CN1982507A - Process for deposition of crack-free, corrosion resistant and hard chromium and chromium alloy layers - Google Patents

Process for deposition of crack-free, corrosion resistant and hard chromium and chromium alloy layers Download PDF

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Publication number
CN1982507A
CN1982507A CNA2006100735893A CN200610073589A CN1982507A CN 1982507 A CN1982507 A CN 1982507A CN A2006100735893 A CNA2006100735893 A CN A2006100735893A CN 200610073589 A CN200610073589 A CN 200610073589A CN 1982507 A CN1982507 A CN 1982507A
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CN
China
Prior art keywords
electrolyte composition
chromium
salt
sulpho
layer
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Pending
Application number
CNA2006100735893A
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Chinese (zh)
Inventor
赫尔穆特·赫斯特姆克
马蒂亚斯·本特勒
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MacDermid Enthone Inc
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Enthone Inc
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Application filed by Enthone Inc filed Critical Enthone Inc
Publication of CN1982507A publication Critical patent/CN1982507A/en
Pending legal-status Critical Current

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    • 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
    • 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

Abstract

The invention relates to a method for forming chromium-containing electrolyte deposition functional chromium layer on basement and electrolyte composition. The electrolyte composition of the invention comprises sulfonic acetate. The said method can be implemented in current density of about 20-150A/dm<SUP>2</SUP> and with current efficiency of above 30%, wherein the hardness of the deposition layer is above 800HV 0.1 and the corrosion resistance is above 200 hours.

