US2432894A - Electrodeposition of iron-tungsten alloys - Google Patents
Electrodeposition of iron-tungsten alloys Download PDFInfo
- Publication number
- US2432894A US2432894A US496478A US49647843A US2432894A US 2432894 A US2432894 A US 2432894A US 496478 A US496478 A US 496478A US 49647843 A US49647843 A US 49647843A US 2432894 A US2432894 A US 2432894A
- Authority
- US
- United States
- Prior art keywords
- iron
- tungsten
- bath
- electrodeposition
- tungsten alloys
- 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
- 229910001080 W alloy Inorganic materials 0.000 title description 7
- 238000004070 electrodeposition Methods 0.000 title description 5
- JHOPGIQVBWUSNH-UHFFFAOYSA-N iron tungsten Chemical group [Fe].[Fe].[W] JHOPGIQVBWUSNH-UHFFFAOYSA-N 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 12
- 229910052721 tungsten Inorganic materials 0.000 description 11
- 239000010937 tungsten Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- GXBKELQWVXYOPN-UHFFFAOYSA-N iron tungsten Chemical compound [W][Fe][W] GXBKELQWVXYOPN-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000007747 plating Methods 0.000 description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution 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
- This invention relates to the electrodeposition of iron-tungsten alloys.
- An object of the invention is to improve the electrodeposition of iron-tungsten alloys, and the methods and compositions used therefor.
- An electrodeposit of iron containing small percentages of tungsten can provide a highly desirable facing for many commercial applications, such as where a hard or abrasion resistant surface is desired. It also has some advantages where corrosion resistance is required.
- Tungstates have a marked effect on an iron plating bath. A rapid drop in current efficiency occurs as the tungstate concentration is increased. There is also a tendency for non-metallic deposits to be produced. This is perhaps due to the formation of a film on the cathode allowing passage of hydrogen ions but not the heavier metallic ions, which may be deposited in the film as insoluble basic compounds.
- an iron plating bath containing tungstates such as sodium tungstate, can be electrolyzed to obtain smooth, adherent metallic deposits of iron-tungsten alloys on the cathode.
- the percentage of tungsten in the deposit can be increased by agitation or by rotating the cathode.
- One suitable iron-tungsten plating bath contained:
- a standard sodium tungstate solution acidified to about pH 3 with sulfuric acid, was used for addition of tungsten to the iron bath.
- the acidification of the tungstate solution was necessary to prevent the precipitation of an insoluble iron tungstate upon the addition of sodium tungstate to the ferrous sulfate solution.
- the bath as made up had a pH of about 3, and it was adjusted to lower pH values by the addition of 3.5 N sulfuric acid.
- Plating was carried out at a temperature of about 75 C. using an iron anode.
- the cathode basis metal was copper although bras-s, iron, steel, nickel, or any of the other common basis metals either plain or with a preliminary flash or plated coating of copper may be used.
- composition of the resulting electrodeposit and its character was dependent upon the current density and the rate of motion of the oathode or agitation of the solution.
- the current efficiency of alloy deposition is very poor at the lower current densities and it increases rapidly with increased current density.
- the alloy plates obtained at the higher current densities were metallic in appearance, whereas those obtained at lower current densities were much less metallic and perhaps contained oxides.
- a current density between 8 and 12 amperes per square decimeter is preferred for still baths and results in a deposit containing about 8 to 12% by weight of tungsten. By rotating the cathode the percentage of tungsten in the alloy deposit can be increased, however with a decrease in cathode efiiciency.
- the conditions of electrolysis and composition of the bath may be varied to obtain different proportions of tungsten in the alloy deposit. Deposits containing from a trace up to 25% or more of tungsten can be obtained.
- the amount of tungsten in the bath may be between 0.2 and 10 grams per liter and is added as sodium tungstate or other soluble compounds of tungsten, such as potassium tungstate, ammonium tungstate, or phospho tungstic acid. Usually 1 to 2 gram of tungsten per liter is preferred.
- the ferrous ammonium sulfate can also be varied widely in concentration.
- the pH of the bath should be maintained between 1.5 and 3, the preferred acidity being a pH of 2 although higher pH values, such as a pH of 2.5, increase the current efficiency somewhat.
