US2428404A - Electrodeposition of molybdenumcobalt alloys - Google Patents

Electrodeposition of molybdenumcobalt alloys Download PDF

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Publication number
US2428404A
US2428404A US532526A US53252644A US2428404A US 2428404 A US2428404 A US 2428404A US 532526 A US532526 A US 532526A US 53252644 A US53252644 A US 53252644A US 2428404 A US2428404 A US 2428404A
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cobalt
per liter
grams per
molybdenum
alloys
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US532526A
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Leonard F Yntema
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President & Board Of Trustees
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President & Board Of Trustees
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Priority to US532526A priority Critical patent/US2428404A/en
Priority to FR913357D priority patent/FR913357A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • 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

Definitions

  • the invention relates to the electrocodeposition of an alloy of molybdenum and a metal of the class consisting of cobalt and iron from aqueous solutions.
  • alloys may be codeposited from aqueous solutions when the molybdenum is present in the solution in the hexavalent form, when free alkali metal hydroxide is present and when there is an addition agent capable of holding the cobalt or iron in solution.
  • the molybdenum is added to the water in the form of the alkali metal salt, or, if desired, it may be added as molybdic acid or its anhydride, in which case it is converted into the molybdate form by the free alkali hydroxide. It is essential that free alkali hydroxide be present in the electrolyte during the electrodeposition and it is preferable that the electrolyte also contain alkali metal carbonate.
  • the cobalt or iron is added in the form of a salt such as sulfate, chloride, etc., but to maintain the same in solution it is necessary to add an organic compound having a hydroxyl group and capable of forming complexes with the cobalt or iron. Examples of such organic compounds are sugars, glycerine, glycols and tartaric acid. Inorganic compounds such as phosphates, sulfates and cyanides will not function for this purpose. Preferably I use dextrose.
  • the electrolyte must be strongly alkaline and good deposits are obtained from a solution containing 250 grams per liter of sodium hydroxide and 80 grams per liter of sodium carbonate.
  • the current density may be varied from 0.03 ampere per square decimeter to 0.5 or higher. Deposits may be obtained at room temperatures or at higher temperatures. I have obtained satisfactory deposits on cathodes of copper and iron.
  • the molybdenum-cobalt plates are bright, very hard and adherent, and are resistant to tarnishing by the atmosphere and to the action of a 3% sodium chloride solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Description

