US3523873A - Electrodeposition of strippable metal coatings and compositions and artiticles useful therefor - Google Patents

Electrodeposition of strippable metal coatings and compositions and artiticles useful therefor Download PDF

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Publication number
US3523873A
US3523873A US513854A US3523873DA US3523873A US 3523873 A US3523873 A US 3523873A US 513854 A US513854 A US 513854A US 3523873D A US3523873D A US 3523873DA US 3523873 A US3523873 A US 3523873A
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United States
Prior art keywords
copper
sulfur
compositions
electrodeposited
metal
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Expired - Lifetime
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US513854A
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English (en)
Inventor
Eugene Mitchell Elkin
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Canadian Copper Refiners Ltd
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Canadian Copper Refiners Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • C25C7/08—Separating of deposited metals from the cathode

Definitions

  • This invention relates to the electrodeposition of metals. More particularly, this invention relates to the electrodeposition of metals onto a substrate, such as a metal or electrically conductive substrate, under conditions such that the electrodepositioned metal is readily separable or stripable from the substrate.
  • this invention is directed to a method of making a metal cathode starting sheet, such as a continuous, coherent, essentially holefree copper cathode starting sheet, useful in the electrorefining of metals.
  • this invention is directed to an electrically conductive substrate coated with a parting agent, which permits the ready separation of electrodeposited metal from the coated substrate.
  • this invention is directed to a parting agent composition useful in the manufacture of metal cathode starting sheets, such as copper cathode starting sheets, employed in the electrorefining of metals.
  • this invention is directed to a parting agent composition useful in electroforming operations.
  • copper is electrodeposited upon a smooth metal sheet or blank, such as a smooth plate of rolled copper, which has been coated with a parting agent.
  • the essential functions of the parting agent are to provide a suitable surface for the electrodeposition of copper, to prevent adherence of the electrodeposited copper to the copper plate and to facilitate the removal or stripping of the electrodeposited copper from the copper plate in the form of a continuous, coherent, subsubstantially hole-free sheet.
  • a film of a petroleum derived parting agent or dressing usually comprising a lubricating oil, transformer oil, diesel oil or fuel oil or mixtures thereof, including lubricating greases and gasoline.
  • a petroleum derived parting agent or dressing usually comprising a lubricating oil, transformer oil, diesel oil or fuel oil or mixtures thereof, including lubricating greases and gasoline.
  • Such dressings or parting agents are usually applied by hand swabs or rollers or by dipping in a tank containing such dressings and by other means.
  • Yet another specific object of this invention is to provide a coated metal substrate particularly useful in the electrorefining of metal.
  • a dressing or parting agent composition comprising an aqueous emulsion containing minor amounts by weight of a polar, saturated, substantially water-insoluble, aliphatic organic compound and a sulfur-containing material is useful and yields improved results when employed in an operation for the preparation of metal cathode starting sheets, such as copper cathode starting sheets.
  • an electrically conductive substrate such as a metal substrate, coated with a parting agent in accordance with this invention and comprising an aqueous emulsion containing a polar, saturated, substantially water-insoluble, aliphatic, organic compound and a sulfur-containing material, permits the ready separation of electrodeposited metal from the coated substrate or surface.
  • the polar, saurated, substantially water-insoluble, aliphatic, organic compound which may be of commercial grade or reagent grade quality comprising one of the components of the parting agent composition in accordance with this invention is selected from the group comprising fatty acids, fatty alcohols and derivatives thereof, such as esters and glycerides.
  • the polar, saturated, organic compound may be liquid or solid at a temperature in the range from about 60 F. to about 100 F., more or less. It is required, however, that the polar, saturated, organic compound be substantially water-insoluble at such temperatures. Specifically, the polar, saturated, organic compound should have a water-solubility not in excess of about 5% by weight at about 150 F. based on the resulting solution.
  • the purpose of the polar, saturated, organic compound in the parting agent composition of this invention is to form a film or barrier on the substrate or surface to which it is applied such that after electrodeposition of metal thereon the electrodeposited metal can be stripped therefrom with little difficulty and substantially in the shape or outline of the substrate surface itself.
