US2318592A - Electrodeposition - Google Patents

Electrodeposition Download PDF

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Publication number
US2318592A
US2318592A US320566A US32056640A US2318592A US 2318592 A US2318592 A US 2318592A US 320566 A US320566 A US 320566A US 32056640 A US32056640 A US 32056640A US 2318592 A US2318592 A US 2318592A
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bath
electrodeposition
sulfamate
metal
electrodeposited
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US320566A
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Martin E Cupery
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper

Definitions

  • Sulfamates are compounds which contain the -SO3-NH2 group. It will be understood that I may use hydrogen sulfamate, or so-called sulfamic acid, as well as sodium, potassium, or ammonium sulfamates. The sulfamate of a metal to be plated may be used.
  • metals such as zinc, cadmium, nickehcopper, lead, and iron may be electrodeposited from sulfamate electrolytes' Plating baths according to this invention may be made up using a sulfamate of the metal to be electrodeposited or by using another sulfamate together with a soluble compound of the metal. Any acid or alkali may be used to adjust the pH of the platingbath to the desired condition whether it be basic, neutral, or acidic.
  • compositions for electrodeposition may be offered to the trade in the form of mixtures of sulfamates with other constituents to be used in an electrodepositing bath. It may under some conditions be found desirable, for instance, to sell mixtures of sulfamic acid, which is a dry product, together with a soluble compound of a metal to be electrodeposited. Alternatively, it may be found preferable to efier to the trade a sulfamate of the metal to be electrodeposited either, alone or together with other bath constituents.
  • the concentration of electrolytes employing sulfamates according to the present invention may be widely varied following considerations known to the art in conjunction with other electrolytes. In general, it may be said that electrolytes may vary in concentration from those barely strong enough to conduct an electrical current up to saturated solutions. More specifically, it will usually be preferable to use fairly concentrated solutions so that relatively large amounts of a metal to be electrodeposited may exist in the bath in the form of a sulfamate.
  • Example 1 An electrolyte for electrodeposition of copper was made up as follows:
  • An electrolytic solution for the electrodeposition of lead was made up with the following:
  • This bath contained no undissolved precipitate. Upon electrolysis, a grey-white deposit was obtained at moderately low current densities and a grey-black deposit was obtained at higher current densities.
  • Example 3 Another bath was made up as follows:
  • Nickel deposits were of the bath.
  • Example 4 A bath was made up as follows: Ammonium sulfamate (NHa'SOa-NH2) obtained upon electrolysis rams per liter 50 Sulfamic acid (H-SOa-NHz) do 53.5 Nickel carbonate (2NlCO33Ni(OH)2-4H2O) do 35 Ammonium hydroxide (NHl0H) cc About 10 a. through an aqueous 1.
  • the step comprising effecting deposition by passing an electric current through an aqueous electrolyte consisting essentially of the metal cation and the anionSO3.NHz.
  • An electrodepositing bath for the electrodeposition of lead the bath being an aqueous electrolyte consisting essentially of the lead cation and the anion-SO: :NHz.
  • An electrodepositing bath for the electrodeposition of a metal selected from the group consisting of nickel, copper, and lead the bath being an aqueous electrolyte consisting essentially of the metal cation and the anion-SOa-NHa.

