US2938842A - Electrodeposition of fe-cr alloy - Google Patents
Electrodeposition of fe-cr alloy Download PDFInfo
- Publication number
- US2938842A US2938842A US799413A US79941359A US2938842A US 2938842 A US2938842 A US 2938842A US 799413 A US799413 A US 799413A US 79941359 A US79941359 A US 79941359A US 2938842 A US2938842 A US 2938842A
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- US
- United States
- Prior art keywords
- mol
- cathode
- electrodeposition
- solution
- alloy
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- 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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- 229910000599 Cr alloy Inorganic materials 0.000 title claims description 3
- 238000004070 electrodeposition Methods 0.000 title description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 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 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- 238000009713 electroplating Methods 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910017060 Fe Cr Inorganic materials 0.000 description 5
- 229910002544 Fe-Cr Inorganic materials 0.000 description 5
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 5
- -1 iron ion Chemical class 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 229910000604 Ferrochrome Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001430 chromium ion Inorganic materials 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Definitions
- the present invention relates to alloy plating, and more particularly, to electrodeposition of a FeCr alloy on a basis metal in an aqueous plating bath.
- the invention comprises immersing an anode and a cathodic metal into an aqueous plating bath containing bivalent or trivalent chromium ion, bivalent iron ion, and formic acid or a salt thereof, and subjecting the cathodic metal to electrodepositing a FeCr alloy.
- the electrodeposition of chromium is carried out in the hexavalent chromium electroplating bath consisting of chromic anhydride and sulfuric acid.
- the electrodeposition of chromium in the trivalent chromium electrolyte bath is also known.
- the electrodeposition of a Fe-Cr alloy plate has heretofore never been accomplished, because hydrogen evolves at the cathode and oxygen evolves at the anode in the electrodeposition of chromium in which high current densities and high voltage are used so that the hydrogen ion concentration at the cathode decreases, which, it is believed, results in the formation and precipitation of iron hydroxide at the electrodeposited plate surface due to the excess of a hydroxyl group.
- the hydroxide thereof tends to precipitate and impart a greater adverse effect to the electrodeposited plate surface than when iron ions are present as a bivalent state due to the fact that the trivalent iron hydroxide has a less solubility-product than that of bivalent iron. From this point of view, it is preferable that the electroplating bath be of a reducing nature.
- the electroplating bath of hexavalent, trivalent, and bivalent chromium, respectively.
- the electroplating bath of less atomic value is of a reducing nature.
- the electroplating bath of either bivalent or trivalent chromium for the electrodeposition of a Fe-Cr alloy plate since it imparts a reducing nature thereto.
- the bivalent chromium of the bivalent chromium electroplating bath is easily oxidized by the oxygen prevalent in the electroplating tank to the trivalent chromium, therefore it is a disadvantage that the electroplating operation has to be performed in the reducing bath.
- a buffer agent which is sufiiciently strong to inhibit the decrease of hydrogen ion concentration at the cathode in spite of the evolution of hydrogen at the cathode, should be added to the electroplating bath.
- formic acid and salts thereof are effective addition agents which impart a strong bufier function as well as a reducing "ice action to the electroplating bath. These addition agents are effective because they have both reducing and buffer actions. It is to be understood that distinct addition agents, one having a reducing action only and another having a buffer action only may be employed together in place of one addition agent having both actions.
- the electrodeposition of a Fe--Cr alloy plate on the basis metal can be accomplished by electrolyzing in the electroplating bath of either bivalent or trivalent chromium added with the addition agent of the character described and also with bivalent iron ions.
- the Fe-Cr alloy electrodeposited metallic sheet produced by the process of the invention is further improved in the uniformity of the alloy plate and also in corrosion resistance by the hot diffusion treatment, which results in the production of an alloy plated metallic sheet almost equivalent to a stainless steel sheet.
- a method of electrodepositing a FeCr alloy plate on a metallic cathode which comprises making an article to be plated the cathode in an aqueous solution, said solution consisting essentially of 0.5 mol/l. of trivalent chromium sulfate, 4.0 mol/l. of urea, 3.0 mol/l. of ammonium sulfate, 0.05 mol/l. of ferrous sulphate, 0.1 mol/l. of formic acid, and the balance water, maintaining the temperature of the solution 25 C., maintaining pH of the solution 1.6, and passing an electric current of 30 amp/sq. decimeter therethrough between an anode and said cathode.