Description

Deposition of crack-free, corrosion-resistant and hard chromium layer and the method for chromium alloy layer
Present patent application relates to deposition of crack-free, corrosion-resistant and hard chromium layer or the method for chromium alloy layer, and the ionogen that is used to deposit them.
For many years, in the surface working field, the electrochemical plating coated surface is most important.At this, the reason on coated substrate surface can be in order to improve in the surface properties aspect hardness, wearability or the erosion resistance, perhaps also can be for attractive in appearance purely, so that the ornamental appearance of substrate is more attractive.
People know very early with containing chromium ionogen chromium plating surface from the technology of this area.Depend on used ionogen and processing parameter, sedimentary chromium layer very big at the nature difference that shows aspect hardness, erosion resistance and the brightness.
People know the electrolyte composition that utilizes acidic chromium containing (VI) at base metal (base metal) deposition chromium layer from the technology of this area, and this electrolyte composition also has for example catalyzer of sulphate-containing ion.Realize deposition by electroplating in the temperature range between 50 and 70 ℃.Current density used herein is usually 30 and 50A/dm 2Between.As can be known, gained current efficiency is between 12% and 16% from the technology of this area.
Disclosed as DE 43 02 564, add fluorion and alkansulfonic acid and make current efficiency increase to 26%.
Usually, the character of sedimentary chromium layer depend on temperature when sedimentation velocity, used current density and deposition take place especially.At this, interact between each parameter.Therefore, for example, known under 30 ℃ 2 to 8A/dm 2Current density range in from the ionogen of sulfur-bearing hydrochlorate the deposition bright chromium layer, wherein under 40 ℃ with 3 to 18A/dm 2Current density and under 50 ℃ with in addition be 6 to 28A/dm 2Current density, obtain bright layer with substantially the same (imvergleichbaren) ionogen.But, under about 30 ℃ temperature, be lower than 2A/dm 2Current density range in might deposit dark (mat) chromium layer.Depend on temperature, the current density that is used to deposit blindstory increases to 6A/dm 2As can be known, hot chromium plates method from the technology of this area, and for example the ANKOR  1141 of Enthone Inc. company only has 10% current efficiency under 70 ℃, and the hardness of gained settled layer only is 700HV 0.1.In the method, raising current efficiency and increase can cause forming the crack to the mechanical workout of these layers.
European patent EP 0 073 568 discloses the use that contains chromium (VI) coating bath (coating bath), and it makes the dark chromium layer of deposition to the current efficiency in the bright chromium layer process reach about 30% by add carboxylate salt in the coating bath of halide.At this, Potassium Iodate is as halide source.
Based on the technology of this area, the purpose of this invention is to provide corrosion-resistant, leakless of deposition and hard chromium layer and the method with high current efficiency of chromium alloy layer.In addition, the purpose of this invention is to provide and contain the chromium electrolyte composition accordingly, with deposition of crack-free in substrate, corrosion-resistant and hard chromium layer and chromium alloy layer, this contains the chromium electrolyte composition can be especially to be higher than the hard chrome coating that 30% current efficiency and high sedimentation velocity are come deposition of crack-free.
This purpose about this method is achieved by the method that deposits chromium layer or chromium alloy layer in substrate, substrate is contacted with electrolyte composition to deposit, and this electrolyte composition comprises at least a mineral acid (mineral acid) or inorganic acid salt, chromium cpd, oxyhalogen (halogen oxygen) compound, sulfonic acid and sulpho-acetic acid and/or its salt and/or produces the reactant of sulpho-acetic acid.
Between substrate to be coated and counter electrode (counter-electrode), apply electromotive force, to deposit functional chromium layer.At this, current density can be arranged on about 20A/dm according to the present invention 2With about 150A/dm 2Between.
Under the temperature between about 20 ℃ and about 90 ℃, implement the method according to this invention.
The current efficiency that the method according to this invention obtains is 30%.With 50A/dm 2Current density, be higher than 1.3 μ m/min according to the sedimentation velocity of the inventive method.
