US3649479A - Process for chromium electroplating using electrolytic solutions containing trivalent chromium - Google Patents
Process for chromium electroplating using electrolytic solutions containing trivalent chromium Download PDFInfo
- Publication number
- US3649479A US3649479A US792787*A US3649479DA US3649479A US 3649479 A US3649479 A US 3649479A US 3649479D A US3649479D A US 3649479DA US 3649479 A US3649479 A US 3649479A
- Authority
- US
- United States
- Prior art keywords
- chromium
- electroplating
- barium
- solution
- solutions containing
- 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000011651 chromium Substances 0.000 title abstract description 20
- 238000009713 electroplating Methods 0.000 title abstract description 19
- 229910052804 chromium Inorganic materials 0.000 title abstract description 18
- 238000000034 method Methods 0.000 title abstract description 10
- 239000008151 electrolyte solution Substances 0.000 title description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 13
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 6
- 159000000009 barium salts Chemical class 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 14
- 238000007747 plating Methods 0.000 description 8
- 229910001422 barium ion Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 150000001553 barium compounds Chemical class 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical class O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
-
- 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
Definitions
- This invention relates to a process for chromium electroplating using electrolytic solutions containing trivalent chromium.
- the electrolytes containing trivalent chromium used for electroplating purposes are subject to variations in the yield of the chromium deposited by the electric current. These variations are due to the formation of parasitic hexavalent chromium in the electrolytic bath, the formation of which increases during the course of the operation.
- the hexavalent chromium diminishes the yield and reduces the quality and the purity of the chromium plating, thereby making the electrolyte unfit for further plating chromium.
- the work of the ap plicant has confirmed these findings. In effect, when hexavalent chromium is introduced into electrolytic solutions containing trivalent chromium, the yield of the chromium plating is lowered and eventually becomes zero.
- the applicant has discovered that by introducing into the electrolytic (plating) bath a compound for rendering insoluble the hexavalent chromium (said hexavalent chromium usually being present in the form of a chromium anhydride C-rO the amount of the hexavalent chromium dissolved in the bath can be reduced or substantially reduced, whereby the electroplating can then be conducted normally with the electrolytic solutions of chromium (III) providing stable electrochemical characteristics.
- the present invention has for its objective a process for substantially eliminating or limiting the presence of soluble hexavalent chromium in electroplating solutions containing trivalent chromium by adding, before or during the electroplating operation, a suitable quantity of a barium compound.
- the barium compound can be added in soluble or as a solid compound. Said addition can be continuous. The amount of the barium compound added will be selected so as to enable the plating operation to continue in an effective manner.
- the insoluble chromate of barium thereby formed are eventually removed from the electroplating bath by continuous or noncontinuous filtration or by any other means, such as centrifuging, decanting, etc.
- the barium salt will be utilized preferably in the form of a convenient salt which is soluble in the electrolytic solution, such as: chloride, nitrate, formate, acetate, oxalate.
- a quantity of barium ions equal to about 10% of the stoichiometric amount to the chromium ions in solution being sufiicient to prevent the presence of chromium (VI) in the electroplating solution.
- the barium salt can be added in an amount to give an excess of barium ions in the solution but this provides no advantageous result and is not necessary.
- the process according to the present invention is in principle limited to the use of electrolytic solutions of trivalent chromium, free of sulfate ions and which have a pH above 2.5. If sulfate ions were present, there would be formed a BaSO, precipitate, which is more insoluble than BaCrO, and eventually if these sulfate ions are present such as impurities e.g. it is necessary to take it into account. Barium chromate is soluble in moderately strong acid (pH 2.5) so the electroplating solution must not be strongly acid.
- the present invention also has for its ojective the products obtained by such an electrolytic treatment.
- EXAMPLE II A procedure for brush tampon plating etc. type was carried out using a platinum anode and a density of current of 150 amp./dm. Chromium metal was effectively plated using the following plating solution.
- the quantity of barium present was suflicient to hinder the formation of chromium (VI). It corresponded to about 20% of the stiochiometric quantity equivalent to the chromium in the solution. The presence of the ammonium salts hindered the precipitation of barium oxalate.
- a chromium electroplating process utilizing an electroplating solution of chromium (I-II) salt, the solution being substantially free of sulfate ions and having a pH above 2.5, the improvement comprising the step of maintaining in said electroplating solution a concentration of barium ions to chromium ions in the range of 1:10 to 1:1 in order to precipitate hexavalent chromium ions formed in the solution during the plating process.