  • Polar, saturated, organic compounds which have been found to be useful in compositions in accordance with this invention include the fatty acids, such as stearic acid, the fatty alcohols, such as decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, i.e. a C straight chain alcohol, hexadecyl alcohol, i.e.
  • a C branched chain alcohol stearyl alcohol, arachidyl alcohol, the aliphatic esters, such as butyl stearate, isopropyl palmitate, isopropyl stearate, glycerol monostearate, ethylene glycol monostearate, diethylene glycol stearate, propylene glycol stearate, sorbitan monostearate and sorbitan tristearate.
  • polar, saturated, aliphatic, organic compounds useful in the preparation of compositions in accordance with this invention include decanoic acid, palmitic acid, ntridecanoic acid and their higher molecular weight homologues.
  • Mixtures of such organic compounds are also usefully employed in the compositions of this invention.
  • the other component of the dressing or parting agent compositions of this invention is a sulfur-containing material.
  • This other component may be prepared by dissolving sulfur in a polar, saturated, fatty, organic compound such as the aforementioned polar, saturated, substantially water-insoluble, aliphatic, organic compound in compositions of this invention.
  • a solution prepared by dissolving sulfur in n-hexadecyl alcohol has been found to yield satisfactory results.
  • Sulfur-containing compounds which have been found to be useful include mercaptopropionic acid, n-butyl-sulfide, n-octyl mercaptan and lauryl mercaptan.
  • sulfur-containing organic compounds such as alkyl sulfides and alkyl mercaptans containing at least four carbon atoms per molecule, such as alkyl sulfides and alkyl mercaptans containing from four to twenty-four carbon atoms per molecule, are useful in the practice of this invention.
  • the amount of sulfur-containing material in compositions in accordance with this invention is small, less than about 1% by weight of the composition. For example, it has been observed that in the manufacture of copper cathode starting sheets employing a dressing or parting agent composition in accordance with this invention if the sulfur-containing material content of the dressing is too high the resulting electrodeposited copper will be lacy i.e. have the appearance of lace.
  • any suitable emulsifying agent may be employed in the preparation of aqueous emulsions containing the polar, saturated, aliphatic, organic compound and the sulfurcontaining material in accordance with this invention. Satisfactory results have been obtained in the manufacture of copper cathode starting sheets when the emulsifying agent employed in the preparation of the parting agent compositions comprises a sodium dodecylbenzene sulfonate.
  • Other useful emulsifying agents include linear alkyl aryl sulfonates and the corresponding water-soluble salts and linear alcohol sulfates and the corresponding watersoluble salts.
  • the polar, saturated, aliphatic, organic compound is usually present in an amount in the range 220% by weight based on the aqueous emulsion and the sulfur-containing material is usually present in the emulsion in an amount in the range 0.05 to 0.15% by weight.
  • the emulsifying agent is present in an amount effective to emulsify the polar, saturated, substantially water-insoluble, aliphatic, organic compound and is usually present in an amount in the range 0.4-4% by weight.
  • the dressing or parting agent composition may be applied by any suitable means to the substrate upon which the metal is to be electrodeposited, such as swabs or rollers, or by spraying or by dipping or immersing the substrate, e.g. the copper starting blank, into the emulsion and then raising the blank and permitting the excess emulsion to drain.
  • suitable means such as swabs or rollers, or by spraying or by dipping or immersing the substrate, e.g. the copper starting blank, into the emulsion and then raising the blank and permitting the excess emulsion to drain.
  • a suitable means to the substrate upon which the metal is to be electrodeposited
  • the substrate e.g. the copper starting blank
  • Copper starting blanks coated with a composition in accordance with this invention were employed in electrolytic cells under commercial copper refining conditions for the preparation of copper cathode starting sheets.
  • the resulting electrodeposited copper cathode starting sheets were smooth and without defect and were readily stripped from the blanks without diificulty.
  • compositions and methods for the preparation of compositions in accordance with this invention Water at a temperature of about -175 F. was introduced to within about 18" from the top into a tank measuring 48" high, 48" long and 18" wide. The tank was also provided with a A horsepower Lightnin mixer which had a shaft about 3 feet long to which were fixed two propellers, each about 3" in diameter. Seventy pounds hexadecyl alcohol and fourteen pounds Sulframin 85 flakes, a sodium n-dodecylbenzene sulfonate were added to the hot water in the tank.
  • More hot water was then added to within 4" from the top of the tank, and the resulting admixture was agitated for at least eight hours by means of the Lightnin mixer.
