EP1798313B1 - Process for depositing crack-free, corrosion resistant and hard chromium and chromium alloy layers - Google Patents
Process for depositing crack-free, corrosion resistant and hard chromium and chromium alloy layers Download PDFInfo
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- 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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- chromium
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- acid
- depositing
- layers
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052804 chromium Inorganic materials 0.000 title claims description 34
- 239000011651 chromium Substances 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 24
- 229910000599 Cr alloy Inorganic materials 0.000 title claims description 11
- 239000000788 chromium alloy Substances 0.000 title claims description 11
- 238000000151 deposition Methods 0.000 title description 28
- 238000005260 corrosion Methods 0.000 title description 14
- 230000007797 corrosion Effects 0.000 title description 14
- 239000000203 mixture Substances 0.000 claims description 29
- 230000008021 deposition Effects 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001845 chromium compounds Chemical class 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 29
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- -1 fluoride ions Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 150000002927 oxygen compounds Chemical class 0.000 description 3
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 2
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical group CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
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
-
- 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 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.
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- 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)
Description
Die vorliegende Patentanmeldung betrifft ein Verfahren zur Abscheidung einer rissfreien, korrosionsbeständigen und harten Chrom- oder Chromlegierungsschicht sowie einen Elektrolyten zur Abscheidung einer solchen.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.
Die Beschichtung von Oberflächen mittels galvanotechnischer Verfahren nimmt seit Jahrzehnten eine führende Position im Bereich der Oberflächenveredelung ein. Hierbei können die Gründe zur Beschichtung von Substratoberflächen eine Verbesserung der Oberflächeneigenschaft hinsichtlich Härte, Abrasivität oder Korrosionsbeständigkeit sein, oder auch rein ästhetisch begründet sein, um das dekorative Aussehen von Substraten gefälliger zu gestalten.The coating of surfaces by means of electroplating processes has for decades occupied a leading position in the field of surface refinement. Here, 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.
Gleichfalls ist es bereits lange aus dem Stand der Technik bekannt, Oberflächen mittels chromhaltiger Elektrolyten zu verchromen. Die abgeschiedenen Chromschichten weisen in Abhängigkeit des eingesetzten Elektrolyten und der Verfahrensparameter ganz unterschiedliche Eigenschaften hinsichtlich Härte, Korrosionsbeständigkeit und Glanz auf.Likewise, it has long been known from the prior art to chrome surfaces by means of chromium-containing electrolytes. Depending on the electrolyte used and the process parameters, the deposited chromium layers have very different properties with respect to hardness, corrosion resistance and gloss.
Aus dem Stand der Technik ist es bekannt, saure Chrom (V1)-haltige Elektrolytzusammensetzungen, welche darüber hinaus beispielsweise einen Sulfationenhaltigen Katalysator aufweisen, zur Abscheidung von Chromschichten auf einem Basismetall einzusetzen. Die Abscheidung erfolgt galvanisch bei Temperaturen in einem Bereich zwischen 50 und 70°C. Die hierbei eingesetzte Stromdichte liegt üblicherweise in einem Bereich zwischen 30 und 50 A/dm2. Die aus dem Stand der Technik bekannte, resultierende Stromausbeute liegt im Bereich von 12 bis 16%.It is known from the prior art to use acidic chromium (V1) -containing electrolyte compositions, which, for example, also contain a sulfate ion-containing catalyst for depositing chromium layers on a base metal. The deposition is carried out galvanically at temperatures in a range between 50 and 70 ° C. The current density used here is usually in a range between 30 and 50 A / dm 2 . The resulting current efficiency known in the art is in the range of 12 to 16%.
