic acid or aldehydomethanesulfonic acid.
  • the electrolyte composition according to the invention contains the sulfoacetic acid or a salt thereof or a reactant from which it is formed in a concentration of between about 0.03 and about 0.3 mol / l, preferably between 0.05 and 0.15 mol / l , and more preferably between about 0.06 and about 0.12 mol / l.
  • alkali metal and / or alkaline earth halide oxygen compounds have proved to be suitable halogenated oxygen compounds in the electrolyte composition according to the invention.
  • the composition may contain the alkali or alkaline earth halide oxygen compound in a concentration between about 0.001 and about 0.1 mol / l, preferably between about 0.005 and about 0.08 mol / l, and more preferably between about 0.007 and 0.03 mol / l.
  • a particularly suitable halogenated oxygen compound has proved to be potassium iodate in the electrolyte composition according to the invention.
  • halogenated oxygen compounds increases the current efficiency and leads to improved layer properties.
  • the electrolyte composition advantageously comprises sulfuric acid as the mineral acid.
  • the pH of the electrolyte composition according to the invention is in a range of pH ⁇ 1.
  • the electrolyte composition for depositing functional chromium layers contains the chromium compound in a concentration between about 0.5 mol / l and about 5 mol / l, preferably between about 1 mol / l and about 4 mol / l, more preferably between about 2 mol / l and about 3 mol / l.
  • chromium trioxide has proven to be a suitable chromium compound in the electrolyte compositions of the invention.
  • the electrolyte composition contains at least one mono- or disulfonic acid as sulfonic acids.
  • Particularly suitable is methanesulfonic acid or methanedisulfonic acid.
  • the sulfonic acid may be present in the electrolyte composition of the invention at a concentration between about 0.01 mol / l and about 0.1 mol / l, preferably between about 0.015 mol / l and about 0.06 mol / l, more preferably between about 0.02 be contained mol / l and about 0.04 mol / l.
  • the base electrolyte has 280 g / l of chromium trioxide and 2.8 g of sulfuric acid.
  • All deposited layers have a hardness greater than 800 HV 0.1 and a corrosion resistance according to DIN 5002165 of more than 200 hours.
  • the base material is inductively hardened CK45 steel. No. Concentration of 3-hydroxypropane-1-sulfonic acid in ml / l Concentration of halogen-oxygen compound in g / l Concentration of additional sulfonic acid in g / l Current in A Current density in A / dm 2 Current efficiency in% Separation rate in ⁇ m / min. Exposure time in min.

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)
  • Physical Vapour Deposition (AREA)
EP06004787.5A 2005-12-13 2006-03-09 Verfahren zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom- und Chromlegierungsschichten Active EP1798313B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102005059367.4A DE102005059367B4 (de) 2005-12-13 2005-12-13 Elektrolytzusammensetzung und Verfahren zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom- und Chromlegierungsschichten

Publications (3)

Publication Number Publication Date
EP1798313A2 EP1798313A2 (de) 2007-06-20
EP1798313A3 EP1798313A3 (de) 2008-06-18
EP1798313B1 true EP1798313B1 (de) 2017-12-13

Family

ID=37847008

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06004787.5A Active EP1798313B1 (de) 2005-12-13 2006-03-09 Verfahren zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom- und Chromlegierungsschichten

Country Status (6)

Country Link
US (1) US20070131558A1 (ja)
EP (1) EP1798313B1 (ja)
JP (1) JP2007162123A (ja)
KR (1) KR20070062898A (ja)
CN (1) CN1982507A (ja)
DE (1) DE102005059367B4 (ja)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10255853A1 (de) 2002-11-29 2004-06-17 Federal-Mogul Burscheid Gmbh Herstellung strukturierter Hartchromschichten
DE102004019370B3 (de) 2004-04-21 2005-09-01 Federal-Mogul Burscheid Gmbh Herstellung einer strukturierten Hartchromschicht und Herstellung einer Beschichtung
DE102006022722B4 (de) * 2006-05-12 2010-06-17 Hueck Engraving Gmbh & Co. Kg Verfahren und Vorrichtung zur Oberflächenstrukturierung eines Pressbleches oder eines Endlosbandes
DE102008017270B3 (de) 2008-04-04 2009-06-04 Federal-Mogul Burscheid Gmbh Strukturierte Chrom-Feststoffpartikel-Schicht und Verfahren zu deren Herstellung sowie beschichtetes Maschinenelement
ES2766775T3 (es) * 2013-09-05 2020-06-15 Macdermid Enthone Inc Composición acuosa de electrolito que tiene una emisión aérea reducida
DE102014116717A1 (de) * 2014-11-14 2016-05-19 Maschinenfabrik Kaspar Walter Gmbh & Co Kg Elektrolyt und Verfahren zur Herstellung von Chromschichten
CN104476939B (zh) * 2014-12-25 2017-07-14 东莞运城制版有限公司 一种版辊的镀铬方法及保管方法
KR101646160B1 (ko) 2015-11-13 2016-08-08 (주)에스에이치팩 내식성이 우수한 크롬도금액
DE102018133532A1 (de) * 2018-12-21 2020-06-25 Maschinenfabrik Kaspar Walter Gmbh & Co Kg Elektrolyt und Verfahren zur Herstellung von Chromschichten

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US3758390A (en) * 1971-06-18 1973-09-11 M & T Chemicals Inc Novel cromium plating compositions
US4472249A (en) * 1981-08-24 1984-09-18 M&T Chemicals Inc. Bright chromium plating baths and process
US4588481A (en) * 1985-03-26 1986-05-13 M&T Chemicals Inc. Chromium plating bath for producing non-iridescent, adherent, bright chromium deposits at high efficiencies and substantially free of cathodic low current density etching
US4828656A (en) * 1987-02-09 1989-05-09 M&T Chemicals Inc. High performance electrodeposited chromium layers
US4810336A (en) * 1988-06-21 1989-03-07 M&T Chemicals Inc. Electroplating bath and process for depositing functional, at high efficiencies, chromium which is bright and smooth
JPH0379786A (ja) * 1989-09-01 1991-04-04 M & T Chem Inc クロムメツキ浴
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
DE4302564C2 (de) * 1993-01-29 2003-05-15 Hans Hoellmueller Maschb Gmbh Vorrichtung zum Ätzen, Beizen oder Entwickeln plattenförmiger Gegenstände, insbesondere von elektrischen Leiterplatten
US6251253B1 (en) * 1999-03-19 2001-06-26 Technic, Inc. Metal alloy sulfate electroplating baths

Non-Patent Citations (1)

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None *

Also Published As

Publication number Publication date
KR20070062898A (ko) 2007-06-18
JP2007162123A (ja) 2007-06-28
DE102005059367B4 (de) 2014-04-03
EP1798313A3 (de) 2008-06-18
DE102005059367A1 (de) 2007-06-14
EP1798313A2 (de) 2007-06-20
CN1982507A (zh) 2007-06-20
US20070131558A1 (en) 2007-06-14

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