  • the order and the rate of addition of the components are not critical. It is preferable, however, to first add the polar, saturated, aliphatic, organic compound, such as the fatty alcohol, and then to add the emulsifying a ent.
  • the resulting emulsion now contained hexadecyl alcoholabut 5 by weight Sulfrarnin *85-about 1% by weight mercaptopropionic acidabout 0.1% by welght.
  • the sulfur-containing material such as the thiolactic acid
  • the sulfur-containing material is usually added last since sulfur-containing materials, particularly the organic sulfur-containing compounds, have an unpleasant odor, especially when warmed. Cooling of the emulsion before the addition of the sulfur-containing material is a matter of convenience and preference so as to decrease the odor.
  • the mercaptopropionic acid Upon the addition of the mercaptopropionic acid the emulsion is ready for use by immersing therein the copper blanks.
  • the copper blanks are placed in commercial copper electrolytic cells and substantially pure copper electrodeposited thereon.
  • the blanks containing the electrodeposited copper are removed from the cells and the resulting formed electrodeposited copper starting sheets are pulled or stripped therefrom as smooth, continuous, coherent, essentially hole-free sheets.
  • aqueous emulsions found to be useful and to yield satisfactory results in accordance with the practices of this invention include aqueous emulsions having the compositions:
  • a sulfur solution prepared by the addition of 4 grams of elemental sulfur per 1000 cc. of hexadecyl alcohol followed by heating to a temperature in the range about 180-l90 F. to dissolve the sulfur, thereby yielding a sulfur solution containing 0.4% by weight sulfur has been found to be useful, particularly in combination with hexadecyl alcohol as the polar, saturated, substantially water-insoluble, aliphatic, organic compound.
  • sulfur-containing materials found to be useful include n-lauryl mercaptan and n-octyl mercaptan. These may be added directly to the agitated emulsion.
  • the practice of this invention is not only applicable to the manufacture of copper cathode starting sheets but would also appear to be applicable to the manufacture of nickel cathode starting sheets and the like. Also, as indicated herein, the practice of this invention is applicable to electroforming operations to improve and aid in the release of the electrodeposited metal from the substrate material.
  • a material comprising an electrically conductive substrate coated with a film or layer of a composition comprising 220% by weight of a polar, saturated, substantially water-insoluble, aliphatic, organic compound selected from the group consisting of fatty acids, fatty alcohols and ester and glyceride derivatives thereof and a minor amount in the range 0.054% by weight of a sulfur-containing material.
  • said electrically conductive substrate is a smooth plate of rolled copper.
  • a parting agent serving as an aid for the stripping and removal of metal subsequently electrodeposited on said substrate
  • the improvement which comprises employing as said parting agent a composition comprising an aqueous emulsion containing 2-20% by weight of a polar, saturated, substantially water-insoluble, aliphatic, organic compound selected from the group consisting of fatty acids, fatty alcohols and ester and glyceride derivatives thereof and about 0.05-1% by weight of a sulfur-containing material.
  • said electrodeposited metal is a metal selected from the group consisting of copper, nickel and the like.
  • sulfur-containing material is selected from the group consisting of sulfur solutions, mercaptopropionic acid, nbutyl sulfide, n-octyl mercaptan and lauryl mercaptan.
  • a method of making copper cathode starting sheets which comprises applying to the surface of a smooth copper plate an aqueous emulsion comprising a minor amount in the range 220% by weight of a polar, saturated, substantially Water-insoluble, aliphtaic, organic compound selected from the group consisting of fatty acids, fatty alcohols and ester and glyceride derivatives thereof and a minor amount in the range of 0.05-1% by weight of a sulfur-containing material and a minor amount of an emulsifying agent for said polar, organic compound, electrodepositing substantially pure copper on the surface of the thus-coated copper plate and stripping the resulting electrodeposited copper from said copper plate su'bsantially in the form of a smooth, coherent, essentially holefree, copper sheet.
  • a polar, saturated, substantially Water-insoluble, aliphtaic, organic compound selected from the group consisting of fatty acids, fatty alcohols and ester and glyceride derivatives thereof and a minor amount in the range of
  • sulfur-containing material is selected from the group consisting of alkyl sulfides and alkyl mercaptans containing from 4 to 24 carbon atoms per molecule.
  • a method in accordance with claim 7 wherein said sulfur-containing material is prepared by the addition of elemental sulfur to hexadecyl alcohol in the proportion 7 8 of about 4 grams of elemental sulfur per 1000 cc. of FOREIGN PATENTS hexadecyl alcohol.