Der Zusatz von Fluoridionen und Alkansulfonsäuren erlaubt, wie in
Im allgemeinen sind die Eigenschaften der abgeschiedenen Chromschichten insbesondere von der Abscheidegeschwindigkeit, der eingesetzten Stromdichte und der Temperatur, bei welcher abgeschieden wird, abhängig. Hierbei beeinflussen sich die einzelnen Parameter gegenseitig. So ist es z. B. bekannt bei 30°C in einem Stromdichtebereich zwischen 2 und 8 A/dm2 glänzende Chromschichten aus sulfathaltigen Elektrolyten abzuscheiden, wobei bei 40°C in vergleichbaren Elektrolyten bei Stromdichten von 3 bis 18 A/dm2, und bei 50°C sogar zwischen 6 und 28 A/dm2 glänzende Schichten erhalten werden. Dem hingegen ist die Abscheidung matter Chromschichten bei Temperaturen um 30°C in einem Bereich unter 2 A/dm2 möglich. In Abhängigkeit der Temperatur steigt die Stromdichte zur Abscheidung matter Schichten bis auf 6 A/dm2 an. Aus dem Stand der Technik bekannte Heißchromverfahren wie beispielsweise ANKOR® 1141 der Firma Enthone Inc. ermöglichen bei 70° C lediglich eine Stromausbeute von 10% bei einer erhaltenen Härte der abgeschiedenen Schicht von 700 HV 0,1. Eine Erhöhung der Stromausbeute in diesem Verfahren führt zur Rißbildung, ebenso wie die mechanische Nachbearbeitung dieser Schichten.In general, 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. Here, 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. In contrast, the deposition of matt chromium layers at temperatures around 30 ° C in a range below 2 A / dm 2 is possible. Depending on the temperature, the current density for depositing matt layers increases up to 6 A / dm 2 . 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.
Aus dem europäischen Patent
Vor dem Hintergrund des Standes der Technik ist es die Aufgabe der vorliegenden Erfindung, ein geeignetes Verfahren zur Abscheidung korrosionsfester, rissfreier und harter Chrom- und Chromlegierungsschichten mit hoher Stromausbeute zur Verfügung zu stellen. Darüber hinaus ist es die Aufgabe der vorliegenden Erfindung, eine entsprechende chromhaltige Elektrolytzusammensetzung zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom und Chromlegierungsschichten auf Substraten zur Verfügung zu stellen, welche die Abscheidung rissfreier Hartchromschichten bei hohen Stromausbeuten, insbesondere größer 30% und hohen Abscheidegeschwindigkeiten ermöglicht.Against the background of the prior art, it is 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.
Gelöst wird die Aufgabe durch die Merkmale des Anspruchs 1 (Elektrolytzusammensetzung) und die Merkmale des Anspruchs 5 (Verfahren zur Abscheidung einer Chrom-oder Chromlegierungsschicht.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.
Zur Abscheidung der funktionellen Chromschicht wird eine elektrische Spannung zwischen zu beschichtendem Substrat und einer Gegenelektrode angelegt. Hierbei kann erfindungsgemäß eine Stromdichte zwischen ungefähr 20 A/dm2 und ungefähr 150 A/dm2 eingestellt werden.For depositing the functional chromium layer, an electrical voltage is applied between the substrate to be coated and a counterelectrode. In this case, according to the invention, a current density between approximately 20 A / dm 2 and approximately 150 A / dm 2 can be set.
Das erfindungsgemäße Verfahren wird bei einer Temperatur zwischen ungefähr 20°C und ungefähr 90°C betrieben.The process of the invention is operated at a temperature between about 20 ° C and about 90 ° C.
Die mit dem erfindungsgemäßen Verfahren erzielte Stromausbeute ist 30%. Die Abscheidegeschwindigkeit des erfindungsgemäßen Verfahrens ist bei einer Stromdichte von 50 A/dm2 größer als 1,3 µm/min.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 μm / min at a current density of 50 A / dm 2 .
Die aus dem erfindungsgemäßen Elektrolyten mittels des erfindungsgemäßen Verfahrens abgeschiedenen Chromschichten sind hart und weisen eine Härte größer 800 HV 0,1 auf.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.
Darüber hinaus sind die erfindungsgemäß abgeschiedenen Chromschichten äußerst korrosionsbeständig und weisen eine Korrosionsbeständigkeit gemäß DIN 50021 SS bei 25 µm von mehr als 200 Stunden auf.In addition, 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 μm of more than 200 hours.
Aus dem erfindungsgemäßen Elektrolyten werden mittels des erfindungsgemäßen Verfahrens matte, graue Chromschichten abgeschieden, welche mittels geeigneter mechanischer Bearbeitungsverfahren wie beispielsweise Schleifen oder Läppen in glänzende Chromschichten überführt werden können. Auch nach einer solchen mechanischen korrosionsfester, rissfreier und harter Chrom- und Chromlegierungsschichten mit hoher Stromausbeute zur Verfügung zu stellen. Darüber hinaus ist es die Aufgabe der vorliegenden Erfindung, eine entsprechende chromhaltige Elektrolytzusammensetzung zur Abscheidung rissfreier, korrosionsbeständiger und harter Chrom- und Chromlegierungsschichten auf Substraten zur Verfügung zu stellen, welche die Abscheidung rissfreier Hartchromschichten bei hohen Stromausbeuten, insbesondere größer 30% und hohen Abscheidegeschwindigkeiten ermöglicht.By means of the method according to the invention, 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.