Patente cl Oct. 7, 1 947 UNITED STATES PATENT" mm j ELECTRODEPOSITI'ON- oF MOLYBDENUM- I COBALT ALLOYS Leonard F. Yntemm Waukegan, Ill., 'assignor' to President &- Board of Trustees of St. Louis University, St. Louis, Mo'.
No Drawing, Application April 24,1944; Serial No. 532,526
The invention relates to the electrocodeposition of an alloy of molybdenum and a metal of the class consisting of cobalt and iron from aqueous solutions.
I have discovered that such alloys may be codeposited from aqueous solutions when the molybdenum is present in the solution in the hexavalent form, when free alkali metal hydroxide is present and when there is an addition agent capable of holding the cobalt or iron in solution.
In preparing the electrolyte, the molybdenum is added to the water in the form of the alkali metal salt, or, if desired, it may be added as molybdic acid or its anhydride, in which case it is converted into the molybdate form by the free alkali hydroxide. It is essential that free alkali hydroxide be present in the electrolyte during the electrodeposition and it is preferable that the electrolyte also contain alkali metal carbonate. The cobalt or iron is added in the form of a salt such as sulfate, chloride, etc., but to maintain the same in solution it is necessary to add an organic compound having a hydroxyl group and capable of forming complexes with the cobalt or iron. Examples of such organic compounds are sugars, glycerine, glycols and tartaric acid. Inorganic compounds such as phosphates, sulfates and cyanides will not function for this purpose. Preferably I use dextrose.
The electrolyte must be strongly alkaline and good deposits are obtained from a solution containing 250 grams per liter of sodium hydroxide and 80 grams per liter of sodium carbonate. The current density may be varied from 0.03 ampere per square decimeter to 0.5 or higher. Deposits may be obtained at room temperatures or at higher temperatures. I have obtained satisfactory deposits on cathodes of copper and iron. The molybdenum-cobalt plates are bright, very hard and adherent, and are resistant to tarnishing by the atmosphere and to the action of a 3% sodium chloride solution.
I have been unable to obtain alloys of molybdenum with nickel, zinc, tin or bismuth. While I do not wish to be limited to any particular theory as to the operation of my process, it is my understanding that cobalt and iron function as they do because their hydroxides are slightly soluble in strong alkalies. It is possible that the hydrogen, which is discharged as atomic hydrogen along with the cobalt or ron and is dissolved in or is absorbed by them, reduces the molybdenum compounds to the metal by a secondary reaction. This picture of the mechanism of the reaction is based on the facts that no molybdenum is 5 Claims. (01. 204-43) deposited as metal unless cobalt or iron is present, that nickel does not function because its hydroxide is not soluble in the alkaline solutions, and that iron functions better when in the ferric state, which should be more soluble in the strong alkali than the ferrous form. It is my understanding that atomic hydrogen does not dissolve as readily in zinc, tin, and bismuth and therefore these metals do not function.
The following is an example of a suitable electrolyte for codeposition of an alloy of molybdenum and cobalt in accordance with my invention:
What I claim as my invention is:
1. The process for electrodepositing an alloy of molybdenum and a metal of the class consisting of cobalt and iron which consists in passing a current between an anode and the work to be plated as a cathode in an aqueous electrolyte consisting essentially of 10 to 30 grams per liter of a hexavalent molybdate compound, 5 to 15 grams per liter of a soluble compound of a metal of the class consisting of cobalt and iron, to 300 grams per liter of free alkali metal hydroxide and 10 to 30 grams per liter of an organic compound having a hydroxyl group of the class consisting of sugars, glycerine, glycols and tartaric acid.
2. The process for electrocodepositing an alloy of molybdenum and cobalt which consists in passing a current between an anode and the work to be plated as a cathode in an aqueous electrolyte consisting essentially of 10 to 30 grams per liter of a hexavalent molybdate compound, 5 to 15 grams per liter of a soluble cobalt compound, 100 to 300 grams per liter of free alkali metal hy- .droxide, and 10 to 30 grams per liter f an organic compound having a hydroxyl group of the class consisting of sugars, glycerine, glycols and tartaric acid.
3. The process for electrocodepositing an alloy of molybdenum and cobalt which consists in passing a current between an anode and the work to be plated as a cathode in an aqueous electrolyte consisting essentially of alkali metal molybdate from 10 to 30 grams per liter, cobalt sulfate 5 to 15 grams per liter, alkali metal hydroxide 100 to 300 grams per liter, alkali metal carbonate 40 to 120 grams per liter and an organic Sodium molybdate grams Cobalt sulfate do 1 Sodium hydroxide do 250 Sodium carbonate do 80' Dextrose do to 30 5. The process for electrocodepositing an alloy of molybdenum and cobalt which consists ln'pa ss ing a current between an anode and the work to V be plated as a cathode in an aqueous electrolyte consisting essentially of alkali metal molybdate from 10 to grams per liter, cobalt sulfate 5 to 15 grams per liter, alkali metal hydroxide to 300 grams per liter, alkali metal carbonate 40 to grams per liter, and dextrose 10 td 30;
grams per liter. 7 a I LEONARD F.- YNTEMA.
REFERENCES cI'rEn Water liters The following references are of record in the a file of this patent: UNITED STATES PATENTS Number Name Date 1,885,700 V Fink Nov. 1, 1932 FOREIGN PATENTS Number Country Date 1,183 Great Britain 1852 582,528
Germany May 22, 1934
US532526A 1944-04-24 1944-04-24 Electrodeposition of molybdenumcobalt alloys Expired - Lifetime US2428404A (en)

Priority Applications (2)

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US532526A US2428404A (en) 1944-04-24 1944-04-24 Electrodeposition of molybdenumcobalt alloys
FR913357D FR913357A (en) 1944-04-24 1945-08-14 Process for the preparation of novel compounds, in particular of piperonylaldehyde derivatives

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2599178A (en) * 1950-03-10 1952-06-03 Wisconsin Alumni Res Found Electrodeposition of alloys of molybdenum with cobalt, nickel, and iron
US2653127A (en) * 1946-11-08 1953-09-22 Brenner Abner Methods of and baths for electrodepositing cobalt or cobalt-molybdenum alloys

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1885700A (en) * 1927-04-12 1932-11-01 Colin G Fink Electroplating and process of producing same
DE582528C (en) * 1929-06-07 1934-05-22 I G Farbenindustrie Akt Ges Process for the electrolytic production of thin, molybdenum, tungsten, vanadium, beryllium, bismuth and tantalum-containing coatings on base metals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1885700A (en) * 1927-04-12 1932-11-01 Colin G Fink Electroplating and process of producing same
DE582528C (en) * 1929-06-07 1934-05-22 I G Farbenindustrie Akt Ges Process for the electrolytic production of thin, molybdenum, tungsten, vanadium, beryllium, bismuth and tantalum-containing coatings on base metals

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2653127A (en) * 1946-11-08 1953-09-22 Brenner Abner Methods of and baths for electrodepositing cobalt or cobalt-molybdenum alloys
US2599178A (en) * 1950-03-10 1952-06-03 Wisconsin Alumni Res Found Electrodeposition of alloys of molybdenum with cobalt, nickel, and iron

Also Published As

Publication number Publication date
FR913357A (en) 1946-09-05

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