From ionogen according to the present invention and according to the sedimentary chromium layer of method of the present invention is hard, and hardness is greater than 800HV 0.1.
In addition, sedimentary chromium layer is extremely corrosion-resistant according to the present invention, and according to DIN 50021 SS, it is that the erosion resistance of 25 μ m was greater than 200 hours.
From ionogen according to the present invention, deposit dull gray (mat grey) chromium layer according to method of the present invention, for example polish or polish, this layer can be converted into bright chromium layer by suitable machining process.After the mechanical workout, sedimentary layer has high erosion resistance and hardness according to the present invention.
Present invention will be described in more detail by exemplary that following table is listed, and wherein the present invention is not limited to these exemplary.
For electrolyte composition, by the chromium electrolyte composition deposits functional chromium layer and chromium alloy layer is realized this purpose with containing in substrate, this electrolyte composition comprises at least a mineral acid or inorganic acid salt, chromium cpd, oxyhalogen (halogen oxygen) compound, sulfonic acid and sulpho-acetic acid and/or its salt and/or produces the reactant of sulpho-acetic acid.Reactant can be for example 3-hydroxy propane-1-sulfonic acid, hydroxyl methanesulfonic or aldehyde radical methanesulfonic.
The reactant that advantageously contains sulpho-acetic acid or its salt or formation sulpho-acetic acid according to electrolyte composition of the present invention, its concentration about 0.03 and about 0.3mol/l between, preferably 0.05 and 0.15mol/l between, more preferably about 0.06 and about 0.12mol/l between.
Especially, proved that basic metal oxyhalogen compound and/or alkaline-earth metal oxyhalogen compound are the oxyhalogen compounds that is fit in the electrolyte composition of the present invention.Said composition can contain basic metal (alkali) oxyhalogen compound or alkaline-earth metal (alkali earth) oxyhalogen compound, its concentration about 0.001 and about 0.1mol/l between, preferably about 0.005 and about 0.08mol/l between, more preferably about 0.007 and about 0.03mol/l between.
Found that Potassium Iodate is a particularly suitable oxyhalogen compound in the electrolyte composition of the present invention.
Add the character that oxyhalogen compound has improved current efficiency and improved layer.
As mineral acid, electrolyte composition advantageously comprises sulfuric acid.According to the present invention, the pH value of electrolyte composition is in the scope of pH＜1.
The electrolyte composition that is used to deposit functional chromium layer contains chromium cpd, and its concentration is between about 0.5mol/l and about 5mol/l, preferably between about 1mol/l and about 4mol/l, more preferably between about 2mol/l and about 3mol/l.
Especially, found that chromium trioxide is the chromium cpd that is fit to according in the electrolyte composition of the present invention.
Electrolyte composition advantageously contains at least a single sulfonic acid or disulfonic acid (disulphonicacid) is used as sulfonic acid.Methanesulfonic or methane-disulfonic acid are especially suitable.
Can contain sulfonic acid according to electrolyte composition of the present invention, its concentration is between about 0.01mol/l and about 0.1mol/l, preferably between about 0.015mol/l and about 0.06mol/l, more preferably between about 0.02mol/l and about 0.04mol/l.
Add the hardness increase that sulfonic acid causes the chromium layer that deposits, and do not damage and deposit relevant current efficiency or sedimentation velocity.
Exemplary
From base electrolyte, following table has been listed according to different ionogen of the present invention with by the layer of these electrolyte deposition and according to processing parameter shown in the present.
Base electrolyte comprises 280g/l chromium trioxide and 2.8g/l sulfuric acid.
Hardness of all sedimentary layers are greater than 800HV 0.1, erosion resistance according to DIN 5002165 greater than 200 hours.High-frequency induction (inductively) hardened CK45 steel is as base material.
Numbering The concentration ml/l of 3-hydroxy propane-1-sulfonic acid The concentration g/l of oxyhalogen compound The concentration g/l of other sulfonic acid Strength of current A Current density A/dm 2 Current efficiency % Sedimentation velocity μ m/min Expose (exposure) time min
1 8 0 0 10 50 37.3 1.396 30
2 10 2 0 10 50 37.07 1.388 30
3 10 3.4 0 14 70 36.76 n.d. 30
4 12 3.4 0 14 70 38.79 n.d 30
5 8 2 0 10 50 40.23 1.506 30
6 8 2 0 14 70 37.33 2.010 30
7 10 2 0 14 70 39.67 n.d. 30
8 10 2 2.25 10 50 33.88 n.d. 30
9 10 3.4 2.25 10 50 35.68 1.335 30
10 10 3.4 2.25 14 70 37.36 1.958 30
N.d.=does not determine

