EP0025694B1 - Bad zum Glanzvernickeln und Verfahren und Zusammensetzung hierfür - Google Patents

Bad zum Glanzvernickeln und Verfahren und Zusammensetzung hierfür Download PDF

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Publication number
EP0025694B1
EP0025694B1 EP80303183A EP80303183A EP0025694B1 EP 0025694 B1 EP0025694 B1 EP 0025694B1 EP 80303183 A EP80303183 A EP 80303183A EP 80303183 A EP80303183 A EP 80303183A EP 0025694 B1 EP0025694 B1 EP 0025694B1
Authority
EP
European Patent Office
Prior art keywords
sulfonated
nickel
acetylenic compound
compound
per liter
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
Application number
EP80303183A
Other languages
English (en)
French (fr)
Other versions
EP0025694A1 (de
Inventor
Kenneth William Lemke
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.)
M&T Chemicals Inc
Original Assignee
M&T Chemicals Inc
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Filing date
Publication date
Application filed by M&T Chemicals Inc filed Critical M&T Chemicals Inc
Priority to AT80303183T priority Critical patent/ATE6873T1/de
Publication of EP0025694A1 publication Critical patent/EP0025694A1/de
Application granted granted Critical
Publication of EP0025694B1 publication Critical patent/EP0025694B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/16—Acetylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt

Definitions

  • This invention relates to improved processes and compositions for the electrodeposition of nickel and alloys thereof.
  • this invention relates to an improved process and composition for the preparation of nickel or nickel alloy electrodeposits which comprises passing current from an anode to a cathode through an aqueous acidic electroplating solution containing:
  • concentrations of said compounds are with a preferred range of
  • Class I brighteners as used herein, and as described in Modern Electroplating, Third Edition, F. Lowenheim, Editor, is meant to include aromatic sulfonates, sulfonamides, sulfonimides, etc., as well as aliphatic or aromatic-aliphatic olefinically unsaturated sulfonates, sulfonamides, sulfonimides, etc. Specific examples of such plating additives are:
  • plating additive compounds which may be used singly or in suitable combinations, are desirably employed in amounts ranging from about 0.5 to 10 grams per liter and provide the advantages described in the above reference and which are well known to those skilled in the art of nickel electroplating.
  • Class II brighteners as used herein, and as described in Modern Electroplating, Third Edition, F. Lowenheim, Editor, is meant to include plating additive compounds such as reaction products of epoxides with alpha-hydroxy acetylenic alcohols such as diethoxylated 2-butyne-1,4-diol N-heterocyclics, dye-stuffs, acetylenic amines, etc.
  • a Class II brightener When used alone or in combination, desirably in amounts ranging from about 5 to 1000 milligrams per liter, a Class II brightener may produce no visual effect on the electrodeposit, or may produce semi-lustrous, fine-grained deposits. However, best results are obtained when Class II brighteners are used with one or more Class I brighteners in order to provide optimum deposit luster, rate of brightening, leveling, bright plate current density range, low current density coverage, etc.
  • anti-pitting or wetting agents as used herein is meant to include a material which functions to prevent or minimize gas pitting.
  • An anti-pitting agent when used alone or in combination, desirably in amounts ranging from about 0.05 to 1 gram per liter, may also function to make the baths more compatible with contaminants, such as oil, grease, etc. by their emulsifying, dispersing, solubilizing, etc. action on such contaminants and thereby promote attaining of sounder deposits.
  • Preferred anti-pitting agents may include sodium lauryl sulfate, sodium lauryl ether-sulfate and sodium di- alkylsulfosucbinates.
  • the nickel compounts employed for electrodepositing nickel are typically added as the sulfate, chloride, sulfamate, or fluoborate salts.
  • the sulfate, chloride, sulfamate and fluoborate salts of nickel are employed in concentrations sufficient to provide nickel in the electroplating solutions of this invention in concentrations ranging from about 10 to 150 grams per liter.
  • the nickel compounds employed for electrodepositing nickel are typically added as the sulfate, grams per liter, preferably about 45 grams per liter of boric acid or other buffering agents to control the pH (e.g.; from about 3.0-5.0, preferably 4.0) and to prevent high current density burning.
  • solution agitation may be employed. Air agitation, mechanical stirring, pumping, cathode rod and other means of solution agitation are all satisfactory. Additionally, the solutions may be operated without agitation.
  • the operating temperature of the electroplating baths of this invention may range from about 40°C to about 70°C, preferably from about 50°C to 62°C.
  • the average cathode current density may range from about 0.5 .to 12 amperes per square decimeter, with 3 to 6 amperes per square decimeter providing an optimum range.
  • Typical aqueous nickel-containing electroplating solutions include the following wherein all concentrations are in grams per liter (g/l) unless otherwise indicated.
  • the pH may normally tend to rise and may be adjusted with acids such as hydrochloric acid, sulfuric acid, etc.
  • Anodes used in the above baths may be electrolytic or sulfur containing nickel bars, strips or small chunks in titanium baskets. All anodes are usually suitably covered with cloth or plastic bags of desired porosity to minimize introduction into the bath of metal particles, anode slime, etc. which may migrate to the cathode either mechanically or electrophoretically to give roughness in cathode deposits.
  • the substrates on which the nickel electrodeposits of this invention may be applied may be metal or metal alloys such as are commonly electrodeposited and used in the art of electroplating such as nickel, cobalt, nickel-cobalt, copper, tin, brass, etc.
  • Other typical substrate basis metals from which articles to be plated are manufactured may include ferrous metals such as iron, steel, alloy steels, copper, tin and alloys thereof such as with lead, alloys of copper such as brass, bronze, etc., zinc, particularly in the form of zinc-base die castings; all of which may bear plates of other metals, such as copper, etc.
  • Basis metal substrates may have a variety of surface finishes depending on the final appearance desired, which in turn depends on such factors as luster, brilliance, leveling, thickness, etc. of the nickel electroplate applied on such substrates.

