US3668081A - Production of electrolytic metal - Google Patents

Production of electrolytic metal Download PDF

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Publication number
US3668081A
US3668081A US125423A US3668081DA US3668081A US 3668081 A US3668081 A US 3668081A US 125423 A US125423 A US 125423A US 3668081D A US3668081D A US 3668081DA US 3668081 A US3668081 A US 3668081A
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United States
Prior art keywords
nickel
process according
chromium
pattern
resist
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Expired - Lifetime
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US125423A
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English (en)
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William Gerard Borner
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Huntington Alloys Corp
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International Nickel Co Inc
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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
    • C25C7/02—Electrodes; Connections thereof

Definitions

  • ABSTRACT Metals such as nickel are electroformed upon a matrix or mandrel having an epoxy resist pattern thereon to provide foraminous or dividable electrodeposited metal separable from the matrix wherein the matrix is prepared by depositing from 2 to 30microinches of standard chromium thereon and the desired resist pattern is applied to the chromium-plated surface in the form of a thermoset epoxy ink or paint containing dicyandiamide as a heat-curing agent and then heat curing the resist pattern to provide a repeatedly reuseable matrix.
  • electroforrning provides an economical method for providing screen made of nickel, copper or other metals on a continuous basis.
  • a matrix or mandrel having a pattern of nonconductive spots corresponding with the openings desired in the electroformed screen is prepared.
  • metal is electrodeposited upon the conductive areas of the matrix but does not deposit upon the non-conductive spots, thus yielding a foraminous metal sheet when the electrodeposit is stripped from the matrix.
  • the electrodeposited metal produced upon such mandrels could be separated from the mandrel and divided along lines corresponding to the initial lines of resist applied upon the faces of the mandrel.
  • the present invention is directed to a means for providing highly retentive resist areas upon an electroplating matrix or mandrel for use in electroforrning.
  • the present invention is directedto a process forelectroforming metals, including nickel, cobalt and iron, upon a mandrel which may be made of stainless steel, titanium, aluminum, iron and nickel, etc., wherein the mandrel is prepared by chromium plating faces thereof, applying to the chromium plated faces a thermosettingepoxy ink or paint containing dicyandiarnide as a hardener in the desired pattern as by, for example, silk screen printing, curing the ink or paint film by heating, and thereafter electrodepositing metal thereupon.
  • a mandrel which may be made of stainless steel, titanium, aluminum, iron and nickel, etc.
  • the mandrel is prepared by chromium plating faces thereof, applying to the chromium plated faces a thermosettingepoxy ink or paint containing dicyandiarnide as a hardener in the desired pattern as by, for example, silk screen printing, curing the ink or paint film by heating, and thereafter electrodepositing
  • the ink or paint film may be applied to any desired pattern and may, for example, form a continuous pattern of interconnecting lines or areas upon the face of the mandrel so as to define conductive areas having the desired shape and size for the plated shapes to be produced.
  • chromium plating which is advantageous in accordance with the invention, can be accomplished in any standard chromium plating bath.
  • chromium plating baths are usually aqueous and contain at least about 50 grams per liter (gpl) of chromic acid (C10 and a-catalyst such as sulfuric acid, with the weight ratio of chromic acid to sulfuric acid being about 50:1 to about 250: 1, e.g., 100: 1.
  • a satisfactory aqueous chromium plating bath for purposes of the invention, contains about 250 gpl of chromic acid and 2.5 gpl of sulfuric acid.
  • Chromium can be deposited-upon the face of the mandrel at a cathode current density from about to about 200 amperes per square foot with a bath temperature of about F. to about F. being employed.
  • the chromium deposit may be from about 2 to about 30 microinches in thickness.
  • the chromium deposit may be left upon the exposed areas of the mandrel with beneficial effects in connection with the electroforming of relatively thin foraminous materials, e.g., screen, which usually are plated to a thickness range of about 0.0001 to about 0.001 inches.
  • the epoxy ink or paint pattern would be discontinuous, e.g., a system of dots.
  • the chromium deposit advantageously is removed from the exposed areas of the mandrel prior to electrodeposition of metal thereon.
  • This may be accomplished, for example, by anodic dissolution in an alkaline solution, e.g., sodium carbonate or sodium hydroxide water solution.
  • an aqueous solution containing about 20 to about 50 gpl of sodium hydroxide may beernployed and current may be passed from the mandrel as anode at a current density of about 10 to about 60 amperes per square foot.
  • a mandrel can be produced on which adhesion of heavy deposits, e.g., at least about as inches thick of, for example, nickel, is facilitated.
