GB1602404A - Electroplating of chromium - Google Patents
Electroplating of chromium Download PDFInfo
- Publication number
- GB1602404A GB1602404A GB13458/78A GB1345878A GB1602404A GB 1602404 A GB1602404 A GB 1602404A GB 13458/78 A GB13458/78 A GB 13458/78A GB 1345878 A GB1345878 A GB 1345878A GB 1602404 A GB1602404 A GB 1602404A
- Authority
- GB
- United Kingdom
- Prior art keywords
- bath
- anolyte
- anode
- catholyte
- chromium
- 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.)
- Expired
Links
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 19
- 239000011651 chromium Substances 0.000 title claims description 18
- 229910052804 chromium Inorganic materials 0.000 title claims description 18
- 238000009713 electroplating Methods 0.000 title claims description 17
- 239000012528 membrane Substances 0.000 claims abstract description 27
- 230000002999 depolarising effect Effects 0.000 claims abstract description 14
- 238000005341 cation exchange Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007747 plating Methods 0.000 claims description 17
- -1 sulphate ions Chemical class 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BDJXVNRFAQSMAA-UHFFFAOYSA-N quinhydrone Chemical compound OC1=CC=C(O)C=C1.O=C1C=CC(=O)C=C1 BDJXVNRFAQSMAA-UHFFFAOYSA-N 0.000 claims description 8
- 229940052881 quinhydrone Drugs 0.000 claims description 8
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Inorganic materials [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 4
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 4
- 238000001246 colloidal dispersion Methods 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 3
- 230000037427 ion transport Effects 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- 230000003019 stabilising effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 229920000557 Nafion® Polymers 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 206010067484 Adverse reaction Diseases 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000006838 adverse reaction Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
Abstract
Process for depositing metals, employing an electrolytic bath which has an anolyte and a catholyte which are separated by a cation exchange membrane. The membrane consists of a perfluorinated film. The anolyte preferably contains a depolarising addition in order to reduce the electrode potential of the anode. The pH of the anolyte is set in such a way that a transfer of hydrogen through the membrane takes place which compensates for the generation of hydrogen on the cathode while the bath is used. The anode is arranged in the bath within a sheath which consists at least in part of a perfluorinated cation exchange membrane. The anolyte is likewise situated within the sheath.
Description
(54) ELECTROPLATING OF CHROMIUM
(71) We, INTERNATIONAL BUSINESS
MACHINES CORPORATION, a Corporation organized and existing under the laws of the
State of New York, in the United States of
America, of Armonk, New York 10504,
United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to the electroplating of chromium, and more particularly to an electroplating bath for depositing chromium having an anolyte separated from the catholyte by a cation exchange membrane.
The use of membranes in electroplating baths has been suggested but has been inhibited by the fact that formerly they have exhibited high electrical resistance and consequently produced unacceptably high plating voltages in electroplating baths. Also the use of membranes required expensive structural modification of existing electroplating baths.
The present invention provides an electroplating bath for depositing chromium having an anolyte separated from a catholyte by a perfluorinated cation exchange membrane, in which the anolyte includes sulphate ions, and in which the catholyte includes chromium (III) sulphate as the source of chromium and anions for reducing the plating voltage; and said bath having an anode immersed in the anolyte, the material of the anode and the anolyte being determined by their chemical reaction.
The bath of the present invention prevents adverse anode reactions with negligible increase in the plating voltage. One such adverse reaction is the oxidation of Cr(III) ions to Cr(VI), since the accumulation of
Cr(VI) ions in a trivalent chromium plating solution ultimately results in the cessation of plating.
The anolyte preferably has a depolarising species therein capable of reducing the electrode potential of the anode when the bath is in use. In addition the pH of the catholyte can be stabilised by arranging the pH of the anolyte to allow hydrogen transport through the membrane to compensate for hydrogen evolution at the cathode.
A preferred perfluorinated cation exchange membrane is a sheet of NAFION.