Description

Pdteil edlyls ii,
UNITED STATES PATENT OFFICE EmcTn gr zsnloN Martin, E. Cupery, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation 01' Delaware No Drawing.
4 Claims. (Cl. 204-49) It is an object of this invention to provide novel electrolytes which may be usedin the electrodeposition or metals. It is a further object of this invention to provide electrolytes in which most of the metals ordinarily electrodeposited are highly soluble. It is a still further object of this invention to provide electrodepositing solutions which maybe used at either a low or a high pH, that'is, either acidic or basic. It is a still further object to provide electrodepositing processes and solutions which are simple to operate and maintain. Still further objects of this invention will become apparent hereinafter.
The foregoing and other objects of this invention are attained by the use of an electrolyte containing a sulfamate. Sulfamates of the metals ordinarily electrodeposited are highly soluble and plating baths containing them are of unusually good character. Unlike cyanides which must be used in alkaline baths, and unlik silicofluorides which are ordinarily used in acid baths, sulfamates may be used in either acid or alkaline baths.
Sulfamates are compounds which contain the -SO3-NH2 group. It will be understood that I may use hydrogen sulfamate, or so-called sulfamic acid, as well as sodium, potassium, or ammonium sulfamates. The sulfamate of a metal to be plated may be used. I
According to the processes of this invention metals such as zinc, cadmium, nickehcopper, lead, and iron may be electrodeposited from sulfamate electrolytes' Plating baths according to this invention may be made up using a sulfamate of the metal to be electrodeposited or by using another sulfamate together with a soluble compound of the metal. Any acid or alkali may be used to adjust the pH of the platingbath to the desired condition whether it be basic, neutral, or acidic.
It will be understood that compositions for electrodeposition may be offered to the trade in the form of mixtures of sulfamates with other constituents to be used in an electrodepositing bath. It may under some conditions be found desirable, for instance, to sell mixtures of sulfamic acid, which is a dry product, together with a soluble compound of a metal to be electrodeposited. Alternatively, it may be found preferable to efier to the trade a sulfamate of the metal to be electrodeposited either, alone or together with other bath constituents.
The concentration of electrolytes employing sulfamates according to the present invention may be widely varied following considerations known to the art in conjunction with other electrolytes. In general, it may be said that electrolytes may vary in concentration from those barely strong enough to conduct an electrical current up to saturated solutions. More specifically, it will usually be preferable to use fairly concentrated solutions so that relatively large amounts of a metal to be electrodeposited may exist in the bath in the form of a sulfamate.
In order that the invention may be better understood, reference should be had to the following illustrative examples:
Example 1 An electrolyte for electrodeposition of copper was made up as follows:
Grams per liter Ammonium sulfamate (NH4-SO3'NH2) 100 Copper sulfate (CuSO4'5H20) 130 Sodium hydroxide (NaOH) 7.5
An electrolytic solution for the electrodeposition of lead was made up with the following:
Grams per liter Sulfamic acid (H-SOz-NI-Iz) 107 Litharge (PbO) 36.6
This bath contained no undissolved precipitate. Upon electrolysis, a grey-white deposit was obtained at moderately low current densities and a grey-black deposit was obtained at higher current densities.
Example 3 Another bath was made up as follows:
Grams per liter Sulfamic acid (H-SOr-NHz) 107 Nickel carbonate (2NiCO3-3Ni(OH) z-4H2O) The bath constituents dissolved completely.
Nickel deposits were of the bath.
Example 4 A bath was made up as follows: Ammonium sulfamate (NHa'SOa-NH2) obtained upon electrolysis rams per liter 50 Sulfamic acid (H-SOa-NHz) do 53.5 Nickel carbonate (2NlCO33Ni(OH)2-4H2O) do 35 Ammonium hydroxide (NHl0H) cc About 10 a. through an aqueous 1. In a process for the electrodeposition of lead, the step comprising effecting deposition by passing an electric current through an aqueous electrolyte consisting essentially of the metal cation and the anionSO3.NHz.
2. An electrodepositing bath for the electrodeposition of lead, the bath being an aqueous electrolyte consisting essentially of the lead cation and the anion-SO: :NHz.
3. In a. process for the electrodeposition of a metal selected from the group consisting of nickel. copper, and lead, the step comprising effecting deposition by passing an electric current electrolyte consisting essentially of the metal cation and the anion SOa-NHz.
4. An electrodepositing bath for the electrodeposition of a metal selected from the group consisting of nickel, copper, and lead, the bath being an aqueous electrolyte consisting essentially of the metal cation and the anion-SOa-NHa.
MARTIN E. CUPERY.
US320566A 1940-02-24 1940-02-24 Electrodeposition Expired - Lifetime US2318592A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2415169A (en) * 1942-09-22 1947-02-04 Du Pont Electrodeposition of lead
US2430304A (en) * 1942-10-03 1947-11-04 Du Pont Anodizing iron group metals in lead sulfamate bath
US2458839A (en) * 1944-04-19 1949-01-11 Indium Corp America Electrodeposition of indium and its alloys
US2460252A (en) * 1946-02-09 1949-01-25 Harshaw Chem Corp Lead-tin alloy plating
US2484540A (en) * 1945-10-03 1949-10-11 Republic Steel Corp Lead coating process
US2488246A (en) * 1944-08-25 1949-11-15 United Chromium Inc Process of electroplating zinc, and baths and compositions for use therein
US2810006A (en) * 1953-11-02 1957-10-15 Ruben Samuel Electric current producing cell
US3152973A (en) * 1960-07-26 1964-10-13 Udylite Corp Electrodeposition of lustrous nickel
US3244603A (en) * 1962-06-08 1966-04-05 Gen Electric Electrodeposition of a nickel-manganese alloy
US3326782A (en) * 1963-05-22 1967-06-20 Int Nickel Co Bath and method for electroforming and electrodepositing nickel
US3360445A (en) * 1965-01-04 1967-12-26 Du Pont Electrodeposition of nickel from the sulfamate bath
US3522155A (en) * 1964-07-10 1970-07-28 M & T Chemicals Inc Method of electrodepositing a tinbismuth alloy and compositions therefor
US3536481A (en) * 1967-06-12 1970-10-27 Xerox Corp Electrolytic process of forming a xerographic belt
US4067781A (en) * 1977-01-10 1978-01-10 Rapids Felix R Method for electroplating
US4521282A (en) * 1984-07-11 1985-06-04 Omi International Corporation Cyanide-free copper electrolyte and process
EP0559384A2 (en) * 1992-03-04 1993-09-08 AT&T Corp. Devices with tape automated bonding
US20050025893A1 (en) * 2003-07-31 2005-02-03 Smith Clifford L. Composite tool coating system
WO2008051390A1 (en) * 2006-10-26 2008-05-02 Carestream Health, Inc. Metal substrate having electronic devices formed thereon