- the iron-tungsten alloy plate can be used to improve the appearance of the basis metal, to improve its corrosion resistance properties and to produce a hard durable surface for building up worn parts. It could also be used to produce an alloy surface which is suitable for special treatment such as nitriding, oarbonizing, and the like.
- the method of electrodepositing an irontungsten alloy which comprises passing an electric current through a bath consisting of an aqueous solution of 350 g. of ferrous ammonium sulfate, 1 g. of sodium tungstate and 3.5 N sulfuric acid in one liter of the solutiomsaid solution having a pH of about 2.0, and the electrodeposition being performed at about 75 C.
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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
Patented Dec. 16, 1947 ELECTRODEPOSITION F IRON-TUNGSTEN ALLOYS Matthew Leslie Holt, Madison, Wis., and Rodney E. Black, Philadelphia, Pa, assignors to P. R. Mallory & 00., Inc., Indianapolis, Ind., acorporation of Delaware No Drawing. Application July 28, 1943, Serial No.496,478
2 Claims. 1
This invention relates to the electrodeposition of iron-tungsten alloys.
An object of the invention is to improve the electrodeposition of iron-tungsten alloys, and the methods and compositions used therefor.
Other objects of the invention will be apparent from the description and claims.
An electrodeposit of iron containing small percentages of tungsten can provide a highly desirable facing for many commercial applications, such as where a hard or abrasion resistant surface is desired. It also has some advantages where corrosion resistance is required.
Tungstates have a marked effect on an iron plating bath. A rapid drop in current efficiency occurs as the tungstate concentration is increased. There is also a tendency for non-metallic deposits to be produced. This is perhaps due to the formation of a film on the cathode allowing passage of hydrogen ions but not the heavier metallic ions, which may be deposited in the film as insoluble basic compounds.
We have found, however, that under certain conditions an iron plating bath containing tungstates, such as sodium tungstate, can be electrolyzed to obtain smooth, adherent metallic deposits of iron-tungsten alloys on the cathode.
We have also found that the percentage of tungsten in the deposit can be increased by agitation or by rotating the cathode.
One suitable iron-tungsten plating bath contained:
Grams per liter Ferrous ammonium sulfate 350 Sodium tungstate 1 3.5 N sulfuric acid to bring pH to 2 The bath was prepared from stock solutions of ferrous sulfate and ammonium sulfate. The ferrous sulfate solution was treated with iron powder and then acidified with sulfuric acid to a pH of about 2; it was kept in the ferrous state by the presence of metallic iron until used for preparing a bath.
A standard sodium tungstate solution, acidified to about pH 3 with sulfuric acid, was used for addition of tungsten to the iron bath. The acidification of the tungstate solution was necessary to prevent the precipitation of an insoluble iron tungstate upon the addition of sodium tungstate to the ferrous sulfate solution. The bath as made up had a pH of about 3, and it was adjusted to lower pH values by the addition of 3.5 N sulfuric acid.
Plating was carried out at a temperature of about 75 C. using an iron anode.
The cathode basis metal was copper although bras-s, iron, steel, nickel, or any of the other common basis metals either plain or with a preliminary flash or plated coating of copper may be used.
The composition of the resulting electrodeposit and its character was dependent upon the current density and the rate of motion of the oathode or agitation of the solution.
The current efficiency of alloy deposition is very poor at the lower current densities and it increases rapidly with increased current density. The alloy plates obtained at the higher current densities were metallic in appearance, whereas those obtained at lower current densities were much less metallic and perhaps contained oxides. A current density between 8 and 12 amperes per square decimeter is preferred for still baths and results in a deposit containing about 8 to 12% by weight of tungsten. By rotating the cathode the percentage of tungsten in the alloy deposit can be increased, however with a decrease in cathode efiiciency.
In general, current densities between 2 and 20 amp./dm. are useful, depending on the temperature, composition and rate of agitation.
The conditions of electrolysis and composition of the bath may be varied to obtain different proportions of tungsten in the alloy deposit. Deposits containing from a trace up to 25% or more of tungsten can be obtained.