(NAFION is the trade mark of the Du Pont
Corporation.) These perfinorinated polymer membranes are thin, have negligible electrical resistance and are mechanically and chemically robust. The depolarising species may include ferrocyanide anions, hydrazine or quinhydrone. The effect of the depolarising species is to significantly reduce the plating voltage. The plating voltage can be further reduced by using highly conducting anions in the catholyte which without the use of a membrane could have produced an adverse anode reaction. An example of this is chloride anions. Chloride anions are desirable as they have high specific conductivity and are obtained from the inexpensive NaCl salt. Their use without a cation exchange membrane is undesirable as chlorine can be evolved at the anode.
The electroplating baths of the present invention, therefore, can avoid deleterious anode reactions, and can reduce the plating voltage by using a perfluorinated cation exchange membrane and by using a suitable anolyte. In this way it is possible to separately optimise both the anolyte and catholyte. In addition the material of the anode is not determined by the plating solution and can be optimised for cost and for its electrochemical reaction with the anolyte.
The anolyte can be contained within an anode arrangement which comprises a compartment having at least a part of its surface formed by a perfiuorinated cation exchange membrane, and having within the compartment an anode. The anolyte preferably has a depolarising species therein capable of reducing the electrode potential of the anode when the bath is in use.
The anode arrangement is such that it can be substantially the same shape and size as a conventional anode and can be immersed and supported in the catholyte without changing the anode supports.
One anode arrangement comprises a compartment consisting of a perfluorinated cation exchange membrane supported on a metal or plastic box-like frame and has an anode supported within the compartment.
Alternatively the membrane may be in the form of a tube. An anolyte is provided in the compartment or tube, surrounding the anode, preferably by a gel, such as an Agar gel, saturated with a depolarising species. In addition the gel may contain a colloidal dispersion of a metal or carbon to increase the conductivity of the anolyte. The membrane is preferablyna NAFION sheet. This anode arrangement provides a rugged, simple and efficient anode which prevents adverse reactions and enables the catholyte to be optimised for plating. Also the acidity of the anolyte can be arranged so that the pH of the catholyte is stabilised when the bath is in use.
The invention will now be described with reference to the following examples:
EXAMPLE I
An electroplating bath for chromium comprises an anolyte and a catholyte have the following constituents.
Anolyte
Potassium Ferrocyanide (K4Fe(CN)6) 1M
Sodium Sulphate (Na2SO4) 2M pH adjusted to 1.6
Catholyte
Chromium (III) Sulphate 0.1M
Sodium thiocyanate 0.2M
Sodium Chloride 2M
Glycine 10 grams/litre
Boric acid 60 grams/litre
Wetting agent (FC98)* 0.1 gram/litre pH adjusted to 3.5
* FC98 is a product of the 3M Corporation.
The anolyte and catholyte were separated by a sheet of NAFION (NAFION is a trade mark of the Du Pont Corporation). The bath was operated at a temperature of 50"C. The effect of using ferrocyanide as a depolariser in the anolyte was to reduce the plating voltage by 17 percent using a platinised titanium anode. The ferrocyanide anions are oxidised to ferricyanide anions during plating so that the ferricyanide anions must be reduced back to ferrocyanide ions after a given plating time. The depolarising species may be reduced electrochemically in a suitable electrolyte or may be reduced by adding a suitable reducing agent, such as sodium dithionite or zinc, to the anolyte.
In addition the pH of the catholyte may be stabilised by adjusting the pH of the anolyte to allow hydrogen ion transport through the membrane to compensate for the increase in the pH of the catholyte by the evolution of hydrogen at the cathode.
Hydrazine and quinhydrone may be substituted for ferrocyanide anions in the anolyte.
EXAMPLE 2 An anode arrangement for a chromium (III) electroplating bath having a composition similar to the catholyte given in Example 1 consists of a compartment of box-like shape. The compartment consisting of a
NAFION membrane supported by a metal or plastics frame. Alternatively the membrane may be in the form of a tube. A carbon anode is supported within the compartment or tube. An anolyte fills the inside of the compartment or tube surrounding the carbon anode. The anolyte consists of an Agar gel saturated with a solution of 2M potassium iodide in 0.1M sulphuric acid. The conductivity of the anolyte can be further increased by including a colloidal dispersion of carbon in the gel. The sulphuric acid concentration can be arranged so that the pH of the catholyte is stablised when the bath is used.
