US3788957A - Electrodeposition of chromium - Google Patents
Electrodeposition of chromium Download PDFInfo
- Publication number
- US3788957A US3788957A US00293860A US3788957DA US3788957A US 3788957 A US3788957 A US 3788957A US 00293860 A US00293860 A US 00293860A US 3788957D A US3788957D A US 3788957DA US 3788957 A US3788957 A US 3788957A
- Authority
- US
- United States
- Prior art keywords
- chromium
- plating
- electrolyte solution
- water
- ions
- 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
Links
- 239000011651 chromium Substances 0.000 title abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title abstract description 16
- 229910052804 chromium Inorganic materials 0.000 title abstract description 16
- 238000004070 electrodeposition Methods 0.000 title description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 33
- 239000000243 solution Substances 0.000 abstract description 18
- 239000008151 electrolyte solution Substances 0.000 abstract description 16
- -1 HALIDE IONS Chemical compound 0.000 abstract description 14
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 4
- 239000003093 cationic surfactant Substances 0.000 abstract description 4
- 150000002462 imidazolines Chemical class 0.000 abstract description 3
- 150000005621 tetraalkylammonium salts Chemical class 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion 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
- 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
Definitions
- This application is directed to the electrodeposition of chromium and more particularly to the use of a surfactant as an ingredient in an improved electrolyte solution.
- chromium deposits As an improvement over chromium plating from conventional aqueous chromic acid baths, a method has been developed whereby chromium deposits, having greatly improved corrosion resistance and exhibiting a very good appearance, can be provided by electrolytic techniques through the use of a plating bath comprising chromium ions, particularly trivalent chromium ions, and a homogeneous mixture of water and a dipolar organic solvent,
- aprotic such as dimethylformamide
- the ratio by volume of water to dimethylformamide may range from 10:90 to 95:5 but preferably between 60:40 and :10. These lower concentrations of dimethylformamide make possible a reduction in the cost of the plating bath without necessarily impairing the plating performance.
- the physical characteristics of the solution e.g., color, pH, and viscosity, have been found to change during storage and the color and adhesion of successive metal deposits from the same bath may deteriorate.
- plating baths containing low concentrations of Water have a relatively low conductivity, while solutions with higher concentrations of water tend to evolve excessive amounts of hydrogen at the cathode during plating. It has been found that the presence of an ammonium salt improves the stability of the solution and reduces the tendency of the bath to evolve hydrogen at high water content.
- ammonium salts Moreover the presence of ammonium salts has been found to significantly reduce the effect of changes in pH on the lower limiting plating current density.
- the ammonium ion should be present at a concentration of at least about 0.2 M and preferably from about 0.6 to about 1 M. At lower concentrations of dimethylformamide, it may be preferable to increase the ammonium ion concentration to above 1 M.
- a prerequisite of successful chromium plating from a dipolar organic solvent is that the trivalent chromium ions shall form small moderately stable complexes with the solvent molecule. If there is no complex formation, then the chromic salts are unlikely to be sufficiently soluble. If the complexes formed are excessively stable, then electrodeposition may be diflicult. It is believed that the highly electronegative oxygen atoms which characterize the dipolar organic compounds of this invention may act as covalent links in the formation of complexes between the chromic ions and the organic molecules. Such solutions by themselves do not, however, give smooth coherent metallic deposits.
- the pH of the solution should be from 1 to 3.5 and preferably about 2. If the pH is too low, hydrogen tends to be evolved at the cathode in preference to chromium. If the pH is too high, basic chromium compounds are liable to precipitate out.
- the pH can be adjusted by the use ofhydrochloric acid or sodium hydroxide as required.
- the current efficiency of the solution may be improved by the addition of boric acid, preferably to a concentration of at least 0.1 M.
- Boric acid is not normally soluble to the extent of more than about 0.2 M.
- electroplating baths of the present invention contain a sodium halide which has been found to increase the plating range and current efliciency.
- Sodium halides are also beneficial in that they enhance the covering power of the bath. It is preferred that the sodium halide be present in a concentration of at least about 0.8 M. Again, however, if lower concentrations of dimethylformamide are to be used, it may be advantageous to increase the halide ion concentration above 5 M, for example from 7 to 10 M.
- the surfactant may be cationic, anionic, amphoteric or non-ionic, but cationic surfactants are preferred.
- Nonionic surfactants tend to give rise to dull deposits, particularly when used in higher concentrations.
- Anionic surfactants such as Na lauryl sulphate, again particularly at higher concentrations, tend to give rise to black specks on the metal deposits.