Claims (14)

1. in substrate, deposit the method for chromium layer or chromium alloy layer, substrate is contacted with electrolyte composition to deposit, and this electrolyte composition comprises at least a mineral acid or inorganic acid salt, chromium cpd, oxyhalogen compound, sulfonic acid and sulpho-acetic acid and/or its salt and/or produces the reactant of sulpho-acetic acid.
2. the method for claim 1 is characterized in that applying electromotive force with deposition chromium layer between substrate to be coated and counter electrode.
3. method as claimed in claim 2 is characterized in that current density is arranged on about 20A/dm 2With about 150A/dm 2Between.
4. as a described method among the claim 1-3, it is characterized in that under the temperature between about 20 ℃ and about 90 ℃, implementing this method.
5. what be used in substrate deposition chromium layer and chromium alloy layer contains chromium electrolyte composition, the reactant that it comprises a kind of mineral acid or inorganic acid salt, chromium cpd, oxyhalogen compound, sulfonic acid and sulpho-acetic acid and/or its salt at least and/or produces sulpho-acetic acid.
6. electrolyte composition as claimed in claim 5, it is characterized in that electrolyte composition advantageously contains sulpho-acetic acid, its salt or the reactant of formation sulpho-acetic acid, described sulpho-acetic acid, its salt or the reactant concn that forms sulpho-acetic acid about 0.03 and about 0.3mol/l between, preferably 0.05 and 0.15mol/l between, more preferably about 0.06 and about 0.12mol/l between.
7. as one in claim 5 and 6 or multinomial described electrolyte composition, it is characterized in that oxyhalogen compound is basic metal oxyhalogen compound and/or alkaline-earth metal oxyhalogen compound.
8. electrolyte composition as claimed in claim 7, it is characterized in that electrolyte composition comprises basic metal oxyhalogen compound and/or alkaline-earth metal oxyhalogen compound, described basic metal oxyhalogen compound and/or alkaline-earth metal oxyhalogen compound concentration are between about 0.001mol/l and about 0.1mol/l, preferably between about 0.005mol/l and about 0.08mol/l, more preferably between about 0.007mol/l and about 0.03mol/l.
9. as a described electrolyte composition in the claim 5 to 8, the pH value that it is characterized in that electrolyte composition is in the scope of pH＜1.
10. as a described electrolyte composition in the claim 5 to 9, it is characterized in that electrolyte composition contains chromium cpd, described chromium cpd concentration is between about 0.5mol/l and about 5mol/l, preferably between about 1mol/l and about 4mol/l, more preferably between about 2mol/l and about 3mol/l.
11. as a described electrolyte composition in the claim 5 to 10, wherein electrolyte composition comprises that single sulfonic acid or disulfonic acid or its salt are with as sulfonic acid.
12. as a described electrolyte composition in the claim 5 to 11, it is characterized in that electrolyte composition comprises another sulfonic acid or its salt, described another sulfonic acid or its salt concn are between about 0.01mol/l and about 0.1mol/l, preferably between about 0.015mol/l and about 0.06mol/l, more preferably between about 0.02mol/l and about 0.04mol/l.
13. according to one the sedimentary chromium layer of method in the claim 1 to 4, the hardness that it is characterized in that layer is greater than 800 HV 0.1.
14. one the sedimentary chromium layer of method according in the claim 1 to 4 is characterized in that, according to DIN 50021 SS, the erosion resistance of layer was greater than 200 hours.
CNA2006100735893A 2005-12-13 2006-04-13 Process for deposition of crack-free, corrosion resistant and hard chromium and chromium alloy layers Pending CN1982507A (en)

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DE102005059367.4A DE102005059367B4 (en) 2005-12-13 2005-12-13 Electrolytic composition and method of depositing crack-free, corrosion-resistant and hard chromium and chromium alloy layers
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EP (1) EP1798313B1 (en)
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DE102004019370B3 (en) 2004-04-21 2005-09-01 Federal-Mogul Burscheid Gmbh Production of optionally coated structurized hard chrome layer, used e.g. for decoration, protection or functional coating on printing roller or stamping, embossing or deep drawing tool uses aliphatic sulfonic acid in acid plating bath
DE102006022722B4 (en) 2006-05-12 2010-06-17 Hueck Engraving Gmbh & Co. Kg Method and device for surface structuring of a press plate or an endless belt
DE102008017270B3 (en) * 2008-04-04 2009-06-04 Federal-Mogul Burscheid Gmbh Structured chromium solid particle layer and method for its production and coated machine element
ES2766775T3 (en) * 2013-09-05 2020-06-15 Macdermid Enthone Inc Aqueous electrolyte composition that has reduced air emission
DE102014116717A1 (en) * 2014-11-14 2016-05-19 Maschinenfabrik Kaspar Walter Gmbh & Co Kg Electrolyte and process for the production of chrome layers
KR101646160B1 (en) 2015-11-13 2016-08-08 (주)에스에이치팩 Chrome plating solution having excellent corrosion resistance
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CN104476939B (en) * 2014-12-25 2017-07-14 东莞运城制版有限公司 The chrome-plating method and keeping method of a kind of roller

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DE102005059367A1 (en) 2007-06-14
EP1798313A2 (en) 2007-06-20
US20070131558A1 (en) 2007-06-14
KR20070062898A (en) 2007-06-18
EP1798313B1 (en) 2017-12-13
EP1798313A3 (en) 2008-06-18
JP2007162123A (en) 2007-06-28
DE102005059367B4 (en) 2014-04-03

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