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2415169A (en) * 1942-09-22 1947-02-04 Du Pont Electrodeposition of lead
US2430304A (en) * 1942-10-03 1947-11-04 Du Pont Anodizing iron group metals in lead sulfamate bath
US2458839A (en) * 1944-04-19 1949-01-11 Indium Corp America Electrodeposition of indium and its alloys
US2488246A (en) * 1944-08-25 1949-11-15 United Chromium Inc Process of electroplating zinc, and baths and compositions for use therein
US2484540A (en) * 1945-10-03 1949-10-11 Republic Steel Corp Lead coating process
US2460252A (en) * 1946-02-09 1949-01-25 Harshaw Chem Corp Lead-tin alloy plating
US2810006A (en) * 1953-11-02 1957-10-15 Ruben Samuel Electric current producing cell
US3152973A (en) * 1960-07-26 1964-10-13 Udylite Corp Electrodeposition of lustrous nickel
US3244603A (en) * 1962-06-08 1966-04-05 Gen Electric Electrodeposition of a nickel-manganese alloy
US3326782A (en) * 1963-05-22 1967-06-20 Int Nickel Co Bath and method for electroforming and electrodepositing nickel
US3522155A (en) * 1964-07-10 1970-07-28 M & T Chemicals Inc Method of electrodepositing a tinbismuth alloy and compositions therefor
US3360445A (en) * 1965-01-04 1967-12-26 Du Pont Electrodeposition of nickel from the sulfamate bath
US3536481A (en) * 1967-06-12 1970-10-27 Xerox Corp Electrolytic process of forming a xerographic belt
US4067781A (en) * 1977-01-10 1978-01-10 Rapids Felix R Method for electroplating
US4521282A (en) * 1984-07-11 1985-06-04 Omi International Corporation Cyanide-free copper electrolyte and process
EP0559384A2 (en) * 1992-03-04 1993-09-08 AT&T Corp. Devices with tape automated bonding
EP0559384A3 (en) * 1992-03-04 1993-10-20 AT&T Corp. Devices with tape automated bonding
KR100288405B1 (en) * 1992-03-04 2001-05-02 엘리 웨이스 , 알 비 레비 Electrical bonding method for semiconductor chip and device therefor
US20050025893A1 (en) * 2003-07-31 2005-02-03 Smith Clifford L. Composite tool coating system
WO2008051390A1 (en) * 2006-10-26 2008-05-02 Carestream Health, Inc. Metal substrate having electronic devices formed thereon
US20080115350A1 (en) * 2006-10-26 2008-05-22 Kerr Roger S Metal substrate having electronic devices formed thereon
US20100129945A1 (en) * 2006-10-26 2010-05-27 Kerr Roger S Metal substrate having electronic devices formed thereon
US20100129965A1 (en) * 2006-10-26 2010-05-27 Kerr Roger S Metal substrate having electronic devices formed thereon
US7913381B2 (en) 2006-10-26 2011-03-29 Carestream Health, Inc. Metal substrate having electronic devices formed thereon
US8015702B2 (en) * 2006-10-26 2011-09-13 Carestream Health, Inc. Metal substrate having electronic devices formed thereon
US8132318B2 (en) * 2006-10-26 2012-03-13 Carestream Health, Inc. Metal substrate having electronic devices formed thereon

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