The depolarisation reaction comprises the oxidation of I- ions to I 3. This reaction is reversible allowing the depolarising species to be regenerated (reduced) in an aqueous electrolyte or in the electroplating bath itself by making the anode arrangement a temporary cathode.
Alternatively depolarising species to the iodide anions include ferrocyanide anions, hydrazine, quinhydrone or ferrous ions. Materials other than carbon may be used for the anode. Suitable materials are stainless steel, platinised titanium, magnetite or chromium depending on the specific depolarising species.
EXAMPLE 3
An electroplating bath for chromium comprises an anolyte and a catholyte having the following constituents:
Anolyte
10% by volume sulphuric acid (approximately 2M) and quinhydrone (to saturation at 18"C) pH adjusted to 1.0
Catholyte
Chromium Sulphate 0.1M Sodium thiocyanate 0.2M
Sodium chloride 2M
Glycine 10 grams/litre
Boric acid 60 grams/litre
Wetting agent (FC98) 0.1 gram/litre pH adjusted to 3.5
The anolyte and catholyte were separated by a sheet of NAFION membrane. The bath was operated at a temperature of 50"C. The use of quinhydrone reduced plating voltage by 15% using a platinised titanium anode mesh.
WHAT WE CLAIM IS:
1. An electroplating bath for depositing chromium having an anolyte separated from a catholyte by a perfluorinated cation exchange membrane, in which the anolyte includes sulphate ions, and in which the catholyte includes chromium (III) sulphate as the source of chromium and anions for reducing the plating voltage; and said bath having an anode immersed in the anolyte, the material of the anode and the anolyte being determined by their chemical reaction.
2. A bath as claimed in claim 1, in which the anolyte has a depolarising species therein capable of reducing the electrode potential of the anode when the bath is in use.
3. A bath as claimed in claim 2, in which the depolarising species are ferrocyanide anions, hydrazine, quinhydrone, potassium iodide ions in sulphuric acid solution or ferrous ions.
4. A bath as claimed in any one of the preceding claims, in which the pH of the anolyte is arranged to allow hydrogen ion transport through the membrane to compensate for hydrogen evolution at the cathode thereby stabilising the pH of the catholyte.
5. A bath as claimed in any one of the preceding claims, in which the anolyte is contained within a compartment immersed in the catholyte, the compartment having at least a part of its surface provided by the membrane.
6. A bath as claimed in claim 5, in which the anolyte is a gel.
7. A bath as claimed in claim 6, in which the gel has a colloidal dispersion of a metal or carbon therein.
8. A bath as claimed in any one of claims 5, 6 or 7, in which the compartment comprises a metal or plastic box-like frame, or in which the compartment is in the form of a tube.
9. A bath as claimed in any one of the preceding claims, in which the anode is of carbon, platinised titanium, stainless steel, magnetite or chromium.
10. An electroplating bath for depositing chromium substantially as described with reference to Examples 1, 2 or 3.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (10)
1. An electroplating bath for depositing chromium having an anolyte separated from a catholyte by a perfluorinated cation exchange membrane, in which the anolyte includes sulphate ions, and in which the catholyte includes chromium (III) sulphate as the source of chromium and anions for reducing the plating voltage; and said bath having an anode immersed in the anolyte, the material of the anode and the anolyte being determined by their chemical reaction.
2. A bath as claimed in claim 1, in which the anolyte has a depolarising species therein capable of reducing the electrode potential of the anode when the bath is in use.
3. A bath as claimed in claim 2, in which the depolarising species are ferrocyanide anions, hydrazine, quinhydrone, potassium iodide ions in sulphuric acid solution or ferrous ions.
4. A bath as claimed in any one of the preceding claims, in which the pH of the anolyte is arranged to allow hydrogen ion transport through the membrane to compensate for hydrogen evolution at the cathode thereby stabilising the pH of the catholyte.
5. A bath as claimed in any one of the preceding claims, in which the anolyte is contained within a compartment immersed in the catholyte, the compartment having at least a part of its surface provided by the membrane.
6. A bath as claimed in claim 5, in which the anolyte is a gel.
7. A bath as claimed in claim 6, in which the gel has a colloidal dispersion of a metal or carbon therein.
8. A bath as claimed in any one of claims 5, 6 or 7, in which the compartment comprises a metal or plastic box-like frame, or in which the compartment is in the form of a tube.
