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
  • C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
• • 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
  • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
• • 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
  • C25D3/56—Electroplating: Baths therefor from solutions of alloys

Definitions

• the present invention relates to plating bath compositions and a process for depositing functional chromium layers by electroplating.
• Functional chromium layers deposited by electroplating are used to improve wear and corrosion resistance of products such as shock absorbers, hydraulic pistons and the like.
• the plating bath compositions used comprise chromic acid, sulfate ions, water and an alkyl-sulfonic acid or salt thereof.
• Alkyl-sulfonic acid catalysts having a molar ratio S : C ⁇ 1 : 3 are disclosed in EP 0 196 053 B1 .
• suitable alkyl-sulfonic acids are methyl-sulfonic acid, ethyl-sulfonic acid, propyl-sulfonic acid, methane-disulfonic acid and 1,2-ethane-disulfonic acid. Said alkyl-sulfonic acids improve the cathodic current efficiency during plating.
• alkyl-polysulfonic acids halogenated alkyl-polysulfonic acids and corresponding salts such as methane-disulfonic acid for reducing the corrosion of lead anodes during plating is disclosed in EP 0 452 471 B1 .
• Aromatic-trisulfionic acids as an additive in plating bath compositions for depositing functional chromium layers are disclosed in US 2,195,409 .
• the chromium layers obtained from such plating bath compositions are bright and uniform.
• a plating bath composition for depositing a functional chromium layer with an improved cathodic current efficiency comprising propane-1,2,3-trisulfonic acid is disclosed in DE 43 05 732 A1 .
• the objective of the present invention is to provide a plating bath composition and a process utilizing said plating bath composition for depositing functional chromium layers having an improved corrosion resistance.
• the functional chromium layers deposited from the aqueous plating bath and by the process according to the present invention have an increased corrosion resistance compared to functional chromium layers deposited from conventional electroplating bath compositions comprising known alkyl-sulfonic acid.
• the aqueous electroplating bath according to the present invention comprises a source for chromium(VI) ions, sulfate ions, methane-trisulfonic acid, or a salt thereof, and optionally a surface active agent.
• the source for chromium(VI) ions is preferably a chromium(VI) compound soluble in the plating bath such as CrO 3 , Na 2 Cr 2 O 7 and K 2 Cr 2 O 7 , most preferably CrO 3 .
• the concentration of chromium(VI) ions in the electroplating bath according to the present invention preferably ranges from 80 to 600 g/I, more preferably from 100 to 200 g/l.
• Sulfate ions present in the electroplating bath are preferably added in form of sulfuric acid or a plating bath soluble sulfate salt such as Na 2 SO 4 .
• concentration of sulfate ions in the electroplating bath preferably ranges from 1 to 15 g/I, more preferably from 2 to 6 g/I.
• the ratio of the concentration in wt.-% of chromic acid to sulfate preferably ranges from 25 to 200, more preferably from 60 to 150.
• the alkyl-sulfonic acid in the electroplating bath is either methane-trisulfonic acid (HC(SO 2 OH) 3 ) or a mixture of methane-trisulfonic acid and other alkyl-sulfonic acids.
• Corresponding salts such as sodium, potassium and ammonium salts of the aforementioned sulfonic acids can also be employed instead of or as a mixture with the free alkyl-sulfonic acids.
• a precursor of methane-trisulfonic acid or a salt thereof which is oxidized in the electroplating bath according to the present invention to methane-trisulfonic acid or a salt thereof may be used as part or sole source of methane-trisulfonic acid or a salt thereof.
• the concentration of methane-trisulfonic acid or a salt thereof in the plating bath according to the present invention preferably ranges from 6 to 80 mmol/l, more preferably from 12 to 60 mmol/l.
• the overall concentration of methane-trisulfonic acid and other alkyl-sulfonic acids or salts of the aforementioned in case a mixture of alkyl-sulfonic acids is employed preferably ranges from 12 to 160 mmol/l, more preferably from 24 to 120 mmol/l.
• micro-cracks inside the functional chromium layer deposited is desired because thereby a high corrosion resistance and desirable mechanical properties such as a reduced internal stress are achieved.
• Micro-cracks in contrast to macro-cracks within a functional chromium layer do not extend to the surface of the underlying substrate and thus do not result in corrosion of the underlying substrate material, which usually is steel.
• Methane-trisulfonic acid or a salt thereof or constituent of a mixture with other alkyl-sulfonic acid(s) enables a high number of desired micro-cracks in the range of 200 to 1000, more preferably 450 to 750 micro-cracks per cm of the functional chromium layer surface as determined after etching in an aqueous solution containing sodium hydroxide and K 3 [Fe(CN) 6 ] with an optical microscope.
• the number of micro-cracks and the corrosion resistance is increased with methane-trisulfonic acid or a salt thereof as the catalyst compared with methane-disulfonic acid sodium salt or propane-1,2,3-trisulfonic acid sodium salt as the sole alkyl-sulfonic acid. This is shown in Examples 1 to 3.