Landscapes

  • 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)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Materials For Photolithography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Paints Or Removers (AREA)

Claims (12)

1. Verfahren zur Herstellung einer galvanischen Beschichtung die Glanznickel enthält, bei dem Strom von einer Anode zu einer Kathode durch ein wässeriges, saures Galvanisierbad geleitet wird, das wenigstens eine Nickelverbindung, 0,2-10 g/1 Saccharin und 20-500 ppm Zinkionen enthält, dadurch gekennzeichnet, daß im Galvanisierbad 0,01-1,0 g/I wenigstens einer sulfonierten acetylenischen Verbindung oder eines Salzes derselben enthalten sind, wobei die acetylenische Bindung und der Sulfonatrest direckt durch eine Kohlenstoffatom oder durch eine Kohlenstoffkette von nicht mehr als 6 Kohlenstoffatomen verbunden sind.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung 2-Butin-1 ,4-disulfonsäure ist.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die sulfonierte acetylenische Bindung 2-Butinsulfonsäure ist.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung Propinsulfonsäure ist.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung 1-Butinsulfonsäure ist.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung 1-Pentinsulfonsäure ist.
7. Wässeriges saures Galvanisierbad mit einem Gehalt an wenigstens einer Nickelverbindung, weiche Nickelionen zur galvanischen Abscheidung von Nickel liefert, 0,2-10 g/I Saccharin und 20―500 ppm Zinkionen, dadurch gekennzeichnet, daß es 0,01 g/l―1,0 g/l wenigstens einer sulfonierten acetylenischen Verbindung oder eines Salzes derselben enthält, wobei die acetylenische Bindung und der Sulfonatrest direkt durch ein Kohlenstoffatom oder eine Kohlenstoffkette mit nicht mehr als 6 C-Atomen verbunden sind.
8. Galvanisierbad nach Anspruch 7, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung 2-Butin-1,4-disulfonsäure. ist.
9. Galvanisierbad nach Anspruch 7, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung 2-Butinsulfonsäure ist.
10. Galvanisierbad nach Anspruch 7, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung Propinsulfonsäure ist.
11. Galvanisierbad nach Anspruch 7, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung 1-Butinsulfonsäure ist.
12. Galvanisierbad nach Anspruch 7, dadurch gekennzeichnet, daß die sulfonierte acetylenische Verbindung 1-Pentinsulfonsäure ist.
EP80303183A 1979-09-13 1980-09-10 Bad zum Glanzvernickeln und Verfahren und Zusammensetzung hierfür Expired EP0025694B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80303183T ATE6873T1 (de) 1979-09-13 1980-09-10 Bad zum glanzvernickeln und verfahren und zusammensetzung hierfuer.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7495379A 1979-09-13 1979-09-13
US74953 1987-07-17