9. A bath as claimed in any one of the preceding claims, in which the anode is of carbon, platinised titanium, stainless steel, magnetite or chromium.
10. An electroplating bath for depositing chromium substantially as described with reference to Examples 1, 2 or 3.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB13458/78A GB1602404A (en) | 1978-04-06 | 1978-04-06 | Electroplating of chromium |
| CH133079A CH639430A5 (en) | 1978-04-06 | 1979-02-12 | Process for the electrolytic deposition of metals |
| FR7905103A FR2421962A1 (en) | 1978-04-06 | 1979-02-20 | BATH AND ANODE ARRANGEMENT FOR THE DEPOSIT OF METALS BY GALVANOPLASTY AND THEIR METHOD OF USE |
| JP54033443A JPS59595B2 (en) | 1978-04-06 | 1979-03-23 | Electroplating bath for chromium deposition |
| IT21366/79A IT1166721B (en) | 1978-04-06 | 1979-03-28 | METAL ELECTROPLATING |
| DE19792912351 DE2912351A1 (en) | 1978-04-06 | 1979-03-29 | DEVICE AND BATHROOM FOR ELECTRIC PLATING AND METHOD OF BATH REGENERATION |
| NL7902628A NL7902628A (en) | 1978-04-06 | 1979-04-04 | ELECTROLYTIC DEPOSITION OF METAL LAYERS. |
| CA000324906A CA1120427A (en) | 1978-04-06 | 1979-04-04 | Electroplating metals |
| SE7903037A SE429980B (en) | 1978-04-06 | 1979-04-05 | ELECTROPLETING BATHROOM FOR CHROME PROPOSITION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB13458/78A GB1602404A (en) | 1978-04-06 | 1978-04-06 | Electroplating of chromium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1602404A true GB1602404A (en) | 1981-11-11 |
Family
ID=10023343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB13458/78A Expired GB1602404A (en) | 1978-04-06 | 1978-04-06 | Electroplating of chromium |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS59595B2 (en) |
| CA (1) | CA1120427A (en) |
| CH (1) | CH639430A5 (en) |
| DE (1) | DE2912351A1 (en) |
| FR (1) | FR2421962A1 (en) |
| GB (1) | GB1602404A (en) |
| IT (1) | IT1166721B (en) |
| NL (1) | NL7902628A (en) |
| SE (1) | SE429980B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448648A (en) * | 1981-11-18 | 1984-05-15 | International Business Machines Corporation | Trivalent chromium electroplating baths |
| US4448649A (en) * | 1981-11-18 | 1984-05-15 | International Business Machines Corporation | Trivalent chromium electroplating baths |
| US4472250A (en) * | 1981-11-18 | 1984-09-18 | International Business Machines Corporation | Bath and process for the electrodeposition of chromium |
| US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| US4507178A (en) * | 1982-02-09 | 1985-03-26 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| WO2008014987A2 (en) | 2006-08-01 | 2008-02-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for deposition of chromium layers as hard- chrome plating, electroplating bath and hard- chrome surfaces |
| US7442286B2 (en) | 2004-02-26 | 2008-10-28 | Atotech Deutschland Gmbh | Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys |
| US7780840B2 (en) | 2008-10-30 | 2010-08-24 | Trevor Pearson | Process for plating chromium from a trivalent chromium plating bath |
| US7807035B2 (en) | 1998-07-30 | 2010-10-05 | Ewh Industrieanlagen Gmbh & Co. Kg | Methods of plating zinc-containing coatings under alkaline conditions |
| WO2014079911A2 (en) | 2012-11-21 | 2014-05-30 | Tata Steel Ijmuiden B.V. | Method for electrodeposition of chromium containing coatings from trivalent chromium based electrolytes |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3188361B2 (en) * | 1994-06-27 | 2001-07-16 | ペルメレック電極株式会社 | Chrome plating method |
| DE19848467C5 (en) * | 1998-10-21 | 2006-04-27 | Walter Hillebrand Gmbh & Co. Kg Galvanotechnik | Alkaline zinc-nickel bath |