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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)
US513854A 1965-12-14 1965-12-14 Electrodeposition of strippable metal coatings and compositions and artiticles useful therefor Expired - Lifetime US3523873A (en)

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US51385465A 1965-12-14 1965-12-14

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BE (1) BE691208A (enrdf_load_stackoverflow)
SE (1) SE319946B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997007263A1 (en) * 1995-08-21 1997-02-27 Svedala Skega Ab A cathode element and a method of its manufacture
EP4321652A1 (fr) * 2022-08-11 2024-02-14 John Cockerill SA Dispositif d'extraction d'un metal depose electrolytiquement sur une cathode

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US46203A (en) * 1865-02-07 Improvement in steam-boilers
US630796A (en) * 1898-05-03 1899-08-08 Hermann Becker Method of preparing cathodes for electrodeposition of metals.
GB341246A (en) * 1929-12-27 1931-01-15 Sherard Osborn Cowper Coles New process in connection with the electro-deposition of metals
US2555321A (en) * 1941-08-08 1951-06-05 Western Union Telegraph Co Facsimile recording paper
US3271190A (en) * 1962-08-06 1966-09-06 Eastman Kodak Co Anti-blocking compositions and sheet material treated therewith
US3281339A (en) * 1963-05-10 1966-10-25 Anaconda American Brass Co Process of electroforming using benzotriazole as the stripping agent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US46203A (en) * 1865-02-07 Improvement in steam-boilers
US630796A (en) * 1898-05-03 1899-08-08 Hermann Becker Method of preparing cathodes for electrodeposition of metals.
GB341246A (en) * 1929-12-27 1931-01-15 Sherard Osborn Cowper Coles New process in connection with the electro-deposition of metals
US2555321A (en) * 1941-08-08 1951-06-05 Western Union Telegraph Co Facsimile recording paper
US3271190A (en) * 1962-08-06 1966-09-06 Eastman Kodak Co Anti-blocking compositions and sheet material treated therewith
US3281339A (en) * 1963-05-10 1966-10-25 Anaconda American Brass Co Process of electroforming using benzotriazole as the stripping agent

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997007263A1 (en) * 1995-08-21 1997-02-27 Svedala Skega Ab A cathode element and a method of its manufacture
AU708223B2 (en) * 1995-08-21 1999-07-29 Svedala Skega Ab A cathode element and a method of its manufacture
US6017429A (en) * 1995-08-21 2000-01-25 Svedala Skega Ab Cathode element and a method of its manufacture
EP4321652A1 (fr) * 2022-08-11 2024-02-14 John Cockerill SA Dispositif d'extraction d'un metal depose electrolytiquement sur une cathode

Also Published As

Publication number Publication date
DE1533443B2 (de) 1972-04-13
DE1533443A1 (de) 1970-02-26
BE691208A (enrdf_load_stackoverflow) 1967-06-14
SE319946B (enrdf_load_stackoverflow) 1970-01-26

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