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)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR137944 | 1968-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3649479A true US3649479A (en) | 1972-03-14 |
Family
ID=8645281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US792787*A Expired - Lifetime US3649479A (en) | 1968-01-30 | 1969-01-21 | Process for chromium electroplating using electrolytic solutions containing trivalent chromium |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US3649479A (en)) |
| JP (1) | JPS4832891B1 (en)) |
| BE (1) | BE726828A (en)) |
| CH (1) | CH498940A (en)) |
| DE (1) | DE1903373C3 (en)) |
| DK (1) | DK133832B (en)) |
| ES (1) | ES362632A1 (en)) |
| FR (1) | FR1563847A (en)) |
| GB (1) | GB1253732A (en)) |
| LU (1) | LU57786A1 (en)) |
| NL (1) | NL162147C (en)) |
| SE (1) | SE354489B (en)) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030124483A1 (en) * | 2001-10-24 | 2003-07-03 | Weitao Jia | Dental filling material |
| US20070227895A1 (en) * | 2006-03-31 | 2007-10-04 | Bishop Craig V | Crystalline chromium deposit |
| US20080169199A1 (en) * | 2007-01-17 | 2008-07-17 | Chang Gung University | Trivalent chromium electroplating solution and an electroplating process with the solution |
| US20090211914A1 (en) * | 2008-02-21 | 2009-08-27 | Ching-An Huang | Trivalent Chromium Electroplating Solution and an Operational Method Thereof |
| US8187448B2 (en) | 2007-10-02 | 2012-05-29 | Atotech Deutschland Gmbh | Crystalline chromium alloy deposit |
| US20160362792A1 (en) * | 2015-06-11 | 2016-12-15 | Hideo Yoshida | Film-forming structure on work and film-forming method on work |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51494U (en)) * | 1974-06-18 | 1976-01-06 | ||
| GB2034354B (en) * | 1978-11-11 | 1982-12-01 | Ibm | Elimination of anode hydrogen cyanide formation in trivalent chromium plating |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB235548A (en) * | 1925-05-26 | 1926-04-22 | Mayer & Sohn J | A process for the recovery of chromium as chromate from chromiferous waste materials resulting from the leather industry |
| US1838777A (en) * | 1928-03-26 | 1931-12-29 | Ternstedt Mfg Co | Chromium plating |
| US2088615A (en) * | 1932-06-29 | 1937-08-03 | Schlotter Max | Electrodeposition of chromium |
-
1968
- 1968-01-30 FR FR137944A patent/FR1563847A/fr not_active Expired
-
1969
- 1969-01-13 BE BE726828A patent/BE726828A/fr unknown
- 1969-01-15 CH CH46569A patent/CH498940A/fr not_active IP Right Cessation
- 1969-01-16 DK DK22169AA patent/DK133832B/da not_active IP Right Cessation
- 1969-01-16 LU LU57786D patent/LU57786A1/xx unknown
- 1969-01-17 GB GB2911/69A patent/GB1253732A/en not_active Expired
- 1969-01-17 ES ES362632A patent/ES362632A1/es not_active Expired
- 1969-01-21 US US792787*A patent/US3649479A/en not_active Expired - Lifetime
- 1969-01-21 NL NL6901002.A patent/NL162147C/xx not_active IP Right Cessation
- 1969-01-23 DE DE1903373A patent/DE1903373C3/de not_active Expired
- 1969-01-29 JP JP44006249A patent/JPS4832891B1/ja active Pending
- 1969-01-30 SE SE01253/69A patent/SE354489B/xx unknown
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030124483A1 (en) * | 2001-10-24 | 2003-07-03 | Weitao Jia | Dental filling material |
| 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 |
| US20080169199A1 (en) * | 2007-01-17 | 2008-07-17 | Chang Gung University | Trivalent chromium electroplating solution and an electroplating process with the solution |
| US20100155256A1 (en) * | 2007-01-17 | 2010-06-24 | Chang Gung University | Electroplating Process for Using Trivalent Chromium Electroplating Solution |
| US8187448B2 (en) | 2007-10-02 | 2012-05-29 | Atotech Deutschland Gmbh | Crystalline chromium alloy deposit |
| US20090211914A1 (en) * | 2008-02-21 | 2009-08-27 | Ching-An Huang | Trivalent Chromium Electroplating Solution and an Operational Method Thereof |
| US20160362792A1 (en) * | 2015-06-11 | 2016-12-15 | Hideo Yoshida | Film-forming structure on work and film-forming method on work |
Also Published As
| Publication number | Publication date |
|---|---|
| DK133832C (en)) | 1977-01-17 |
| NL6901002A (en)) | 1969-08-01 |
| DE1903373C3 (de) | 1979-06-28 |
| JPS4832891B1 (en)) | 1973-10-09 |
| SE354489B (en)) | 1973-03-12 |
| DE1903373A1 (de) | 1969-08-28 |
| NL162147B (nl) | 1979-11-15 |
| DK133832B (da) | 1976-07-26 |
| DE1903373B2 (de) | 1978-10-26 |
| ES362632A1 (es) | 1970-11-01 |
| LU57786A1 (en)) | 1969-08-11 |
| FR1563847A (en)) | 1969-04-18 |
| GB1253732A (en) | 1971-11-17 |
| NL162147C (nl) | 1980-04-15 |
| BE726828A (fr) | 1969-07-14 |
| CH498940A (fr) | 1970-11-15 |
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