EP0255558B1 - Bäder auf Basis von einer ein organisches Sulphonat enthaltenden Lösung für das Plattieren von Wismut und Wismutlegierungen - Google Patents

Bäder auf Basis von einer ein organisches Sulphonat enthaltenden Lösung für das Plattieren von Wismut und Wismutlegierungen Download PDF

Info

Publication number
EP0255558B1
EP0255558B1 EP19860113044 EP86113044A EP0255558B1 EP 0255558 B1 EP0255558 B1 EP 0255558B1 EP 19860113044 EP19860113044 EP 19860113044 EP 86113044 A EP86113044 A EP 86113044A EP 0255558 B1 EP0255558 B1 EP 0255558B1
Authority
EP
European Patent Office
Prior art keywords
bismuth
bath
baths
acid
alloy plating
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
EP19860113044
Other languages
English (en)
French (fr)
Other versions
EP0255558A1 (de
Inventor
Seishi Masaki
Kiyotaka Tsuji
Yoshiaki Okuhama
Toshiji Akutsu
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.)
Ishihara Chemical Co Ltd
Daiwa Fine Chemicals Co Ltd
Original Assignee
Ishihara Chemical Co Ltd
Daiwa Fine Chemicals Co Ltd
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
Publication date
Application filed by Ishihara Chemical Co Ltd, Daiwa Fine Chemicals Co Ltd filed Critical Ishihara Chemical Co Ltd
Publication of EP0255558A1 publication Critical patent/EP0255558A1/de
Application granted granted Critical
Publication of EP0255558B1 publication Critical patent/EP0255558B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

Definitions

  • This invention relates to bismuth and bismuth alloy plating baths. More particularly, it is concerned with bismuth and bismuth alloy electroplating baths which use an organic sulfonic acid as a co-soluble complex salt of bismuth and the metal other than bismuth and give smooth electroplated deposits without the emission of highly polluting matter.
  • Bismuth is extensively used as a lubricant in nuclear reactor construction as well as in such newly opened fields as the manufacture of rectifier and ohmic contacts. These applications require relatively thick plates, approximately from 30 to 100 ⁇ m in thickness. With conventional complex salt baths such as perchlorate, glycerate-tartrate, and Trilon baths, however, the resulting deposits free of trees dendrite are at best 10 ⁇ m thick. Ordinary baths using no complex salt provide only coarse-crystal films.
  • Varied Bi-Sn alloy plating baths for example, in the form of sulfate, chloride, perchlorate, borofluoride, and alkali baths, have hitherto been reported. Nevertheless, because of the electric potential difference, it is difficult to codeposit a relatively large proportion of bismuth to tin, and an electrodeposit of the low-melting alloy can hardly be obtained.
  • the Bi-In alloy plating from a perchlorate bath the limitation to the current density range over which the codeposit is formed makes it rarely possible to obtain thick, good alloy plates.
  • the present invention has resulted from investigations made in view of the foregoing. It is aimed at providing a plating bath which consists essentially of an organic sulfonic acid that seldom poses a pollution problem and salts of bismuth and a metal other than bismuth, and gives substantially better electrodeposits than those from conventional inorganic acid baths, and permits easy control of the bath in alloy plating, inasmuch as the electrodeposit composition is close to the metal proportion in the bath.
  • the investigations have led to the discovery of useful acids for the above purpose.
  • the organic sulfonic acids to be used in accordance with the invention are sulfonic acids as aliphatic or nonbenzene alicyclic compounds of the general formula (X1) n -R-SO3H wherein R is a C1 ⁇ 5 alkyl radical, X1 is a halogen atom or hydroxyl, aryl, alkylaryl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of 0 to 3.
  • organic sulfonic acids examples include methanesulfonic, ethanesulfonic, propanesulfonic, 2-propanesulfonic, butanesulfonic, 2-butanesulfonic, pentanesulfonic, chloropropanesulfonic, 2-hydroxyethane-1-sulfonic, 2-hydroxypropane-1-sulfonic, 2-hydroxybutane-1-sulfonic, 2-hydroxypentanesulfonic, allylsulfonic, 2-sulfoacetic, 2- or 3-sulfopropionic, sulfosuccinic, sulfomaleic, sulfofumaric acids. These acids are used alone or as a mixture of two or more. Their bismuth salts and salts of metals other than bismuth are prepared in the usual manner.
  • a bismuth plating bath contains such an organic sulfonic acid and its bismuth salt.
  • a bismuth alloy plating bath such an organic sulfonic acid, its bismuth salt, and another or two or more metal salts are contained.
  • the total concentration of bismuth and another metal or metals is, in terms of the metals, from 0.5 to 200 g/l, preferably from 10 to 100 g/l.
  • the concentration of the free organic sulfonic acid to be present in the plating bath is stoichiometrically at least an equivalent to the bismuth or other metal ions in the bath.
  • the concentration of the free organic sulfonic acid is 30-400 g/l.
  • the plating bath of the invention may contain peptone, gelatin, nonionic surfactant, or other additive effective in avoiding burnt deposits due to excessive current intensity and in inhibiting dendritic growth.
  • concentration of the additive usually ranges from 0.01 to 50 g/l, preferably from 0.05 to 20 g/l.
  • typical nonionic surfactants for this use are "Evan 740", “Liponox N-105", and "Neugen EN" (all trade names).