- Cationic surfactants that may be used according to the invention are tetraalkylammonium salt of the general formula /f ⁇ R: R4 X and substituted imidazoline of the general formula wherein R is an alkyl having 8 to 18 carbon atoms, R,, R and R are alkyls having from 1 to 2 carbon atoms,
- R is selected from the group consisting of aliphatic short chain alcohol having up to 6 carbon atoms of the general formula C H OH and sodium salt of a carboxylic acid of the general formula C H OC 'H ,CO'ONa, R is an alkyl having 9 to 17 carbon atoms, R, is an alkyle ne having 1 to 4 carbon atoms, and X is a halogen selected from the group consisting of bromine, chlorine and iodine, and n and n are 1 to 6, the proportion of water to dipolar aprotic solvent being from about :90 to about 90:10.
- An electrolyte solution according to claim 1 having ammonium ions in a concentration of at least 0.2 M and halogen ions in a concentration at least 0.8 M.
- An electrolyte solution according to claim 4 having halogen ions in a concentration of at least 5 M.
- An electrolyte solution according to claim 3 having between about 5 p.p.m. and about 20 p.p.m. of said surfactant.
- An electrolyte solution according to claim 3 having said surfactant in a concentration of between 5 p.p.m. and such amount as causes foaming of the electrolyte solution.
- An electrolyte solution according to claim 3 having ammonium ions in a concentration of between about 0.6 M and about 1 M.
- An electrolyte solution according to claim 3 having a pH between about 1 and 3.5.
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)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4566971A GB1368749A (en) | 1971-09-30 | 1971-09-30 | Electrodeposition of chromium |
| GB4568971A GB1305156A (enrdf_load_stackoverflow) | 1970-12-10 | 1971-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3788957A true US3788957A (en) | 1974-01-29 |
Family
ID=26265633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00293860A Expired - Lifetime US3788957A (en) | 1971-09-30 | 1972-10-02 | Electrodeposition of chromium |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3788957A (enrdf_load_stackoverflow) |
| AU (1) | AU471915B2 (enrdf_load_stackoverflow) |
| DE (1) | DE2247840C3 (enrdf_load_stackoverflow) |
| FR (1) | FR2154725B1 (enrdf_load_stackoverflow) |
| GB (1) | GB1368749A (enrdf_load_stackoverflow) |
| NL (1) | NL7213209A (enrdf_load_stackoverflow) |
Cited By (6)
| 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 |
| USRE29749E (en) * | 1973-12-13 | 1978-08-29 | Albright & Wilson Ltd. | Trivalent chromium electroplating baths and electroplating therefrom |
| US4472249A (en) * | 1981-08-24 | 1984-09-18 | M&T Chemicals Inc. | Bright chromium plating baths and process |
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4686017A (en) * | 1981-11-05 | 1987-08-11 | Union Oil Co. Of California | Electrolytic bath and methods of use |
| US4755265A (en) * | 1985-06-28 | 1988-07-05 | Union Oil Company Of California | Processes for the deposition or removal of metals |
| US4801511A (en) * | 1985-06-28 | 1989-01-31 | Union Oil Company Of California | Battery cell electrolyte |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1304844A (enrdf_load_stackoverflow) * | 1969-04-24 | 1973-01-31 | ||
| AU2348470A (en) * | 1969-12-29 | 1972-07-06 | International Lead Zinc Research Organization | Aqueous chromium plating baths |
-
1971
- 1971-09-30 GB GB4566971A patent/GB1368749A/en not_active Expired
-
1972
- 1972-09-28 AU AU47217/72A patent/AU471915B2/en not_active Expired
- 1972-09-29 DE DE2247840A patent/DE2247840C3/de not_active Expired
- 1972-09-29 FR FR7234499A patent/FR2154725B1/fr not_active Expired
- 1972-09-29 NL NL7213209A patent/NL7213209A/xx not_active Application Discontinuation
- 1972-10-02 US US00293860A patent/US3788957A/en not_active Expired - Lifetime
Cited By (8)
| 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 |
| US4053374A (en) * | 1975-08-27 | 1977-10-11 | Albright & Wilson Limited | Chromium electroplating baths |
| US4472249A (en) * | 1981-08-24 | 1984-09-18 | M&T Chemicals Inc. | Bright chromium plating baths and process |
| 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 |
|---|---|
| NL7213209A (enrdf_load_stackoverflow) | 1973-04-03 |
| AU4721772A (en) | 1974-04-04 |
| DE2247840A1 (de) | 1973-04-05 |
| GB1368749A (en) | 1974-10-02 |
| AU471915B2 (en) | 1976-05-06 |
| FR2154725A1 (enrdf_load_stackoverflow) | 1973-05-11 |
| DE2247840C3 (de) | 1978-06-08 |
| DE2247840B2 (de) | 1977-10-20 |
| FR2154725B1 (enrdf_load_stackoverflow) | 1976-06-04 |
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