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US2835630A - Treatment of metals prior to electro-plating - Google Patents

Treatment of metals prior to electro-plating Download PDF

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Publication number
US2835630A
US2835630A US286444A US28644452A US2835630A US 2835630 A US2835630 A US 2835630A US 286444 A US286444 A US 286444A US 28644452 A US28644452 A US 28644452A US 2835630 A US2835630 A US 2835630A
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copper
metal
metals
shot
treatment
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US286444A
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Huddle Roy Alfred Ulfketel
Flint Oliver
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • C25D5/46Pretreatment of metallic surfaces to be electroplated of actinides
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • C25D5/38Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel

Definitions

  • This invention relates to the electrodeposition of metals upon metallic surfaces for the purpose of giving protection or a desired finish to the surfaces, and is concerned primarily with the preparation of such surfaces to receive electrodeposits.
  • metal surfaces are initially sand blasted to remove scale and oxide or other corrosion deposits, after which further mechanical preparation, including polishing, and an electrochemical cleaning operation are ordinarily performed to prepare the surface for the electroplating operation. It has now been observed that if such electrochemical cleaning is carried out on the metals uranium, zirconium, titanium, tantalum, niobium, molybdenum, tugsten or vanadium, electrodeposits on the surfaces so cleaned show poor adherence and give little protection to the metals. The poor quality of such deposits is believed to be due to the presence of a hydrous oxide coating on the metals, which is not removed by usual anodic electrolytic treatments and may even be induced by such treatments.
  • the object of the invention is to provide a pretreatment for the metals specified which will allow of satisfactory adherent deposits of other metals to be laid down on such metals by normal methods of electrodeposition.
  • surfaces of the metals are subjected to shot blasting preferably by ferrous metal shot to remove hydrous oxide coating normally present, and the surfaces so treated are given a coating of copper, preferably by displacement from a copper salt solution.
  • the metals are found to be relatively inert towards the atmosphere, even at raised temperatures, and to aqueous electrolytes. They may be subjected to electroplating operations by normal methods and take on electrodeposits which show good adherence.
  • the copper salt is preferably copper sulphate which is employed in aqueous solution acidified by sulphuric acid.
  • the coating of copper may result from displacement of copper by the metal alone or deposition may be assisted by passage of current between a copper electrode in the solution and the metal surface, the latter being the cathode.
  • the shot blasting besides removing hydrous oxide coatings, appear to induce some passivation of the surface, owing probably to either the presence of a very thin anhydrous oxide film (of the order of molecular thickness), or a similar film of iron compound which does not prevent or adversely affect subsequent electrodeposition on the surface.
  • Example A surface of zirconium metal is shot blasted employing 120 grit of iron and an air pressure of lbs. per square inch. Each part of the surface is subjected to action of the shot blast for approximately 30 seconds. The zirconium metal surface is then immersed in the following solution for approximately 5 minutes.
  • the zirconium with its copper coating is Washed with water and may then be arranged in a. usual plating bath, for example a nickel bath and an electrodeposit formed on it by usual methods.
  • a. usual plating bath for example a nickel bath and an electrodeposit formed on it by usual methods.
  • the copper coating applied to the metals set out above may serve not only as a protective finish to the metal until a further deposit of a protective metal is applied, but also as an aid in rolling, drawing or pressing of the metal.
  • any of the metals uranium, titanium, tantalum, niobium, molybdenum, tungsten or vanadium may be substituted for zirconium in the example with like effect.
  • a method of treating the surface of a metal of the group consisting of uranium, zirconium, titanium, tantalum, niobium, molybdenum, tungsten and vanadium which consists in the steps of subjecting the surface to shot blasting using ferrous metal shot, coating the shotblasted surface with copper, and electrodepositing upon the copper a protective metal.
  • a method of treating the surface of a metal of the group consisting of uranium, zirconium, tantanium, tantalum, niobium, molybdenum, tungsten and vanadium which consists in the steps of shot-blasting the surface employing grit of iron for approximately 30 seconds on each part of the surface, immersing the shot-blasted surface in an aqueous solution containing copper sulphate, sulphuric acid, aluminum sulphate and a surface active agent for approximately 5 minutes to form a coating of copper thereon, washing the surface, then making it the cathode in a nickel electroplating bath and forming an electrodeposit of nickel thereon.

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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

