US1542549A - Process for the electrolytic deposition of metallic chromium - Google Patents
Process for the electrolytic deposition of metallic chromium Download PDFInfo
- Publication number
- US1542549A US1542549A US703602A US70360224A US1542549A US 1542549 A US1542549 A US 1542549A US 703602 A US703602 A US 703602A US 70360224 A US70360224 A US 70360224A US 1542549 A US1542549 A US 1542549A
- Authority
- US
- United States
- Prior art keywords
- acid
- chromium
- oxide
- weight
- metallic 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
Links
- 238000000034 method Methods 0.000 title description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title description 13
- 229910052804 chromium Inorganic materials 0.000 title description 13
- 239000011651 chromium Substances 0.000 title description 13
- 230000008021 deposition Effects 0.000 title description 2
- 239000002253 acid Substances 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 11
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- 102100035683 Axin-2 Human genes 0.000 description 1
- 101700047552 Axin-2 Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 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 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
Definitions
- This invention relates to .an improved process of electrolytically depositing metallic chromium from chromium compounds, and more especially to a type of process of electrolytic deposition of chromium by means of a bath which contains a mixture of chromic oxide and an acid and used in the proportions by weight of acid and oxide of chromium approximately equal or a smaller quantity of chromium oxide but not less than half the weight of the acid, the relative proportion being as far as possible maintained constant during the operation, and to which acid is added and t e temperature kept constant.
- Chromium has previously been proposed to deposit chromium from a solution of chromic sulphate, chromic anhydride and boric acid also being present in the solution, and also from a solution of chromic and boric or tartaric acid with an average current density of 0.20 amperes er square centimetre at a pressure of 20 v0 ts. Chromium has previousl been deposited from a solution of the sulp ates but in this process avery high current density is required, say of between 2 and 5 amps. per sq. cm. at a pressure of 3 to 6 volts but the'deposit resulting is brittle and easily flakes ofi'.
- a process of the type described according to this invention is characterized in that the ac1d added to the chromium oxide 1S hydrochloric acid or acetic acid, with the addition of a suitable conduct-ing acid or salt, for example, boric acid, tartaric acid, citric acid, or sulphuric acid, which produces a non-colloidal solution.
- a suitable conduct-ing acid or salt for example, boric acid, tartaric acid, citric acid, or sulphuric acid
- the proportion by weight of hydrochloric acid or acetic acid to chromium oxide of approximately 2 to 1 has been found to give a good result.
- This strength of the solution requires to be maintained during the working of the solution, and one doing this is to add fresh materials to the solution, while working with suitable anodes.
- the additional subsidiary conducting acids such as boric acid, tartaric acid,
- citric acid or sulphuric acid are used in small quantlties.
- a coating can be deposited on many metals commonly used for commercial purposes, any desired thickness being obtainablef This process enables chromium to be deposited in such a condition that it can be highly polished.
- A. process of electrolytically depositng metallic chromium consisting in providing a bath containing a mixture of chromic oxide and a non-oxidizing acid in the proportions by weight of oxide of chromium more than half the weight of the acid, maintainlng the relative proportions substantially constant during the operation, adding a suitable conducting acid which produces a non-colloidal solution, and maintaining the temperature constant.
- a process of electrolytically depositnig metallic chromium consisting in providing a bath containing a mixture of chromic oxide and a non-oxidizing acid and used in the proportions by weight of oxide of chromium more than half the weight of the acid, maintaining the relative proportions substantially constant during the operation, adding a suitable conducting acid which produces a non-colloidal solution, maintaining the temperature constant, and supplying current density of about 2 to 3 amperes per square decimetre at a constant temperature of about 18 degrees centigrade and a voltage of not less than 2 and not more than 4.
- a process of electrolytically depositing metallic chromium consisting in providing a bath containing a mixture of chromic oxide and a non-oxidizing acid and used in the proportions by weight of acid and oxide of chromium approximately 4 to 3, maintaining the relative proportions substantially constant during the operation, adding a sultable conducting acid which produces a non-colloidal solution and maintaining the temperature constant.
- a process of-electrolytlcally deposting metallic chromium consisting 1n providing a bath containing a mixture of chromlc oxide and a non-oxidizing acid and used in the proportions by weight of oxide of chromium more than half the weight of the acid, maintaining the relative proportions substantially constant during the operation, adding boric acid, and maintaining the tempera ture constant.
