US3833485A - Electroplating chromium and chromium alloys - Google Patents
Electroplating chromium and chromium alloys Download PDFInfo
- Publication number
- US3833485A US3833485A US00228083A US22808372A US3833485A US 3833485 A US3833485 A US 3833485A US 00228083 A US00228083 A US 00228083A US 22808372 A US22808372 A US 22808372A US 3833485 A US3833485 A US 3833485A
- Authority
- US
- United States
- Prior art keywords
- ions
- electrolyte
- concentration
- process according
- 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 - Lifetime
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000011651 chromium Substances 0.000 title claims abstract description 32
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 31
- 238000009713 electroplating Methods 0.000 title claims abstract description 18
- 229910000599 Cr alloy Inorganic materials 0.000 title claims abstract description 9
- 239000000788 chromium alloy Substances 0.000 title claims abstract description 9
- -1 sulphate ions Chemical class 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000003792 electrolyte Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 29
- 150000003868 ammonium compounds Chemical class 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 15
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 12
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 31
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004202 carbamide Substances 0.000 abstract description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract description 3
- 150000002830 nitrogen compounds Chemical class 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 238000007747 plating Methods 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000001166 ammonium sulphate Substances 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000002585 base Substances 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
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 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 description 2
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 2
- 239000011696 chromium(III) sulphate Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
-
- 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
-
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- ABSTRACT An improved process for electroplating chromium and chromium alloys from a substantially aqueous electrolyte containing trivalent chromium ions as the source of chromium and containing oxyanions (preferably sulphate ions) as the major anion component.
- the improvement comprises incorporating into said electrolyte chlorine ions in an amount of at least 0.1 gram ions per litre or bromine ions in an amount of at least 0.05 grams ions per litre, and a nitrogen compound selected from the group consisting of ammonium compounds, hydroxylamine, hydrazine, urea, aliphatic amines and hetercyclic amines; and utilizing a carbon anode and electroplating chromium from said electrolyte with said carbon anode immersed in said electrolyte.
- the chlorine ion is preferred and the use of ammonium compounds is preferred.
- oxygen-containing anions presently used oxygen is liberated at an inert anode. If the latter is of carbon it is attacked by the oxygen with consequent erosion. Also particles of carbon are produced which may deposit on the cathode causing faults in the plated article.
- the present invention provides an electroplating process employing a carbon anode and an electrolyte wherein a major proportion of the anions are oxy anions and which further comprises chlorine or bromine ions and a dissolved nitrogen-containing compound which will react with chlorine or bromine in aqueous medium to form nitrogen.
- an electrolyte By use of such an electrolyte the advantageous plating characteristics afforded by use of oxygen containinganions are substantially retained whilst the gaseous products of the electrolysis evolved in the vicinity of the anode consist wholly or in part of nitrogen instead of oxygen, thus lessening or preventing the erosion of the carbon anode.
- the operative principle in the novel process is obtaining an electrolyte in which the species having the lowest discharge potential of all anionic species present, including hydroxyl ion, is chlorine or bromine ion. These ions tend therefore to be preferentially discharged during the electrolysis, giving free halogen which then reacts with the nitrogen-containing compound to generate nitrogen. Surprisingly, however, only a small proportion of the nitrogen-containing compound and halogen ions relative to-the main oxygen containing anion need to be present in order to make a substantial change in the nature of the gas evolved near the anode from oxygen to nitrogen.
- halogen ion and nitrogen-containing compound employed in the novel process will depend upon the overall characteristics of the system rendering it vunerable to the maleficient effects of oxygen and upon the degree of the consequent impairment which can be tolerated.
- anodes whose physical characteristics give them a comparatively high resistance to oxygen attack may be used without disadvantage with electrolytes having lower halide ions and/or nitrogen compound concentrations than would be suitable for less resistant anodes.
- decreasing the anode size and increasing the current density in a given system will make for increased oxygen attack of the electrode.
- chlorine ions are employed in the electrolyte they are present in a concentration of at least 0.1 gramzions per litre, with bromine the preferred minimum is 0.05 gram ions per litre although in both cases concentrations down to as little as 0.01 gram ionsper litre may have beneficial effects.