The amount of tungsten in the bath may be between 0.2 and 10 grams per liter and is added as sodium tungstate or other soluble compounds of tungsten, such as potassium tungstate, ammonium tungstate, or phospho tungstic acid. Usually 1 to 2 gram of tungsten per liter is preferred. The ferrous ammonium sulfate can also be varied widely in concentration.
The pH of the bath should be maintained between 1.5 and 3, the preferred acidity being a pH of 2 although higher pH values, such as a pH of 2.5, increase the current efficiency somewhat.
Good deposits are best obtained at elevated temperatures, the range between 40 C. and 95 C. being most suitable. The current efliciency reaches a maximum at about 50 C. and then falls ofi somewhat for higher temperatures. Deposits obtained from the bath at C. had the best appearance. The amount of tungsten in the alloy deposit increases somewhat regularly with increase of bath temperature.
The iron-tungsten alloy plate can be used to improve the appearance of the basis metal, to improve its corrosion resistance properties and to produce a hard durable surface for building up worn parts. It could also be used to produce an alloy surface which is suitable for special treatment such as nitriding, oarbonizing, and the like.
While specific embodiments of the invention have been described, it is intended to cover the invention broadly within the spirit and scope of the appended claims.
What is claimed is:
1. The method of electrodepositing an irontungsten alloy which comprises passing an electric current through a bath consisting of an aqueous solution of 350 g. of ferrous ammonium sulfate, 1 g. of sodium tungstate and 3.5 N sulfuric acid in one liter of the solutiomsaid solution having a pH of about 2.0, and the electrodeposition being performed at about 75 C.
2. A plating bath for iron-tungsten alloy plating, said bath consisting of an aqueous solution REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Name Date Armstrong et a1. May 30, 1939 OTHER REFERENCES Transactions of the American Electrochemical Society, vol. 82, pages 205-226, 1942.
Number
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US496478A US2432894A (en) | 1943-07-28 | 1943-07-28 | Electrodeposition of iron-tungsten alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US496478A US2432894A (en) | 1943-07-28 | 1943-07-28 | Electrodeposition of iron-tungsten alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2432894A true US2432894A (en) | 1947-12-16 |
Family
ID=23972807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US496478A Expired - Lifetime US2432894A (en) | 1943-07-28 | 1943-07-28 | Electrodeposition of iron-tungsten alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2432894A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2461933A (en) * | 1947-12-24 | 1949-02-15 | Paul T Smith | Rhodium alloy coatings and method of making same |
| US2546150A (en) * | 1946-11-08 | 1951-03-27 | Brenner Abner | Method for securing adhesion of electroplated coatings to a metal base |
| US20080149297A1 (en) * | 2005-02-02 | 2008-06-26 | Keiji Nakai | Product Having Improved Zinc Erosion Resistance |
| US11208731B2 (en) * | 2017-06-09 | 2021-12-28 | The Boeing Company | Iron tungsten coating formulations and processes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2160321A (en) * | 1936-02-06 | 1939-05-30 | Tungsten Electrodeposit Corp | Electrodeposition of tungsten alloys |
-
1943
- 1943-07-28 US US496478A patent/US2432894A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2160321A (en) * | 1936-02-06 | 1939-05-30 | Tungsten Electrodeposit Corp | Electrodeposition of tungsten alloys |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2546150A (en) * | 1946-11-08 | 1951-03-27 | Brenner Abner | Method for securing adhesion of electroplated coatings to a metal base |
| US2461933A (en) * | 1947-12-24 | 1949-02-15 | Paul T Smith | Rhodium alloy coatings and method of making same |
| US20080149297A1 (en) * | 2005-02-02 | 2008-06-26 | Keiji Nakai | Product Having Improved Zinc Erosion Resistance |
| US7896061B2 (en) * | 2005-02-02 | 2011-03-01 | Nomura Plating Co., Ltd. | Product having improved zinc erosion resistance |
| US11208731B2 (en) * | 2017-06-09 | 2021-12-28 | The Boeing Company | Iron tungsten coating formulations and processes |
| US11732375B2 (en) | 2017-06-09 | 2023-08-22 | The Boeing Company | Iron tungsten coating formulations and processes |
| US11773502B2 (en) | 2017-06-09 | 2023-10-03 | The Boeing Company | Iron tungsten coating formulations and processes |
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