US3334029A - Process for selectively anodically dissolving copper from zirconium - Google Patents

Process for selectively anodically dissolving copper from zirconium Download PDF

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Publication number
US3334029A
US3334029A US262852A US26285263A US3334029A US 3334029 A US3334029 A US 3334029A US 262852 A US262852 A US 262852A US 26285263 A US26285263 A US 26285263A US 3334029 A US3334029 A US 3334029A
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US
United States
Prior art keywords
copper
zirconium
covering
article
dissolution
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
Application number
US262852A
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English (en)
Inventor
Delafosse Jacques
Herenguel Jean
Hourquin Robert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
Priority date (The priority date 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 date listed.)
Filing date
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Application granted granted Critical
Publication of US3334029A publication Critical patent/US3334029A/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings

Definitions

  • the present invention relates to a process for the selective anodic dissolution of a metal coating.
  • Elimination of the protective covering, when the deformation operations are completed, can be effected 'by mechanical means, but most often this elimination is either very costly or incomplete, because of intermetallic penetration which can take place between the covering and the article itself.
  • the process of selective anodic dissolution of a metallic coating accordingto the invention does not have the disadvantages mentioned above.
  • the protected part with its metallic covering is treated electrolytically as an anode, by utilising a rapid-action electrolyte of a composition which is substantially independent of the duration of the operation of the dissolution, the metal which is to be uncovered not being attacked by the electrolyte or being covered by a barrier layer under selected conditions for the transfer of the covering metal.
  • a selective electrolytic dissolution process comprises anodising an article comprising zirconium or a zirconium-base alloy having a covering of copper or a copper-base alloy in an electrolyte containing copper ions and sulphate ions.
  • the electrolyte contains 25 to 100 g./l. of sulphuric acid and 50 to 100 g./l. of copper sulphate.
  • the electrolysis potential is from 0.5 to v.
  • cathodic current density is from 0.2 to 15 a./sq. dm. and the cathode-to-anode surface ratio is from 0.1 to 10.
  • the example relates to the anodic dissolution of a copper covering plate-d on to an article of zirconium or an alloy of zirconium with other metals such as uranium.
  • the copper covering which has been applied to the article by a hot extrusion operation, followed if desired by working in the cold or at moderate temperature and annealing in air, is to be removed so that the article itself can be subjected to finishing operations which impart to it the dimensional tolerances and surface state desired.
  • dissolution of the covering is carried out chemically in fluoro-nitric baths or nitric baths which cause the evolution of noxious vapours which must be trapped, neutrilsed and scrubbed.
  • the bath becomes loaded with copper salts and zirconium salts, which necessitates an expensive chemical recovery process.
  • the application of the invention to this particular case consists in effecting the dissolution of the copper covering by anodising, viz, electrolysis as an anode, under the following conditions.
  • the metallic part surrounded by its covering which is to be dissolved away constitutes the anode of the electrolytic cell used.
  • the cathode is constituted by grids of wires or expanded metal located above and below the anode at a minimum distance of 5 mm.
  • the temperature of the electrolysis bath should be from 2030 C.
  • the potential applied between the anode and the cathode is maintained at a value of from 0.5 to 6 volts, the cathodic current density being from 0.5 to 1 a./dm.
  • the speed of dissolution of the copper of the covering constituting the anode is about 1 g. per amp. per hour, the copper being transferred to the cathode where it deposits in a compact form.
  • the thickness of the copper covering diminishes by mm. per lamp. per drn. (current density) per hour.
  • an anodic oxide layer forms which has a thickness of less than 0.1 micron at the temperature and potential and in the electrolyte indicated. It is the same if the anode is of zirconium.
  • the copper which has diffused at the covering/article interface is entirely.
  • the electrolyte Even in the case where electrolysis is carried out for a long time after complete dissolution of the copper, the electrolyte only contains low quantities of zirconiurn and there is zirconium alloyed with copp r in the interditfusion layer which may be formed.
  • the article is of a zirconium-uranium alloy, the manium content of which is less than 6%, the same electrolyte even after prolonged operation only contains very small quantities of uranium, corresponding to an interdiifusion layer formed between the copper and zirconiumuranium alloy.
  • the electrolyte does not undergo any modification of composition and is always ready for use and requires virtually the minimum of maintenance.
  • the electrolyte can be agitated if desired or not.
  • the copper deposited on the cathode can be recovered directly in the metallic state.
  • the process which has been described can be applied to metallic parts which have various different shapes. If the process is applied to an article of great length, this is placed in an electrolytic bath, rolled in a spirial with spacers giving distances of 10-20 mm. between adjacent turns When the article coated with the covering has a tubular or hollow form, an auxiliary cathode is used which penerta-tes into the re-entrant part.

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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)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US262852A 1962-03-21 1963-03-05 Process for selectively anodically dissolving copper from zirconium Expired - Lifetime US3334029A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR891708A FR1327768A (fr) 1962-03-21 1962-03-21 Procédé de dissolution anodique sélective d'un revêtement métallique

Publications (1)

Publication Number Publication Date
US3334029A true US3334029A (en) 1967-08-01

Family

ID=8774973

Family Applications (1)

Application Number Title Priority Date Filing Date
US262852A Expired - Lifetime US3334029A (en) 1962-03-21 1963-03-05 Process for selectively anodically dissolving copper from zirconium

Country Status (7)

Country Link
US (1) US3334029A (xx)
BE (1) BE629890A (xx)
DE (1) DE1195132B (xx)
FR (1) FR1327768A (xx)
GB (1) GB1032293A (xx)
LU (1) LU43371A1 (xx)
NL (1) NL290090A (xx)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0415130A1 (en) * 1989-08-31 1991-03-06 Led Italia S.R.L. Method to eliminate the filling in wrought hollow gold and wrought hollow gold thus processed
US5250507A (en) * 1990-08-17 1993-10-05 Hoechst Aktiengesellschaft Process for producing molded bodies from precursors of oxidic high-temperature superconductors
US20130220530A1 (en) * 2012-02-24 2013-08-29 Kuanping Gong Method of transferring graphene

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1001539A3 (nl) * 1988-03-17 1989-11-21 Bekaert Sa Nv Metaalvezels verkregen door gebundeld trekken.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2196133A (en) * 1936-09-28 1940-04-02 Robert Laing Bruce Gall Photography
US3063917A (en) * 1959-06-29 1962-11-13 Combustion Eng Anodic decontamination of zirconium and hafnium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2196133A (en) * 1936-09-28 1940-04-02 Robert Laing Bruce Gall Photography
US3063917A (en) * 1959-06-29 1962-11-13 Combustion Eng Anodic decontamination of zirconium and hafnium

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0415130A1 (en) * 1989-08-31 1991-03-06 Led Italia S.R.L. Method to eliminate the filling in wrought hollow gold and wrought hollow gold thus processed
US5250507A (en) * 1990-08-17 1993-10-05 Hoechst Aktiengesellschaft Process for producing molded bodies from precursors of oxidic high-temperature superconductors
US20130220530A1 (en) * 2012-02-24 2013-08-29 Kuanping Gong Method of transferring graphene
US9039886B2 (en) * 2012-02-24 2015-05-26 Cheil Industries, Inc. Method of transferring graphene

Also Published As

Publication number Publication date
NL290090A (xx)
BE629890A (xx)
DE1195132B (de) 1965-06-16
LU43371A1 (xx) 1963-05-16
GB1032293A (en) 1966-06-08
FR1327768A (fr) 1963-05-24

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