35,630 Patented May 20, 1958 TREATMENT @F NtETAl-LS PRIOR TO ELECTRGPLATEIG N Drawing. Application May 6, 1952 Serial No. 286,444
(Cl. ze a-1.5
Claims.
This invention relates to the electrodeposition of metals upon metallic surfaces for the purpose of giving protection or a desired finish to the surfaces, and is concerned primarily with the preparation of such surfaces to receive electrodeposits.
Normally in electroplating operations metal surfaces are initially sand blasted to remove scale and oxide or other corrosion deposits, after which further mechanical preparation, including polishing, and an electrochemical cleaning operation are ordinarily performed to prepare the surface for the electroplating operation. It has now been observed that if such electrochemical cleaning is carried out on the metals uranium, zirconium, titanium, tantalum, niobium, molybdenum, tugsten or vanadium, electrodeposits on the surfaces so cleaned show poor adherence and give little protection to the metals. The poor quality of such deposits is believed to be due to the presence of a hydrous oxide coating on the metals, which is not removed by usual anodic electrolytic treatments and may even be induced by such treatments.
The object of the invention is to provide a pretreatment for the metals specified which will allow of satisfactory adherent deposits of other metals to be laid down on such metals by normal methods of electrodeposition.
According to the invention surfaces of the metals are subjected to shot blasting preferably by ferrous metal shot to remove hydrous oxide coating normally present, and the surfaces so treated are given a coating of copper, preferably by displacement from a copper salt solution.
After the treatment of the invention, the metals are found to be relatively inert towards the atmosphere, even at raised temperatures, and to aqueous electrolytes. They may be subjected to electroplating operations by normal methods and take on electrodeposits which show good adherence.
The copper salt is preferably copper sulphate which is employed in aqueous solution acidified by sulphuric acid. The coating of copper may result from displacement of copper by the metal alone or deposition may be assisted by passage of current between a copper electrode in the solution and the metal surface, the latter being the cathode.
With the metals specified the shot blasting, besides removing hydrous oxide coatings, appear to induce some passivation of the surface, owing probably to either the presence of a very thin anhydrous oxide film (of the order of molecular thickness), or a similar film of iron compound which does not prevent or adversely affect subsequent electrodeposition on the surface.
The following is a preferred way of carrying the invention into efiect as applied by way of example to zirconium.
Example A surface of zirconium metal is shot blasted employing 120 grit of iron and an air pressure of lbs. per square inch. Each part of the surface is subjected to action of the shot blast for approximately 30 seconds. The zirconium metal surface is then immersed in the following solution for approximately 5 minutes.
Copper sulphate gms. per litre 200 Sulphuric acid do 48 Aluminum sulphate dou 24 Surface active agent percent 0.1
At the conclusion of the treatment the zirconium with its copper coating is Washed with water and may then be arranged in a. usual plating bath, for example a nickel bath and an electrodeposit formed on it by usual methods.
The copper coating applied to the metals set out above may serve not only as a protective finish to the metal until a further deposit of a protective metal is applied, but also as an aid in rolling, drawing or pressing of the metal.
Any of the metals uranium, titanium, tantalum, niobium, molybdenum, tungsten or vanadium may be substituted for zirconium in the example with like effect.
We claim:
1. A method of treating the surface of a metal of the group consisting of uranium, zirconium, titanium, tantalum, niobium, molybdenum, tungsten and vanadium which consists in the steps of subjecting the surface to shot blasting using ferrous metal shot, coating the shotblasted surface with copper, and electrodepositing upon the copper a protective metal.
2. A method according to claim 1 wherein the copper is applied to the shot-blasted surface by displacement from a solution of a copper salt.
3. A method according to claim 1 wherein the protective metal is nickel. I
4. A method of treating the surface of a metal of the group consisting of uranium, zirconium, tantanium, tantalum, niobium, molybdenum, tungsten and vanadium which consists in the steps of shot-blasting the surface employing grit of iron for approximately 30 seconds on each part of the surface, immersing the shot-blasted surface in an aqueous solution containing copper sulphate, sulphuric acid, aluminum sulphate and a surface active agent for approximately 5 minutes to form a coating of copper thereon, washing the surface, then making it the cathode in a nickel electroplating bath and forming an electrodeposit of nickel thereon.
References Cited in the file of this patent UNITED STATES PATENTS 2,149,253 Cooper Mar. 7, 1939 2,443,651 Cannizzaro June 22, 1948 2,555,372 Ramage June 5, 1951 2,646,396 Dean July 17, 1953 FOREIGN PATENTS 10,317 Great Britain of 1899 534,614 Great Britain Mar. 12, 1941 OTHER REFERENCES Modern Electroplating, pub. in 1942 by The Electro- Chemical Soc., pp. 258-263.

Claims (1)