• micro-cracks Furthermore, an increased number of desired micro-cracks is also obtained at higher current densities (Example 3) whereas the number of micro-cracks is decreasing at higher current densities in case of known alkyl-sulfonic acids such as methane-disulfonic acid (Example 1). Higher current density values during plating are desired because the plating speed is increased thereby.
• the electroplating bath according to the present invention optionally further comprises a surface active agent which reduces formation of undesired foam on top of the plating liquid.
• the surface active additive is selected from the group comprising perfluorinated sulfonate tenisdes, perfluorinated phosphate ten-sides, perfluorinated phosphonate tensides, partially fluorinated sulfonate ten-sides, partially fluorinated phosphate tensides, partially fluorinated phosphonate tensides and mixtures thereof.
• the concentration of the optional surface active agent preferably ranges from 0.05 to 4 g/I, more preferably from 0.1 to 2.5 g/I.
• the current density applied during plating preferably ranges from 10 to 250 A/dm 2 , more preferably from 40 to 200 A/dm 2 .
• the substrate to be plated with a functional chromium layer serves as the cathode during electroplating.
• Cathodic current efficiency is the percentage of current, which is actually used for the deposition of the metal (chromium) at the cathode during electroplating of the functional chromium layer.
• the preferred current efficiency of the process according to the present invention is ⁇ 22 % at a current density of 50 A/dm 2 .
• the temperature of the electroplating bath according to the present invention is held during plating preferably in a range of 10 to 80 °C, more preferably in a range of 45 to 70 °C and most preferably from 50 to 60 °C.
• Inert anodes are preferably applied in the process according to the present invention.
• Suitable inert anodes are for example made of titanium or a titanium alloy coated with one or more platinum group metal, alloys thereof and/or oxides thereof.
• the coating preferably consists of platinum metal, iridium oxide or a mixture thereof.
• the plating bath according to the present invention can also be operated with conventional lead anodes.
• Chromium(III) ions are formed when using such inert anodes.
• Methane-trisulfonic acid and/or a salt thereof as the alkyl-sulfonic acid in a chromium(VI) ion based functional chromium electroplating bath is very sensitive to chromium(III) ions.
• cations of a further metal such as silver ions, lead ions and mixtures thereof are added to the electroplating bath.
• concentration of ions of a further metal preferably ranges from 0.005 to 5 g/I, more preferably from 0.01 to 3 g/I.
• the present invention provides a functional chromium electroplating bath and a process for depositing a functional chromium layer onto a substrate having an increased corrosion resistance which is also obtained at high current densities.
• the number of micro-cracks was determined with an optical microscope after etching the surface of the chromium layer in an aqueous solution containing sodium hydroxide and K 3 [Fe(CN) 6 ].
• the number of micro-cracks along several lines having the same length is determined from which the average number of micro-cracks is calculated and then divided by the line length given in cm to provide the "average number of micro-cracks" in cracks/cm.
• the corrosion resistance of the functional chromium layers was determined according ISO 9227 NSS (neutral salt spray test).
• aqueous electroplating bath stock solution containing 250 g/l CrO 3 , 3.2 g/I sulfate ions and 2 ml/I of a surface active agent was used throughout examples 1 to 3. Different amounts of alkyl-sulfonic acids were added to this stock solution prior to depositing the functional chromium layers.
• the alkyl-sulfonic acid was methane-disulfonic acid disodium salt added to the stock solution in a concentration of 2 to 12 g/l (7.6 to 45.4 mmol/l).
• This alkyl-sulfonic acid is disclosed in EP 0 452 471 B1 .
• Table 1 summarizes the average number of micro-cracks determined at different concentrations of methane-disulfonic acid disodium salt as the sole alkyl-sulfonic acid (plating bath temperature: 58 °C, current density: 50 A/dm 2 ).
• the number of desired micro-cracks is declining with increased current density.
• Formation of undesired red rust was determined after 192 h of neutral salt spray test according to ISO 9227 NSS (> 0.1 % of the surface area covered with red rust after 192 h).
• the alkyl-sulfonic acid was propane-1,2,3-trisulfonic acid trisodium salt added to the stock solution in a concentration of 14.3 mmol/l (5 g/l). This alkyl-disulfonic acid is disclosed in DE 43 05 732 A1 .
• the current efficiency at 50 A/dm 2 and a plating bath temperature of 55 °C is 17.4 % and the number of micro-cracks in the chromium layer deposited under these conditions is 160 cracks/cm.
• the alkyl-sulfonic acid was methane-trisulfonic acid trisodium salt added to the stock solution in concentrations of 6.2 to 37.2 mmol/l (2 to 12 g/l).
• Table 3 summarizes the average number of micro-cracks determined at different concentrations of methane-trisulfonic acid trisodium salt as the sole alkyl-sulfonic acid (plating bath temperature: 58 °C, current density: 50 A/dm 2 ).

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Electroplating And Plating Baths Therefor (AREA)
• Electroplating Methods And Accessories (AREA)

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• 2013
  • 2013-04-17 EP EP13164188.8A patent/EP2792770B1/en active Active
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• 2014
  • 2014-01-22 KR KR1020157025920A patent/KR102194114B1/ko active IP Right Grant
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