  • any of the standard acid, aqueous nickel electroplating or electrorefining baths e.g., the sulfate-chloride (Watts) bath, the all-chloride bath, the sulfamate bath, the sulfate-sulfamate bath, etc.
  • These baths usually are buffered with boric acid and are operated within the pH range of about two to about four, at temperatures of about 110 to about F. and at cathode current densities of about 20 to about 50 amperes per square foot (a.s.f.
  • the baths may contain usual brightening or leveling agents, e.g., hydracrylonitrile in the amount of about 15 milligrams to about 75 milligrams per liter, and may contain agents to incorporate a small amount of sulfur in the nickel deposited, e.g., about 0.005 to about 0.025 grams per liter (g.p.l.) of sulfur dioxide, amounts which will provide about 0.005 to about 0.025 percent of sulfur in the deposited nickel. Alloy deposits may also be produced, e.g., nickel-cobalt alloy deposits, again using standard bath compositions for this purpose. Standard cobalt and iron plating solutions may also be used, as disclosed in Modern Electroplating, edited by F. A. Lowenheim, John Wiley and Sons, lnc.,.( 1963.).
  • hydracrylonitrile in the amount of about 15 milligrams to about 75 milligrams per liter
  • agents to incorporate a small amount of sulfur in the nickel deposited e.g., about 0.00
  • nickel percent of sulfur dioxide in the electrolyte, will usually provide a stress level of preferably 2 5,000 pounds per square inch in the nickel.
  • Such nickel is useful as nickel electroplating material because of its high chemical and electrochemical activity,'as ,isdiscussed in the Renzoni et al US. Pat. No.
  • Ten type 304 stainless steel blanks about 29 inches wide by 40 inches-long by 0.125 inches thick and having a pickled finish'were prepared by subjecting them to cathodic alkaline, cleaning and water rinsing, and were then plated with about 10 microinches of chromiumby passing current thereto for about 2% minutes at l ampere per square inch in a chromium plating bath containing 250 gpl chromic acid and 2.5 gpl sulfuric acid. The temperature of the chromium plating bath was ll 3 F The chromium plated blanks were then hot water rinsed and dried.
  • the dried blanks were then silk screen printed to define apattem of uncoated, conductive circular areas aboutfive-eighths inch in diameter in staggered rows with a minimum spacing of three-eighths inch between the circular areas using as a resist material an epoxy ink containing in parts, by weight of efi'ective ingredients, about 12 parts of diglycidyl ether of bisphenol A (epoxy resin), about 7 parts of weight per cent titanium dioxide, 80 weight per cent calcium carbonate pigment and about 1 part of dicyandiamide hardener.
  • the silk screened blanks were oven-cured at about 350? F. for about 40 minutes to set the epoxy resin.
  • the chromium was removed from the exposed areas of the mandrels by exposing them as anode for about 10 minutes in an aqueous solution 'containing'45 gpl sodium hydroxide at an anode current density of 10 asf.'The blanks were then plated in an electrorefining cell containing an aqueous sulfatechloride nickel electrolyte to build upon on each face thereof a thickness of nickel of about three-eighths inch.
  • the plating bath contained about 55 gpl nickel, 20 gpl sodium, gpl chloride, 20 gpl boric acid, 85 gpl sulfate and 0.02 gpl sulfur dioxide.
  • the plating process proceeded for about ten days and the nickel deposit contained about 0.025 percent sulfur. No adherence problem arose in plating. After plating, the blanks were removed'from the tanks, and the nickel deposit in the form of circular segments was stripped from each face thereof. The blanks were returned for further plating without overhaul of the epoxy resin film pattern. The process was repeated about 10 times without overhaul of the epoxy film pattemeing necessary;
  • the epoxy resin used in the ink formulation which is a mixture of glycidyl ethers of bis-phenol, should itself have a viscosity in the range of about 400 to about 600 centipoise at 38 C. since, as those skilled in the art known, viscosity of the resin is a useful indirect measure of the epoxide content.
  • the pigment component of theink performs a useful function in that pigmented films assist in inspection of the blanks for film damage.
  • the pigment preferably'titanium dioxide, which may be extended with, for example, calcium carbonate.
  • the pigment is not essential to the performance of the epoxy resist material. It is to be appreciated that the electrodeposited metal grows across the resist material during plating. Thus, in order to yield a deposit which isreadily" separable into segments, the minimum width of the'resist areas should not be substantially less than the thickness of the electrodeposited metal to be plated.
  • the ink may contain a small amount of colloidal silica (Aerosil”) to provide a thixotropic effect. I
  • the improvement for providing a strongly adherent pattern of said resist material upon said matrix surface which comprises chromium plating said surface, applying to said chromium plated surface a resist pattern of an epoxy-base ink containing dicyandiamide as a hardener, heat-curing said resist ink pattern and electrodepositing nickel upon said matrix bearing said cured ink pattern whereby said matrix may be employed repeatedly without damage to'said cured resist pattern.