- a method of electrodepositing a Fe-Cr plate on a metallic cathode which comprises making an article to be plated the cathode in an aqueous solution, said solution consisting essentially of 0.5 mol/l. of trivalent chromium sulfate, 4.0 mol/l. of urea, 3.0 mol/l. of ammonium sulfate, 0.05 mol/l. of ferrous sulphate, 0.1 mol/l. of formate, and the balance water, maintaining the temperature of the solution 25 C., maintaining pH of the solution 1.6, and passing an electric current of 30 amp/sq. decimeter therethrough between an anode and said cathode.
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)
Description
United States Patent ELECTRODEPOSITION 0F Fe-Cr ALLOY Hajime Nitto, Wakamatsu City, Fukuoka, Japan, assignor to Yawata Iron and Steel Co., Ltd., Tokyo, Japan, a corporation of Japan No Drawing. Filed Mar. 16, 1959, Ser. No. 799,413
2 Claims. (Cl. 204-43) The present invention relates to alloy plating, and more particularly, to electrodeposition of a FeCr alloy on a basis metal in an aqueous plating bath.
Briefly, the invention comprises immersing an anode and a cathodic metal into an aqueous plating bath containing bivalent or trivalent chromium ion, bivalent iron ion, and formic acid or a salt thereof, and subjecting the cathodic metal to electrodepositing a FeCr alloy.
Heretofore the electrodeposition of chromium is carried out in the hexavalent chromium electroplating bath consisting of chromic anhydride and sulfuric acid. The electrodeposition of chromium in the trivalent chromium electrolyte bath is also known.
In either case, however, the presence of iron ion in the plating bath gives an adverse effect to the electrodeposition of chromium so that an excellent electrodeposited coating on a base metal has never been attained. Ac-
cordingly, the electrodeposition of a Fe-Cr alloy platehas heretofore never been accomplished, because hydrogen evolves at the cathode and oxygen evolves at the anode in the electrodeposition of chromium in which high current densities and high voltage are used so that the hydrogen ion concentration at the cathode decreases, which, it is believed, results in the formation and precipitation of iron hydroxide at the electrodeposited plate surface due to the excess of a hydroxyl group.
It is also believed that if trivalent iron ions are present in the electroplating bath the hydroxide thereof tends to precipitate and impart a greater adverse effect to the electrodeposited plate surface than when iron ions are present as a bivalent state due to the fact that the trivalent iron hydroxide has a less solubility-product than that of bivalent iron. From this point of view, it is preferable that the electroplating bath be of a reducing nature.
Three kinds of the electroplating bath are to be considered: of hexavalent, trivalent, and bivalent chromium, respectively. However, it is clear that the electroplating bath of less atomic value is of a reducing nature. Hence it is advantageous to employ the electroplating bath of either bivalent or trivalent chromium for the electrodeposition of a Fe-Cr alloy plate since it imparts a reducing nature thereto. In this case, however, the bivalent chromium of the bivalent chromium electroplating bath is easily oxidized by the oxygen prevalent in the electroplating tank to the trivalent chromium, therefore it is a disadvantage that the electroplating operation has to be performed in the reducing bath.
Accordingly, a buffer agent, which is sufiiciently strong to inhibit the decrease of hydrogen ion concentration at the cathode in spite of the evolution of hydrogen at the cathode, should be added to the electroplating bath.
After extensive research, I have discovered that formic acid and salts thereof are effective addition agents which impart a strong bufier function as well as a reducing "ice action to the electroplating bath. These addition agents are effective because they have both reducing and buffer actions. It is to be understood that distinct addition agents, one having a reducing action only and another having a buffer action only may be employed together in place of one addition agent having both actions.
In accordance with the invention, the electrodeposition of a Fe--Cr alloy plate on the basis metal can be accomplished by electrolyzing in the electroplating bath of either bivalent or trivalent chromium added with the addition agent of the character described and also with bivalent iron ions.
The operating conditions embodying the invention are as follows:
Anode-Magnetic iron oxide electrode Cathode-Soft steel sheet Bath composition A bright alloy plating consisting of CrzFe=50z50 is obtained on the base metal by subjecting it to electrodeposition under the above operating conditions. Cathode current efficiency is about 8% The Fe-Cr alloy electrodeposited metallic sheet produced by the process of the invention is further improved in the uniformity of the alloy plate and also in corrosion resistance by the hot diffusion treatment, which results in the production of an alloy plated metallic sheet almost equivalent to a stainless steel sheet.