- a process for electrolytically depositing metallic chromium consisting in providing a bath containing a mixture of chromic oxide and acetic acid used in the proportions by weight of oxide of chromium more than half the weight of the acid, maintaining the relative proportions substantially constant during the operation, boric acid and maintaining the temperature constant.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
.tion of Metallic Chromium,
'way of Patented June 16, 1925.
g UNITED STATES 1,542,549 PATENT OFFICE...
RICHARD GRAB, or SHEFFIELD, ENGLAND, assrenon r0 ELECROM LIMITED, or
, g c ,snnrrrnLn, ENGLAND. C
No Drawing. Application filed April 2,
To all whom it may concern: 4
Be it known that I, Rrormno GRAH, of Shefiield, England, a citizen of Germany, have invented a certain new and useful Improved Process for the Electrolytic Deposiof which the following is a specification.
This invention relates to .an improved process of electrolytically depositing metallic chromium from chromium compounds, and more especially to a type of process of electrolytic deposition of chromium by means of a bath which contains a mixture of chromic oxide and an acid and used in the proportions by weight of acid and oxide of chromium approximately equal or a smaller quantity of chromium oxide but not less than half the weight of the acid, the relative proportion being as far as possible maintained constant during the operation, and to which acid is added and t e temperature kept constant.
It has previously been proposed to deposit chromium from a solution of chromic sulphate, chromic anhydride and boric acid also being present in the solution, and also from a solution of chromic and boric or tartaric acid with an average current density of 0.20 amperes er square centimetre at a pressure of 20 v0 ts. Chromium has previousl been deposited from a solution of the sulp ates but in this process avery high current density is required, say of between 2 and 5 amps. per sq. cm. at a pressure of 3 to 6 volts but the'deposit resulting is brittle and easily flakes ofi'.
A process of the type described according to this invention is characterized in that the ac1d added to the chromium oxide 1S hydrochloric acid or acetic acid, with the addition of a suitable conduct-ing acid or salt, for example, boric acid, tartaric acid, citric acid, or sulphuric acid, which produces a non-colloidal solution.
In the above process, in the preferred form, the proportion by weight of hydrochloric acid or acetic acid to chromium oxide of approximately 2 to 1 has been found to give a good result. This strength of the solution requires to be maintained during the working of the solution, and one doing this is to add fresh materials to the solution, while working with suitable anodes. The additional subsidiary conducting acids, such as boric acid, tartaric acid,
rnoonss roarnn ELECTROLYTIC nnrosr'rioivon METALLIC omtomrum.
1924. Serial No. 703,602.
citric acid, or sulphuric acid are used in small quantlties.
While a proportion of 2 to 1 is maintained,
an increase in current density employed has no appreciable effect on the amount of metal deposlted in a given time. If, however, the proportion employed is 4 to 3 or still higher, 1. -e.,. if the proportion of chromium oxide present in the solution is increased, better results are obtained. The solution is worked at a temperature of 18 to 20 centigrade, using a current density of 2 to 3 amperes per square decimetre and a voltage of 2 to 4. Working the solution as described above,
a coating can be deposited on many metals commonly used for commercial purposes, any desired thickness being obtainablef This process enables chromium to be deposited in such a condition that it can be highly polished.
What I claim and desire to secure by Letters Patent is 1. A. process of electrolytically depositng metallic chromium consisting in providing a bath containing a mixture of chromic oxide and a non-oxidizing acid in the proportions by weight of oxide of chromium more than half the weight of the acid, maintainlng the relative proportions substantially constant during the operation, adding a suitable conducting acid which produces a non-colloidal solution, and maintaining the temperature constant.
2. A process of electrolytically depositnig metallic chromium consisting in providing a bath containing a mixture of chromic oxide and a non-oxidizing acid and used in the proportions by weight of oxide of chromium more than half the weight of the acid, maintaining the relative proportions substantially constant during the operation, adding a suitable conducting acid which produces a non-colloidal solution, maintaining the temperature constant, and supplying current density of about 2 to 3 amperes per square decimetre at a constant temperature of about 18 degrees centigrade and a voltage of not less than 2 and not more than 4.