Gelöst wird die Aufgabe hinsichtlich des Verfahrens durch ein Verfahren zur Abscheidung von Chrom- oder Chromlegierungsschichten auf Substraten, bei welchem zur Abscheidung das Substrat mit einer Elektrolytzusammensetzung kontaktiert wird, welche wenigstens eine Mineralsäure oder ein Mineralsäuresalz, eine Chromverbindung, eine Halogensauerstoffverbindung, eine Sulfonsäure, sowie Sulfoessigsäure und/oder ein Salz dieser und/oder einen Reaktanten, aus dem sich Sulfoessigsäure bildet, aufweist.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.
Zur Abscheidung der funktionellen Chromschicht wird eine elektrische Spannung zwischen zu beschichtendem Substrat und einer Gegenelektrode angelegt. Hierbei kann erfindungsgemäß eine Stromdichte zwischen ungefähr 20 A/dm2 und ungefähr 150 A/dm2 eingestellt werden.For depositing the functional chromium layer, an electrical voltage is applied between the substrate to be coated and a counterelectrode. In this case, according to the invention, a current density between approximately 20 A / dm 2 and approximately 150 A / dm 2 can be set.
Das erfindungsgemäße Verfahren wird bei einer Temperatur zwischen ungefähr 20°C und ungefähr 90°C betrieben.The process of the invention is operated at a temperature between about 20 ° C and about 90 ° C.
Die mit dem erfindungsgemäßen Verfahren erzielte Stromausbeute ist 3 30%. Die Abscheidegeschwindigkeit des erfindungsgemäßen Verfahrens ist bei einer Stromdichte von 50 A/dm2 größer als 1,3 µm/min.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 μ m / min at a current density of 50 A / dm 2 .
Die aus dem erfindungsgemäßen Elektrolyten mittels des erfindungsgemäßen Verfahrens abgeschiedenen Chromschichten sind hart und weisen eine Härte größer 800 HV 0,1 auf.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.
Darüber hinaus sind die erfindungsgemäß abgeschiedenen Chromschichten äußerst korrosionsbeständig und weisen eine Korrosionsbeständigkeit gemäß DIN 50021 SS bei 25 µm von mehr als 200 Stunden auf.In addition, the chromium layers deposited according to the invention are extremely corrosion resistant and have a corrosion resistance according to DIN 50021 SS at 25 μ m of more than 200 hours.
Aus dem erfindungsgemäßen Elektrolyten werden mittels des erfindungsgemäßen Verfahrens matte, graue Chromschichten abgeschieden, welche mittels geeigneter mechanischer Bearbeitungsverfahren wie beispielsweise Schleifen oder Läppen in glänzende Chromschichten überführt werden können. Auch nach einer solchen mechanischen Bearbeitung weisen die erfindungsgemäß abgeschiedenen Schichten eine hohe Korrosionsbeständigkeit und Härte auf.By means of the method according to the invention, 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.
Die Erfindung wird anhand der in der nachfolgenden Tabelle aufgeführten Ausführungsbeispiele näher erläutert, wobei sich die Erfindung jedoch in keinster Weise auf die Ausführungsbeispiele beschränken läßt.The invention will be explained in more detail with reference to the embodiments listed in the following table, but the invention can not be limited in any way to the embodiments.
Hinsichtlich der Elektrolytzusammensetzung wird die Aufgabe durch eine chromhaltige Elektrolytzusammensetzung zur Abscheidung einer funktionellen Chrom- oder Chromlegierungsschicht auf Substraten gelöst, welche wenigstens eine Mineralsäure oder ein Mineralsäuresalz, eine Chromverbindung, eine Halogensauerstoffverbindung, eine Sulfonsäure sowie Sulfoessigsäure und/oder ein Salz dieser und/oder einen Reaktanten, aus dem sich Sulfoessigsäure bildet, aufweist. Reaktanten können beispielsweise 3-Hydroxypropan-1-sulfonsäure, Hydroxymethansulfonsäure oder Aldehydomethansulfonsäure sein.With regard to the electrolyte composition, the object is achieved by 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.
Vorteilhafterweise enthält die erfindungsgemäße Elektrolytzusammensetzung die Sulfoessigsäure oder ein Salz dieser oder einen Reaktanten, aus dem diese sich bildet, in einer Konzentration zwischen ungefähr 0,03 und ungefähr 0,3 mol/l, bevorzugt zwischen 0,05 und 0,15 mol/l, und noch bevorzugter zwischen ungefähr 0,06 und ungefähr 0,12 mol/l.Advantageously, 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.