I claim:
1. A method of electrodepositing a FeCr alloy plate on a metallic cathode which comprises making an article to be plated the cathode in an aqueous solution, said solution consisting essentially of 0.5 mol/l. of trivalent chromium sulfate, 4.0 mol/l. of urea, 3.0 mol/l. of ammonium sulfate, 0.05 mol/l. of ferrous sulphate, 0.1 mol/l. of formic acid, and the balance water, maintaining the temperature of the solution 25 C., maintaining pH of the solution 1.6, and passing an electric current of 30 amp/sq. decimeter therethrough between an anode and said cathode.
2. A method of electrodepositing a Fe-Cr plate on a metallic cathode which comprises making an article to be plated the cathode in an aqueous solution, said solution consisting essentially of 0.5 mol/l. of trivalent chromium sulfate, 4.0 mol/l. of urea, 3.0 mol/l. of ammonium sulfate, 0.05 mol/l. of ferrous sulphate, 0.1 mol/l. of formate, and the balance water, maintaining the temperature of the solution 25 C., maintaining pH of the solution 1.6, and passing an electric current of 30 amp/sq. decimeter therethrough between an anode and said cathode.
References Cited in the file of this patent UNITED STATES PATENTS 2,693,444 Snavely et al. Nov. 2, 1954 2,739,108 Quaely Mar. 20, 1956 2,766,196 Yoshida Oct. 9, 1956 2,822,326 Safranek Feb. 4, 1958 2,824,829 Quaely Feb. 25, 1958
Claims (1)
1. A METHOD OF ELECTRODEPOSITING A FE-CR ALLOY PLATE ON A METALLIC CATHODE WHICH COMPRISES MAKING AN ARTICLE TO BE PLATED THE CATHODE IN AN AQUEOUS SOLUTION, SAID SOLUTION CONSISTING ESSENTIALLY OF 0.5 MOL/1. OF TRIVALENT CHROMIUM SULFATE, 4.0 MOL/1. OF UREA, 3.0 MOL/1. OF AMMONIUM SULFATE, 4.0 MOL/1. OF FERROUS SULPHATE, 0.1 MOL/1. OF FORMIC ACID, AND THE BALANCE WATER, MAINTAINING THE TEMPERATURE OF THE SOLUTION 25*C., MAINTAINING PH OF THE SOLUTION 1.6, AND PASSING AN ELECTRIC CURRENT OF 30 AMP./SQ. DECIMETER THRETHROUGH BETWEEN AN ANODE AND SAID CATHODE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US799413A US2938842A (en) | 1959-03-16 | 1959-03-16 | Electrodeposition of fe-cr alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US799413A US2938842A (en) | 1959-03-16 | 1959-03-16 | Electrodeposition of fe-cr alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2938842A true US2938842A (en) | 1960-05-31 |
Family
ID=25175852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US799413A Expired - Lifetime US2938842A (en) | 1959-03-16 | 1959-03-16 | Electrodeposition of fe-cr alloy |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2938842A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1982003095A1 (en) * | 1981-03-09 | 1982-09-16 | Battelle Development Corp | High-rate chromium alloy plating |
Citations (5)
| 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 |
| US2739108A (en) * | 1952-06-14 | 1956-03-20 | Westinghouse Electric Corp | Electroplating chromium-nickel alloy coatings |
| US2766196A (en) * | 1953-11-09 | 1956-10-09 | Yoshida Tadashi | Process for the electrodeposition of iron-chromium alloys |
| US2822326A (en) * | 1955-03-22 | 1958-02-04 | Rockwell Spring & Axle Co | Bright chromium alloy plating |
| US2824829A (en) * | 1953-02-27 | 1958-02-25 | Westinghouse Electric Corp | Electrodepositing black chromiumvanadium coatings and members therewith |
-
1959
- 1959-03-16 US US799413A patent/US2938842A/en not_active Expired - Lifetime
Patent Citations (5)
| 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 |
| US2739108A (en) * | 1952-06-14 | 1956-03-20 | Westinghouse Electric Corp | Electroplating chromium-nickel alloy coatings |
| US2824829A (en) * | 1953-02-27 | 1958-02-25 | Westinghouse Electric Corp | Electrodepositing black chromiumvanadium coatings and members therewith |
| US2766196A (en) * | 1953-11-09 | 1956-10-09 | Yoshida Tadashi | Process for the electrodeposition of iron-chromium alloys |
| US2822326A (en) * | 1955-03-22 | 1958-02-04 | Rockwell Spring & Axle Co | Bright chromium alloy plating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1982003095A1 (en) * | 1981-03-09 | 1982-09-16 | Battelle Development Corp | High-rate chromium alloy plating |
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