1. A METHOD OF TREATING THE SURFACE OF A METAL OF THE GROUP CONSISTING OF URANIUM, ZIRCONIUM, TITANIUM, TANTALUM, NIOBIUM, MOLYBDENUM, TUNGSTEN AND VANADIUM WHICH CONSITS IN THE STEPS OF SUBJECTING THE SURFACE TO SHOT BLASITNT USING FERROUS METAL SHOT, COATING THE SHOTBLASTED SURFACE WITH COPPER, AND ELECTRODEPOSITING UPON THE COPPER A PROTECTIVE METAL.
US286444A 1952-05-06 1952-05-06 Treatment of metals prior to electro-plating Expired - Lifetime US2835630A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2938841A (en) * 1956-04-13 1960-05-31 Olin Mathieson Preparation of zirconium for cold working
US2999799A (en) * 1958-06-26 1961-09-12 Sylvania Electric Prod Electroplating of niobium
US3063917A (en) * 1959-06-29 1962-11-13 Combustion Eng Anodic decontamination of zirconium and hafnium
US3085949A (en) * 1959-04-17 1963-04-16 Ici Ltd Surface treatment of titanium or titanium base alloy
US3202530A (en) * 1961-11-30 1965-08-24 Olin Mathieson Method of forming a composite metal article
US3310390A (en) * 1962-03-27 1967-03-21 Corning Glass Works Electrically conductive abrasive bodies
US3386896A (en) * 1964-11-05 1968-06-04 Bell Telephone Labor Inc Electroplasting onto molybdenum surfaces
US3439188A (en) * 1965-03-08 1969-04-15 Buehler Corp Method for treating titanium
US3463707A (en) * 1965-06-16 1969-08-26 Pacific Eng & Production Co Electrodeposition of lead dioxide
US3512250A (en) * 1966-05-13 1970-05-19 Horst H Lemet Chromium Van Der Method for mutually connecting workpieces and workpieces mutually connected by said method
US3997409A (en) * 1975-09-03 1976-12-14 The United States Of America As Represented By The Secretary Of The Army Method for electroplating extrusion-resistant lead coatings on uranium and the alloys thereof
US4097347A (en) * 1976-08-23 1978-06-27 Packer Elliot L Electrolytic recovery of metals
US4632734A (en) * 1984-03-21 1986-12-30 Deutsche Lufthansa Ag Process for electrochemically or chemically coating niobium
US5456819A (en) * 1991-12-26 1995-10-10 The United States Of America As Represented By The Secretary Of Commerce Process for electrodepositing metal and metal alloys on tungsten, molybdenum and other difficult to plate metals
US20040256408A1 (en) * 2003-06-20 2004-12-23 Lianrui Chen Cladding products and methods for making same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB189910317A (en) * 1899-05-16 1899-06-24 Emile Louis Dessolle Improved Electro-plating Process and Apparatus therefor.
US2149253A (en) * 1937-05-19 1939-03-07 Harry A Cooper Method of treating metal surfaces to inhibit corrosion
GB534614A (en) * 1939-07-01 1941-03-12 Richard Johnson & Nephew Ltd Improvements relating to coating wire with zinc
US2443651A (en) * 1944-12-05 1948-06-22 Westinghouse Electric Corp Process of electroplating on tungsten
US2555372A (en) * 1944-10-02 1951-06-05 Westinghouse Electric Corp Method of coating refractory readily oxidizable metals
US2646396A (en) * 1949-03-17 1953-07-21 Reginald S Dean Method of making electroformed articles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB189910317A (en) * 1899-05-16 1899-06-24 Emile Louis Dessolle Improved Electro-plating Process and Apparatus therefor.
US2149253A (en) * 1937-05-19 1939-03-07 Harry A Cooper Method of treating metal surfaces to inhibit corrosion
GB534614A (en) * 1939-07-01 1941-03-12 Richard Johnson & Nephew Ltd Improvements relating to coating wire with zinc
US2555372A (en) * 1944-10-02 1951-06-05 Westinghouse Electric Corp Method of coating refractory readily oxidizable metals
US2443651A (en) * 1944-12-05 1948-06-22 Westinghouse Electric Corp Process of electroplating on tungsten
US2646396A (en) * 1949-03-17 1953-07-21 Reginald S Dean Method of making electroformed articles

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2938841A (en) * 1956-04-13 1960-05-31 Olin Mathieson Preparation of zirconium for cold working
US2999799A (en) * 1958-06-26 1961-09-12 Sylvania Electric Prod Electroplating of niobium
US3085949A (en) * 1959-04-17 1963-04-16 Ici Ltd Surface treatment of titanium or titanium base alloy
US3063917A (en) * 1959-06-29 1962-11-13 Combustion Eng Anodic decontamination of zirconium and hafnium
US3202530A (en) * 1961-11-30 1965-08-24 Olin Mathieson Method of forming a composite metal article
US3310390A (en) * 1962-03-27 1967-03-21 Corning Glass Works Electrically conductive abrasive bodies
US3386896A (en) * 1964-11-05 1968-06-04 Bell Telephone Labor Inc Electroplasting onto molybdenum surfaces
US3439188A (en) * 1965-03-08 1969-04-15 Buehler Corp Method for treating titanium
US3463707A (en) * 1965-06-16 1969-08-26 Pacific Eng & Production Co Electrodeposition of lead dioxide
US3512250A (en) * 1966-05-13 1970-05-19 Horst H Lemet Chromium Van Der Method for mutually connecting workpieces and workpieces mutually connected by said method
US3997409A (en) * 1975-09-03 1976-12-14 The United States Of America As Represented By The Secretary Of The Army Method for electroplating extrusion-resistant lead coatings on uranium and the alloys thereof
US4097347A (en) * 1976-08-23 1978-06-27 Packer Elliot L Electrolytic recovery of metals
US4632734A (en) * 1984-03-21 1986-12-30 Deutsche Lufthansa Ag Process for electrochemically or chemically coating niobium
US5456819A (en) * 1991-12-26 1995-10-10 The United States Of America As Represented By The Secretary Of Commerce Process for electrodepositing metal and metal alloys on tungsten, molybdenum and other difficult to plate metals
US20040256408A1 (en) * 2003-06-20 2004-12-23 Lianrui Chen Cladding products and methods for making same

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