Als geeignete Halogensauerstoffverbindungen haben sich in der erfindungsgemäßen Elektrolytzusammensetzung insbesondere Alkali- und/oder Erdalkalihalogensauerstoffverbindungen erwiesen. Die Zusammensetzung kann die Alkali- oder Erdalkalihalogensauerstoffverbindung in einer Konzentration zwischen ungefähr 0,001 und ungefähr 0,1 mol/l, bevorzugt zwischen ungefähr 0,005 und ungefähr 0,08 mol/l, und noch bevorzugter zwischen ungefähr 0,007 und 0,03 mol/l enthalten.In particular, 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.
Als besonders geeignete Halogensauerstoffverbindung hat sich in der erfindungsgemäßen Elektrolytzusammensetzung Kaliumiodat erwiesen.A particularly suitable halogenated oxygen compound has proved to be potassium iodate in the electrolyte composition according to the invention.
Der Zusatz von Halogensauerstoffverbindungen steigert die Stromausbeute und führt zu verbesserten Schichteigenschaften.The addition of halogenated oxygen compounds increases the current efficiency and leads to improved layer properties.
Die Elektrolytzusammensetzung weist als Mineralsäure vorteilhafterweise Schwefelsäure auf. Der pH-Wert der Elektrolytzusammensetzung liegt erfindungsgemäß in einem Bereich von pH < 1.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.
Die Elektrolytzusammensetzung zur Abscheidung funktioneller Chromschichten enthält die Chromverbindung in einer Konzentration zwischen ungefähr 0,5 mol/l und ungefähr 5 mol/l, bevorzugt zwischen ungefähr 1 mol/l und ungefähr 4 mol/l, noch bevorzugter zwischen ungefähr 2 mol/l und ungefähr 3 mol/l.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.
Insbesondere Chromtrioxid hat sich als geeignete Chromverbindung in den erfindungsgemäßen Elektrolytzusammensetzungen erwiesen.In particular, chromium trioxide has proven to be a suitable chromium compound in the electrolyte compositions of the invention.
Vorteilhaft enthält die Elektrolytzusammensetzung als Sulfonsäuren wenigstens eine Mono- oder Disulfonsäure. Insbesondere geeignet ist Methansulfonsäure oder Methandisulfonsäure.Advantageously, the electrolyte composition contains at least one mono- or disulfonic acid as sulfonic acids. Particularly suitable is methanesulfonic acid or methanedisulfonic acid.
Die Sulfonsäure kann in der erfindungsgemäßen Elektrolytzusammensetzung in einer Konzentration zwischen ungefähr 0,01 mol/l und ungefähr 0,1 mol/l, bevorzugt zwischen ungefähr 0,015 mol/l und ungefähr 0,06 mol/l, noch bevorzugter zwischen ungefähr 0,02 mol/l und ungefähr 0,04 mol/l enthalten sein.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.
Der Zusatz einer Sulfonsäure führt zu Erhöhung der Härte der abgeschiedenen Chromschicht, ohne die Abscheidung hinsichtlich Stromausbeute oder Abscheidegeschwindigkeit zu beeinträchtigen.The addition of a sulfonic acid leads to an increase in the hardness of the deposited chromium layer, without impairing the deposition in terms of current efficiency or deposition rate.
In der nachfolgenden Tabelle sind ausgehend von einem Grundelektrolyten unterschiedliche erfindungsgemäße Elektrolyten und die aus diesen Elektrolyten unter den angegebenen erfindungsgemäßen Verfahrensparameters abgeschiedenen Schichten angegeben.In the following table, starting from a base electrolyte, different electrolytes according to the invention and the layers deposited from these electrolytes under the indicated process parameters according to the invention are indicated.
Der Grundelektrolyt weist 280 g/l Chromtrioxid und 2,8 gl Schwefelsäure auf.The base electrolyte has 280 g / l of chromium trioxide and 2.8 g of sulfuric acid.
Alle abgeschiedenen Schichten weisen eine Härte größer 800 HV 0,1 und eine Korrosionsbeständigkeit gemäß DIN 5002165 von mehr als 200 Stunden auf. Als Basismaterial dient induktiv gehärteter CK45-Stahl.