| US7563348B2 (en) * | 2004-06-28 | 2009-07-21 | Lam Research Corporation | Electroplating head and method for operating the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1237143A (en) * | 1968-06-04 | 1971-06-30 | Burroughs Corp | Method and apparatus for electroplating |
| US4006067A (en) * | 1973-03-05 | 1977-02-01 | Gussack Mark C | Oxidation-reduction process |
| GB1431639A (en) * | 1974-12-11 | 1976-04-14 | Ibm Uk | Electroplating chromium and its alloys |
| US4113588A (en) * | 1976-03-09 | 1978-09-12 | Solex Research Corporation Of Japan | Process for recovery of waste H2 SO4 and HCl |
| CH634881A5 (en) * | 1978-04-14 | 1983-02-28 | Bbc Brown Boveri & Cie | METHOD FOR ELECTROLYTICALLY DEPOSITING METALS. |
-
1978
- 1978-04-06 GB GB13458/78A patent/GB1602404A/en not_active Expired
-
1979
- 1979-02-12 CH CH133079A patent/CH639430A5/en not_active IP Right Cessation
- 1979-02-20 FR FR7905103A patent/FR2421962A1/en active Granted
- 1979-03-23 JP JP54033443A patent/JPS59595B2/en not_active Expired
- 1979-03-28 IT IT21366/79A patent/IT1166721B/en active
- 1979-03-29 DE DE19792912351 patent/DE2912351A1/en active Granted
- 1979-04-04 CA CA000324906A patent/CA1120427A/en not_active Expired
- 1979-04-04 NL NL7902628A patent/NL7902628A/en not_active Application Discontinuation
- 1979-04-05 SE SE7903037A patent/SE429980B/en not_active IP Right Cessation
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448648A (en) * | 1981-11-18 | 1984-05-15 | International Business Machines Corporation | Trivalent chromium electroplating baths |
| US4448649A (en) * | 1981-11-18 | 1984-05-15 | International Business Machines Corporation | Trivalent chromium electroplating baths |
| US4472250A (en) * | 1981-11-18 | 1984-09-18 | International Business Machines Corporation | Bath and process for the electrodeposition of chromium |
| US4502927A (en) * | 1981-11-18 | 1985-03-05 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| US4507178A (en) * | 1982-02-09 | 1985-03-26 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| US7807035B2 (en) | 1998-07-30 | 2010-10-05 | Ewh Industrieanlagen Gmbh & Co. Kg | Methods of plating zinc-containing coatings under alkaline conditions |
| US8486235B2 (en) | 1998-07-30 | 2013-07-16 | Ewh Industrieanlagen Gmbh & Co. Kg | Alkaline zinc-nickel bath |
| US7442286B2 (en) | 2004-02-26 | 2008-10-28 | Atotech Deutschland Gmbh | Articles with electroplated zinc-nickel ternary and higher alloys, electroplating baths, processes and systems for electroplating such alloys |
| WO2008014987A2 (en) | 2006-08-01 | 2008-02-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for deposition of chromium layers as hard- chrome plating, electroplating bath and hard- chrome surfaces |
| DE102006035871B3 (en) * | 2006-08-01 | 2008-03-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the deposition of chromium layers as hard chrome plating, plating bath and hard chrome plated surfaces and their use |
| US7780840B2 (en) | 2008-10-30 | 2010-08-24 | Trevor Pearson | Process for plating chromium from a trivalent chromium plating bath |
| WO2014079911A2 (en) | 2012-11-21 | 2014-05-30 | Tata Steel Ijmuiden B.V. | Method for electrodeposition of chromium containing coatings from trivalent chromium based electrolytes |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7902628A (en) | 1979-10-09 |
| CA1120427A (en) | 1982-03-23 |
| FR2421962A1 (en) | 1979-11-02 |
| DE2912351A1 (en) | 1979-10-18 |
| SE7903037L (en) | 1979-10-07 |
| JPS59595B2 (en) | 1984-01-07 |
| IT1166721B (en) | 1987-05-06 |
| DE2912351C2 (en) | 1990-11-15 |
| FR2421962B1 (en) | 1981-10-30 |
| SE429980B (en) | 1983-10-10 |
| IT7921366A0 (en) | 1979-03-28 |
| JPS54134038A (en) | 1979-10-18 |
| CH639430A5 (en) | 1983-11-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19980405 |