- concentration of halogen ion are not critical and in many cases will be determined by considerations of solubility, bearing in mind the need to have enough of the main oxygencontaining ion present in the electroplating system. However we have noticed that in the general case bromine ion tends to reach its maximum effectiveness at concentrations of 0.] to 0.2 gram ions per litre and chlorine ion at 1.0 to 1.5 gram ions per litre.
- the concentration of nitrogen containing compound is not in general critical although it is desirably at least as great as that of the halogen ion and will normally be from one half to twice, e.g. from one to one-and-a-half times that concentration.
- the upper limit of effectiveness of nitrogen-containing compounds appears to be reached at concentrations of about 3 to 5 molar, e.g. 4 molar.
- a convenient way of adding a nitrogen-containing compound and a source of halogen ions is to add a halide of a nitrogen-containing base which has the abovementioned characteristic of reacting with halogen in an aqueous medium to form nitrogen. If the nitrogenous compound is not a halide salt e.g. if it is .urea, the source of halogen ions will normally be the hydrogen halide or an. alkali metal halide.
- bromides may also be usedin carrying out the invention
- the halide which will normally be used is the chloride, and the subsequent description will for the sake of simplicity refer only to chlorides.
- a source of chlorine ions and a nitrogen-containing compound as defined above we believe that the anode reaction proceeds in two stages: first the evolution of chlorine and second the reaction of this chlorine with the nitrogenous compound, although some chlorine may escape in the anodic gas, especially that generated at the top of the anode which has less chance of reaction with the nitrogenous compound in the bulk of the solution.
- the preferred nitrogenous compounds are ammonium salts and we believe that in that case the second stage of the anode reaction is as follows:
- the chlorine ion is substantially regenerated in the solution, only the nitrogen-containing compound needs .to be replenished. If the latter is a base, it partially neutralises the HCL generated by the reaction and thus tends to maintain the pH of the bath.
- the preferred nitrogen-containing compounds are ammonium compounds such as ammonium chloride and sulphate. Also suitable are hydroxylamine, hydra zine, urea and methylamine. Other substances which may be used include aliphatic amides in general including formamide; alphatic amines in general including methylamine and heterocyclic amines including piperidine. In general it is preferred that the nitrogencontaining compounds comprise not more than five, more preferably not more than four carbon atoms per molecule.
- nitrogen-containing compounds e.g. urea
- carbon dioxide' is evolved together with nitrogen and performs a like function in militating against oxygen attack on the anode.
- tion enables carbon anodes to be substituted for soluble 5 anodes in processes where the latter are normally used. Examples of this latter type of process are the plating of zinc, nickel and copper, using metallicanodes. The use of carbon anodes would be advantageous in certain circumstances in these processes, particularly in the plating of zinc, if the problem of erosion could be overcome.
- the invention may be applied to conventional processes using oxygen-containing anions and a non-carbon anode together with a porous diaphragm to separate anode and cathode reactions.
- introduction of halogen ion and nitrogen containing compound into the electrolyte may enable the anode to be of carbon and, in' many cases, the diaphragm to be removed.
- the novel process for chromium plating desirably operates at a pH below 2.5, preferably 2.3, where the halide is chloride, and below 2.6 where the halide is bromide.
- the main example of plating process in which the use of carbon anodes is in practice necessary is the plating of chromium or chromium alloys from a trivalent chromium bath not using a diaphragm. This is due to the fact that if an insoluble metal anode (e.g. lead) is used it assists oxidationof the or to Cr thus spoiling the plating, while if a soluble metal anode other than of chromium is used it causes contamination. If the anode is carbon and the anion in such a bath is $0., the erosion of the carbon anode can be reduced or prevented by means of the invention.
- an insoluble metal anode e.g. lead
- the invention may be applied .to baths having the same constitution, apart from the halide addition, as I those hitherto used.
- the plating baths may include conventional electroplating additives such as brightening and levelling agents.
- the process may find particular use in chromium plating to give a hard finish.
- Previous chromium plating processes being trivalent chromium ion have generally been suitable for forming only decorative finished.
- Preferred processes of the invention are those leading to hard chromium finishes.
- Hard and decorative chromium finishes are known terms of art as recognized, for example, in British Standard 4641 of 1970.
- a normal decorative finish might have a thickness of 20 millionths of an inch or less; a hard finish might have a thickness of from V: to 30, more usually from one to five, thousandths of an inch.