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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 Methods And Accessories (AREA)
  • Holding Or Fastening Of Disk On Rotational Shaft (AREA)
US125423A 1971-03-17 1971-03-17 Production of electrolytic metal Expired - Lifetime US3668081A (en)

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US12542371A 1971-03-17 1971-03-17

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US3668081A true US3668081A (en) 1972-06-06

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US (1) US3668081A (no)
JP (1) JPS5136693B1 (no)
BE (1) BE780890A (no)
CA (1) CA971907A (no)
DE (1) DE2212183C3 (no)
FI (1) FI54614C (no)
FR (1) FR2130341B1 (no)
GB (1) GB1323656A (no)
IT (1) IT960841B (no)
NO (1) NO129639B (no)
YU (1) YU66972A (no)
ZA (1) ZA721472B (no)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040915A (en) * 1976-06-15 1977-08-09 The International Nickel Company, Inc. Method for producing regular electronickel or S nickel rounds from electroplating baths giving highly stressed deposits
US4139430A (en) * 1976-04-01 1979-02-13 Ronald Parkinson Process of electrodeposition and product utilizing a reusable integrated cathode unit
US4147597A (en) * 1978-02-21 1979-04-03 The International Nickel Company, Inc. Method for producing electrolytic nickel in particulate forms under condition of high and variable internal stress
US4158612A (en) * 1977-12-27 1979-06-19 The International Nickel Company, Inc. Polymeric mandrel for electroforming and method of electroforming
EP0059854A1 (en) * 1981-02-27 1982-09-15 Asahi Glass Company Ltd. Cathode and electrolysis
US5359928A (en) * 1992-03-12 1994-11-01 Amtx, Inc. Method for preparing and using a screen printing stencil having raised edges
US5478699A (en) * 1992-03-12 1995-12-26 Amtx, Inc. Method for preparing a screen printing stencil
US5709586A (en) * 1995-05-08 1998-01-20 Xerox Corporation Honed mandrel
US20070117020A1 (en) * 2005-11-18 2007-05-24 Actuant Corporation Storage battery electrodes with integral conductors

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2555419C2 (de) * 1975-12-10 1985-11-21 Weber, Otmar, Dipl.-Kfm., 5000 Köln Kathode zur Herstellung von Nickelkörpern
JPS534732A (en) * 1976-07-02 1978-01-17 Mitsui Mining & Smelting Co Anode for electroplating of trivalent chromium
JP6500937B2 (ja) 2017-05-29 2019-04-17 住友金属鉱山株式会社 金属電着用陰極板及びその製造方法
JP7238524B2 (ja) * 2019-03-25 2023-03-14 住友金属鉱山株式会社 金属電着用の陰極板