3. A process of electrolytically depositing metallic chromium consisting in providing a bath containing a mixture of chromic oxide and a non-oxidizing acid and used in the proportions by weight of acid and oxide of chromium approximately 4 to 3, maintaining the relative proportions substantially constant during the operation, adding a sultable conducting acid which produces a non-colloidal solution and maintaining the temperature constant.
4. A process of-electrolytlcally depos ting metallic chromium consisting 1n providing a bath containing a mixture of chromlc oxide and a non-oxidizing acid and used in the proportions by weight of oxide of chromium more than half the weight of the acid, maintaining the relative proportions substantially constant during the operation, adding boric acid, and maintaining the tempera ture constant.
5. A process for electrolytically depositing metallic chromium conslstlng in roviding a bath containing a mixture of c om1c oxide and acetic acid used in the proportions by weight of oxide of chromium more than half the weight of the acid, maintaining the relative proportions substantially constant during the operation, adding a suitable conductin acid which produces a non-colloidal solution, and maintaining the temperature constant.
6. A process for electrolytically depositing metallic chromium consisting in providing a bath containing a mixture of chromic oxide and acetic acid used in the proportions by weight of oxide of chromium more than half the weight of the acid, maintaining the relative proportions substantially constant during the operation, boric acid and maintaining the temperature constant.
In testimony whereof, I aflix my signature.
RICHARD GRAH.
adding
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US703602A US1542549A (en) | 1923-09-14 | 1924-04-02 | Process for the electrolytic deposition of metallic chromium |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3476022A GB223611A (en) | 1923-09-14 | 1923-09-14 | An improved process for the electro deposition of chromium |
| US703602A US1542549A (en) | 1923-09-14 | 1924-04-02 | Process for the electrolytic deposition of metallic chromium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1542549A true US1542549A (en) | 1925-06-16 |
Family
ID=26262431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US703602A Expired - Lifetime US1542549A (en) | 1923-09-14 | 1924-04-02 | Process for the electrolytic deposition of metallic chromium |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1542549A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2517441A (en) * | 1945-07-09 | 1950-08-01 | Ductile Chrome Process Co | Electrodeposition of chromium |
| US2623847A (en) * | 1947-09-10 | 1952-12-30 | Lloyd O Gilbert | Black chromium plating |
| US2739108A (en) * | 1952-06-14 | 1956-03-20 | Westinghouse Electric Corp | Electroplating chromium-nickel alloy coatings |
| US2739109A (en) * | 1952-06-14 | 1956-03-20 | Westinghouse Electric Corp | Black chromium-nickel-vanadium electrodeposits |
| US2745801A (en) * | 1955-03-14 | 1956-05-15 | Harshaw Chem Corp | Chromium plating |
| US2824829A (en) * | 1953-02-27 | 1958-02-25 | Westinghouse Electric Corp | Electrodepositing black chromiumvanadium coatings and members therewith |
| US4406756A (en) * | 1981-07-13 | 1983-09-27 | Canadian Corporate Management Company Limited | Hard chromium plating from hexavalent plating bath |
-
1924
- 1924-04-02 US US703602A patent/US1542549A/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2517441A (en) * | 1945-07-09 | 1950-08-01 | Ductile Chrome Process Co | Electrodeposition of chromium |
| US2623847A (en) * | 1947-09-10 | 1952-12-30 | Lloyd O Gilbert | Black chromium plating |
| US2739108A (en) * | 1952-06-14 | 1956-03-20 | Westinghouse Electric Corp | Electroplating chromium-nickel alloy coatings |
| US2739109A (en) * | 1952-06-14 | 1956-03-20 | Westinghouse Electric Corp | Black chromium-nickel-vanadium electrodeposits |
| US2824829A (en) * | 1953-02-27 | 1958-02-25 | Westinghouse Electric Corp | Electrodepositing black chromiumvanadium coatings and members therewith |
| US2745801A (en) * | 1955-03-14 | 1956-05-15 | Harshaw Chem Corp | Chromium plating |
| US4406756A (en) * | 1981-07-13 | 1983-09-27 | Canadian Corporate Management Company Limited | Hard chromium plating from hexavalent plating bath |
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