- Chromium metal of 98.8 percent purity (remainder r'nainly oxygen) was produced at 30 percent current efficiency from Bath B.
- the voltage required across the cell was 20 percent lower than in a similar experiment using the same solution in a cell containing a microporous diaphragm, the anolyte being 30 percent sulphuric acid and the anode being 1 percent Ag/Pb alloy.
- Cost of electrical power was thus 20 percent lower than in the prior art diaphragm cell, also operated at 30 percent current efficiency.
- the design of the cell was also simplified, in that microporous diaphragms were not necessary, and a separate anolyte system was not required.
- a process according to claim 3 wherein the concentration of said nitrogen-containing compound in said electrolye is from one-half to twice that of said chlorine ions.
- concentration of said nitrogen-containing compound in said electrolyte is from one-half to twice that of said bromine ions.
- bromine ions are present in said electrolyte in a concentration of at least 0.05 gram ions per litre.
- a process as claimed in claim 1 wherein the concentration of nitrogen-containing compound is less than 10 per cent by weight in the water present.
- a process according to claim 1 wherein the concentration of said nitrogen-containing compounds in said electrolyte is from one-half to twice that of said halogen'ion.
- ammonium compound is present in a concentration of from 3 to 5 molar.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Air Bags (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB527071A GB1378883A (en) | 1971-02-23 | 1971-02-23 | Electroplating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3833485A true US3833485A (en) | 1974-09-03 |
Family
ID=9792933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00228083A Expired - Lifetime US3833485A (en) | 1971-02-23 | 1972-02-22 | Electroplating chromium and chromium alloys |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US3833485A (enrdf_load_stackoverflow) |
| BE (1) | BE779725A (enrdf_load_stackoverflow) |
| CA (1) | CA996498A (enrdf_load_stackoverflow) |
| DE (1) | DE2208327A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2126293B1 (enrdf_load_stackoverflow) |
| GB (1) | GB1378883A (enrdf_load_stackoverflow) |
| NL (1) | NL7202364A (enrdf_load_stackoverflow) |
| NO (1) | NO131649C (enrdf_load_stackoverflow) |
| SE (1) | SE384542B (enrdf_load_stackoverflow) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954574A (en) * | 1973-12-13 | 1976-05-04 | Albright & Wilson Limited | Trivalent chromium electroplating baths and electroplating therefrom |
| US4053374A (en) * | 1975-08-27 | 1977-10-11 | Albright & Wilson Limited | Chromium electroplating baths |
| US4093522A (en) * | 1975-01-10 | 1978-06-06 | Horst Dillenberg | Electrolytic chromic acid bath for chrome plating |
| USRE29749E (en) * | 1973-12-13 | 1978-08-29 | Albright & Wilson Ltd. | Trivalent chromium electroplating baths and electroplating therefrom |
| US4406756A (en) * | 1981-07-13 | 1983-09-27 | Canadian Corporate Management Company Limited | Hard chromium plating from hexavalent plating bath |
| US4543167A (en) * | 1982-03-05 | 1985-09-24 | M&T Chemicals Inc. | Control of anode gas evolution in trivalent chromium plating bath |
| US5196109A (en) * | 1991-08-01 | 1993-03-23 | Geoffrey Scott | Trivalent chromium electrolytes and plating processes employing same |
| US6004448A (en) * | 1995-06-06 | 1999-12-21 | Atotech Usa, Inc. | Deposition of chromium oxides from a trivalent chromium solution containing a complexing agent for a buffer |
| US20070227895A1 (en) * | 2006-03-31 | 2007-10-04 | Bishop Craig V | Crystalline chromium deposit |