Claims (6)
- An electrolytic plating composition containing chrome for coating of a substrate with a chromium or a chromium alloy layer, the composition at least comprises: sulfuric acid, a chromium compound; potassium iodate, sulfoacetic acid and/or a salt thereof and/or a reactant able to generate sulfoacetic acid, and an additional sulfonic acid, wherein the sulfoacetic acid, the salt thereof or the reactant, is present in the electrolytic composition in a concentration between 0.03 mol/l and 0,15 mol/l and the additional sulfonic acid or the salt thereof is present in a concentration between 0.01 mol/l and 0.1 mol/l, and wherein the alkaline or alkaline earth-halogen-oxygen compound is present in the electrolytic composition in a concentration between 0.001 mol/l and 0.1 mol/l.
- Electrolytic composition according to claim 1, characterized in that the electrolytic composition has a pH of < 1.
- Electrolytic composition according to any of claims 1 or 2, characterized in that the composition comprises the chromium compound in a concentration between 0.5 mol/l and 5 mol/l, preferably between 1 mol/l and 4 mol/l, further preferred between 2 mol/l and 3 mol/l.
- Electrolytic composition according to any of claims 1 to 3, wherein the electrolytic composition comprises as a sulfonic acid a mono- or disulfonic acid or a salt thereof.
- A process for electrolytically coating a chromium or a chromium alloy layer on a substrate, wherein for deposition the substrate is contacted with an electrolytic composition according to any of the preceding claims, wherein for the deposition of the chromium coating a voltage is applied between the substrate to be coated and a counter electrode providing a current density between 20 A/dm2 and 150 A/dm2.
- Process according to claim 5, characterized in that the process is performed at a temperature between 20°C and 90°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (3)
| Publication Number | Publication Date |
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| EP1798313A2 EP1798313A2 (en) | 2007-06-20 |
| EP1798313A3 EP1798313A3 (en) | 2008-06-18 |
| EP1798313B1 true EP1798313B1 (en) | 2017-12-13 |
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| EP06004787.5A Active EP1798313B1 (en) | 2005-12-13 | 2006-03-09 | Process for depositing crack-free, corrosion resistant and hard chromium and chromium alloy layers |
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| Country | Link |
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| US (1) | US20070131558A1 (en) |
| EP (1) | EP1798313B1 (en) |
| JP (1) | JP2007162123A (en) |
| KR (1) | KR20070062898A (en) |
| CN (1) | CN1982507A (en) |
| DE (1) | DE102005059367B4 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10255853A1 (en) | 2002-11-29 | 2004-06-17 | Federal-Mogul Burscheid Gmbh | Manufacture of structured hard chrome layers |
| 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 |
| 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 |
| KR101646160B1 (en) | 2015-11-13 | 2016-08-08 | (주)에스에이치팩 | Chrome plating solution having excellent corrosion resistance |
| DE102018133532A1 (en) * | 2018-12-21 | 2020-06-25 | Maschinenfabrik Kaspar Walter Gmbh & Co Kg | Electrolyte and process for the production of chrome layers |
Family Cites Families (9)
| 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 (en) * | 1989-09-01 | 1991-04-04 | M & T Chem Inc | Chromium-plating bath |
| 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 (en) * | 1993-01-29 | 2003-05-15 | Hans Hoellmueller Maschb Gmbh | Device for etching, pickling or developing plate-shaped objects, in particular electrical printed circuit boards |
| US6251253B1 (en) * | 1999-03-19 | 2001-06-26 | Technic, Inc. | Metal alloy sulfate electroplating baths |
-
2005
- 2005-12-13 DE DE102005059367.4A patent/DE102005059367B4/en active Active
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2006
- 2006-03-09 EP EP06004787.5A patent/EP1798313B1/en active Active
- 2006-04-05 JP JP2006103884A patent/JP2007162123A/en active Pending
- 2006-04-13 CN CNA2006100735893A patent/CN1982507A/en active Pending
- 2006-06-30 KR KR1020060060625A patent/KR20070062898A/en not_active Application Discontinuation
- 2006-12-12 US US11/609,672 patent/US20070131558A1/en not_active Abandoned
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| KR20070062898A (en) | 2007-06-18 |
| JP2007162123A (en) | 2007-06-28 |
| DE102005059367B4 (en) | 2014-04-03 |
| EP1798313A3 (en) | 2008-06-18 |
| DE102005059367A1 (en) | 2007-06-14 |
| EP1798313A2 (en) | 2007-06-20 |
| CN1982507A (en) | 2007-06-20 |
| US20070131558A1 (en) | 2007-06-14 |
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