Publications (2)

Publication Number Publication Date
EP0025694A1 EP0025694A1 (de) 1981-03-25
EP0025694B1 true EP0025694B1 (de) 1984-03-28

Family

ID=22122633

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80303183A Expired EP0025694B1 (de) 1979-09-13 1980-09-10 Bad zum Glanzvernickeln und Verfahren und Zusammensetzung hierfür

Country Status (11)

Country Link
EP (1) EP0025694B1 (de)
JP (1) JPS5647583A (de)
AT (1) ATE6873T1 (de)
AU (1) AU532948B2 (de)
BR (1) BR8005852A (de)
DE (1) DE3067275D1 (de)
ES (1) ES495007A0 (de)
HK (1) HK80384A (de)
MX (1) MX153967A (de)
NZ (1) NZ194923A (de)
ZA (1) ZA805658B (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4699696A (en) * 1986-04-15 1987-10-13 Omi International Corporation Zinc-nickel alloy electrolyte and process
DE3632514A1 (de) * 1986-09-22 1988-03-24 Schering Ag (alpha)-hydroxi propinsulfonsaeure und deren salze, saure nickelbaeder enthaltend diese verbindungen sowie verfahren zu ihrer herstellung
KR20190028708A (ko) 2016-07-18 2019-03-19 바스프 에스이 보이드 없는 서브미크론 피쳐 충전을 위한 첨가제를 포함하는 코발트 도금용 조성물
EP3680366A4 (de) * 2017-09-06 2021-06-09 Kanto Denka Kogyo Co., Ltd. Elektrode und herstellungsverfahren dafür sowie herstellungsverfahren für regenerierte elektrode

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719568A (en) * 1970-12-11 1973-03-06 Oxy Metal Finishing Corp Nickel electroplating composition and process
US3825478A (en) * 1972-10-30 1974-07-23 Oxy Metal Finishing Corp Electrolyte and method for electrodepositing microporous chromium-nickel composite coatings
US3884773A (en) * 1973-08-17 1975-05-20 Metalux Corp Electrodeposition of nickel
BR7410536D0 (pt) * 1973-12-27 1975-09-02 Du Pont Aditivo abrilhantador banho e processo de eletrodeposicao bem como processo para fabricar o referido aditivo
US4016051A (en) * 1975-05-02 1977-04-05 Starlite Chemicals, Inc. Additives for bright plating nickel, cobalt and nickel-cobalt alloys
CA1069850A (en) * 1975-12-04 1980-01-15 Mcgean Chemical Company Low temperature bright nickel and bright nickel alloy plating

Also Published As

Publication number Publication date
AU6236580A (en) 1981-03-19
HK80384A (en) 1984-11-02
ZA805658B (en) 1982-03-31
EP0025694A1 (de) 1981-03-25
MX153967A (es) 1987-03-03
DE3067275D1 (en) 1984-05-03
JPS6252035B2 (de) 1987-11-02
NZ194923A (en) 1982-05-25
ES8205437A1 (es) 1982-06-01
ES495007A0 (es) 1982-06-01
BR8005852A (pt) 1981-03-24
ATE6873T1 (de) 1984-04-15
AU532948B2 (en) 1983-10-20
JPS5647583A (en) 1981-04-30

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