| US8187448B2 (en) | 2007-10-02 | 2012-05-29 | Atotech Deutschland Gmbh | Crystalline chromium alloy deposit |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006043507A1 (ja) * | 2004-10-18 | 2006-04-27 | Yamaha Hatsudoki Kabushiki Kaisha | エンジン用部品 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2693444A (en) * | 1951-02-12 | 1954-11-02 | Battelle Development Corp | Electrodeposition of chromium and alloys thereof |
| US2822326A (en) * | 1955-03-22 | 1958-02-04 | Rockwell Spring & Axle Co | Bright chromium alloy plating |
| GB1144913A (en) * | 1966-10-31 | 1969-03-12 | British Non Ferrous Metals Res | Electrodeposition of chromium |
| NL7005999A (enrdf_load_stackoverflow) * | 1969-04-24 | 1970-10-27 |
-
1971
- 1971-02-23 GB GB527071A patent/GB1378883A/en not_active Expired
-
1972
- 1972-02-18 CA CA135,105A patent/CA996498A/en not_active Expired
- 1972-02-21 NO NO72514A patent/NO131649C/no unknown
- 1972-02-22 US US00228083A patent/US3833485A/en not_active Expired - Lifetime
- 1972-02-22 DE DE19722208327 patent/DE2208327A1/de active Pending
- 1972-02-22 SE SE7202186A patent/SE384542B/xx unknown
- 1972-02-22 FR FR7205945A patent/FR2126293B1/fr not_active Expired
- 1972-02-23 BE BE779725A patent/BE779725A/xx unknown
- 1972-02-23 NL NL7202364A patent/NL7202364A/xx unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2693444A (en) * | 1951-02-12 | 1954-11-02 | Battelle Development Corp | Electrodeposition of chromium and alloys thereof |
| US2822326A (en) * | 1955-03-22 | 1958-02-04 | Rockwell Spring & Axle Co | Bright chromium alloy plating |
| GB1144913A (en) * | 1966-10-31 | 1969-03-12 | British Non Ferrous Metals Res | Electrodeposition of chromium |
| NL7005999A (enrdf_load_stackoverflow) * | 1969-04-24 | 1970-10-27 |
Non-Patent Citations (1)
| Title |
|---|
| C. J. Brockman, Electrochemistry-Principles and Practice, pp. 152 153, (1931). TP255 B7. * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954574A (en) * | 1973-12-13 | 1976-05-04 | Albright & Wilson Limited | Trivalent chromium electroplating baths and electroplating therefrom |
| USRE29749E (en) * | 1973-12-13 | 1978-08-29 | Albright & Wilson Ltd. | Trivalent chromium electroplating baths and electroplating therefrom |
| US4093522A (en) * | 1975-01-10 | 1978-06-06 | Horst Dillenberg | Electrolytic chromic acid bath for chrome plating |
| US4053374A (en) * | 1975-08-27 | 1977-10-11 | Albright & Wilson Limited | Chromium electroplating baths |
| US4406756A (en) * | 1981-07-13 | 1983-09-27 | Canadian Corporate Management Company Limited | Hard chromium plating from hexavalent plating bath |
| US4543167A (en) * | 1982-03-05 | 1985-09-24 | M&T Chemicals Inc. | Control of anode gas evolution in trivalent chromium plating bath |
| US5196109A (en) * | 1991-08-01 | 1993-03-23 | Geoffrey Scott | Trivalent chromium electrolytes and plating processes employing same |
| US6004448A (en) * | 1995-06-06 | 1999-12-21 | Atotech Usa, Inc. | Deposition of chromium oxides from a trivalent chromium solution containing a complexing agent for a buffer |
| US20070227895A1 (en) * | 2006-03-31 | 2007-10-04 | Bishop Craig V | Crystalline chromium deposit |
| US7887930B2 (en) | 2006-03-31 | 2011-02-15 | Atotech Deutschland Gmbh | Crystalline chromium deposit |
| US20110132765A1 (en) * | 2006-03-31 | 2011-06-09 | Bishop Craig V | Crystalline chromium deposit |
| US8187448B2 (en) | 2007-10-02 | 2012-05-29 | Atotech Deutschland Gmbh | Crystalline chromium alloy deposit |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2208327A1 (de) | 1972-09-21 |
| NL7202364A (enrdf_load_stackoverflow) | 1972-08-25 |
| CA996498A (en) | 1976-09-07 |
| BE779725A (fr) | 1972-06-16 |
| NO131649B (enrdf_load_stackoverflow) | 1975-03-24 |
| FR2126293B1 (enrdf_load_stackoverflow) | 1975-10-24 |
| FR2126293A1 (enrdf_load_stackoverflow) | 1972-10-06 |
| NO131649C (enrdf_load_stackoverflow) | 1975-07-02 |
| SE384542B (sv) | 1976-05-10 |
| GB1378883A (en) | 1974-12-27 |
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