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2765230A (en) * 1953-02-25 1956-10-02 Buckbee Mears Co Method of forming matrices for the electrodeposition of grids
US2773816A (en) * 1952-08-02 1956-12-11 Int Nickel Co Method for electrorefining metal and improved electrolytic metal plates produced thereby
US3434938A (en) * 1965-12-29 1969-03-25 Budd Co Method and apparatus for producing metal screen sheet
US3489666A (en) * 1966-02-18 1970-01-13 Esb Inc Apparatus for producing flakes of nickel
US3577330A (en) * 1967-11-17 1971-05-04 Int Nickel Co Process for producing electrorefined nickel having controlled size

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2773816A (en) * 1952-08-02 1956-12-11 Int Nickel Co Method for electrorefining metal and improved electrolytic metal plates produced thereby
US2765230A (en) * 1953-02-25 1956-10-02 Buckbee Mears Co Method of forming matrices for the electrodeposition of grids
US3434938A (en) * 1965-12-29 1969-03-25 Budd Co Method and apparatus for producing metal screen sheet
US3489666A (en) * 1966-02-18 1970-01-13 Esb Inc Apparatus for producing flakes of nickel
US3577330A (en) * 1967-11-17 1971-05-04 Int Nickel Co Process for producing electrorefined nickel having controlled size

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
G. R. Schaer, Electroformed Screens with Controlled Hole Size for Battery Plaques, Plating Feb 1968 pp. 130 137 *
T. R. Bates, Photosensitive Resists for Electroforming; Plating Magazine July 1965 pp. 673 676 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4139430A (en) * 1976-04-01 1979-02-13 Ronald Parkinson Process of electrodeposition and product utilizing a reusable integrated cathode unit
US4040915A (en) * 1976-06-15 1977-08-09 The International Nickel Company, Inc. Method for producing regular electronickel or S nickel rounds from electroplating baths giving highly stressed deposits
US4158612A (en) * 1977-12-27 1979-06-19 The International Nickel Company, Inc. Polymeric mandrel for electroforming and method of electroforming
US4147597A (en) * 1978-02-21 1979-04-03 The International Nickel Company, Inc. Method for producing electrolytic nickel in particulate forms under condition of high and variable internal stress
EP0059854A1 (en) * 1981-02-27 1982-09-15 Asahi Glass Company Ltd. Cathode and electrolysis
US5359928A (en) * 1992-03-12 1994-11-01 Amtx, Inc. Method for preparing and using a screen printing stencil having raised edges
US5478699A (en) * 1992-03-12 1995-12-26 Amtx, Inc. Method for preparing a screen printing stencil
US5709586A (en) * 1995-05-08 1998-01-20 Xerox Corporation Honed mandrel
US20070117020A1 (en) * 2005-11-18 2007-05-24 Actuant Corporation Storage battery electrodes with integral conductors
US8088516B2 (en) 2005-11-18 2012-01-03 Acme Aerospace, Inc. Storage battery electrodes with integral conductors

Also Published As

Publication number Publication date
NO129639B (no) 1974-05-06
CA971907A (en) 1975-07-29
ZA721472B (en) 1972-11-29
SU439995A3 (ru) 1974-08-15
FR2130341B1 (no) 1976-08-06
FI54614C (fi) 1979-01-10
DE2212183A1 (de) 1972-09-28
GB1323656A (en) 1973-07-18
DE2212183B2 (de) 1974-11-14
YU66972A (en) 1982-02-28
FR2130341A1 (no) 1972-11-03
FI54614B (fi) 1978-09-29
IT960841B (it) 1973-11-30
BE780890A (fr) 1972-09-18
DE2212183C3 (de) 1975-06-26
JPS5136693B1 (no) 1976-10-09

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