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)

Claims (1)

  1. Wismut- oder Wismutlegierungs-Plattierbad das als wesentliche Bestandteile eine organische Sulfonsäure der allgemeinen Formel



            (X₁)n-R-SO₃H,



    wobei R ein C₁₋₅-Alkylradical, X₁ ein Halogenatom oder ein Hydroxyl-, Carboxyl- oder Sulfonylradikal, das an jeder beliebigen Position des Alkylradikals stehen kann, und n eine ganze Zahl von 0 bis 3 ist, und ein Wismutsalz der Säure oder ein Gemisch des Wismutsalzes der Säure und eines oder mehrerer anderer Metallsalze der Säure enthält, wobei das Wismutsalz oder Salze von Wismut und einem oder mehreren anderen Metall(en) der organischen Säure in einer Konzentration von 0,5 bis 200 g pro Liter des Bades, bezogen auf die betreffenden metallischen Elemente, verwendet sind und die Konzentration der freien organischen Sulfonsäure in dem Plattierbad 30 bis 400 g pro Liter des Bades beträgt und stöchiometrisch mindestens äquivalent zu den Wismut- oder anderen Metallionen in dem Bad ist.
EP19860113044 1986-07-04 1986-09-22 Bäder auf Basis von einer ein organisches Sulphonat enthaltenden Lösung für das Plattieren von Wismut und Wismutlegierungen Expired - Lifetime EP0255558B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61156361A JPH0781196B2 (ja) 1986-07-04 1986-07-04 有機スルホン酸塩からのビスマス及びビスマス合金めつき浴
JP156361/86 1986-07-04

Publications (2)

Publication Number Publication Date
EP0255558A1 EP0255558A1 (de) 1988-02-10
EP0255558B1 true EP0255558B1 (de) 1991-11-27

Family

ID=15626076

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860113044 Expired - Lifetime EP0255558B1 (de) 1986-07-04 1986-09-22 Bäder auf Basis von einer ein organisches Sulphonat enthaltenden Lösung für das Plattieren von Wismut und Wismutlegierungen

Country Status (4)

Country Link
EP (1) EP0255558B1 (de)
JP (1) JPH0781196B2 (de)
CA (1) CA1311713C (de)
DE (1) DE3682679D1 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0765207B2 (ja) * 1988-09-22 1995-07-12 上村工業株式会社 ビスマス―錫合金電気めっき方法
JPH0765206B2 (ja) * 1988-09-22 1995-07-12 上村工業株式会社 ビスマス―錫合金電気めっき方法
ATE105877T1 (de) * 1988-10-14 1994-06-15 Atochem North America Elektroniederschlag von zinn-wismut-legierungen.
AU632464B2 (en) * 1988-10-14 1993-01-07 Atochem North America, Inc. A method, bath and cell for the electrodeposition of tin-bismuth alloys
JP2819180B2 (ja) * 1990-02-22 1998-10-30 信康 土肥 すず―鉛―ビスマス合金めっき浴
US5227046A (en) * 1991-10-07 1993-07-13 Unisys Corporation Low temperature tin-bismuth electroplating system
JP3274232B2 (ja) * 1993-06-01 2002-04-15 ディップソール株式会社 錫−ビスマス合金めっき浴及びそれを使用するめっき方法
JP4728462B2 (ja) * 2000-02-29 2011-07-20 日本リーロナール有限会社 錫電気めっき液及びめっき方法
US6736954B2 (en) 2001-10-02 2004-05-18 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
DE102005016819B4 (de) * 2005-04-12 2009-10-01 Dr.-Ing. Max Schlötter GmbH & Co KG Elektrolyt, Verfahren zur Abscheidung von Zinn-Wismut-Legierungsschichten und Verwendung des Elektrolyten
JP2020169360A (ja) * 2019-04-03 2020-10-15 奥野製薬工業株式会社 電気めっき用Ｂｉ−Ｓｂ合金めっき液
CN113293409B (zh) * 2021-05-28 2022-06-24 中南大学 一种电解制备致密平整铋金属的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5967387A (ja) * 1982-10-08 1984-04-17 Hiyougoken すず、鉛及びすず―鉛合金メッキ浴
US4565609A (en) 1983-12-22 1986-01-21 Learonal, Inc. Bath and process for plating tin, lead and tin-lead alloys
US4565610A (en) 1983-12-22 1986-01-21 Learonal, Inc. Bath and process for plating lead and lead/tin alloys

Also Published As

Publication number Publication date
JPH0781196B2 (ja) 1995-08-30
JPS6314887A (ja) 1988-01-22
DE3682679D1 (de) 1992-01-09
CA1311713C (en) 1992-12-22
EP0255558A1 (de) 1988-02-10

Similar Documents

Publication Publication Date Title
DE69924807T2 (de) Zinn-Kupfer-Legierung Elektroplattierungsbad und Plattierungsverfahren mit diesem Bad
KR100268967B1 (ko) 금속 착물 형성용 수용액, 주석-은 합금도금욕 및 당해도금욕을 사용하는 도금물의 제조방법
US5039576A (en) Electrodeposited eutectic tin-bismuth alloy on a conductive substrate
US4331518A (en) Bismuth composition, method of electroplating a tin-bismuth alloy and electroplating bath therefor
EP0255558B1 (de) Bäder auf Basis von einer ein organisches Sulphonat enthaltenden Lösung für das Plattieren von Wismut und Wismutlegierungen
KR20040111564A (ko) 주석 전기증착물에서 위스커 성장의 최소화
EP1754805B1 (de) Zinn galvanisches Bad und Zinn galvanisches Abscheidungsverfahren
US2436316A (en) Bright alloy plating
US20040149587A1 (en) Electroplating solution containing organic acid complexing agent
US3149058A (en) Bright gold plating process
DE3628361A1 (de) Waessriges saures bad und verfahren zur galvanischen abscheidung von zinklegierungsueberzuegen
US6458264B1 (en) Sn-Cu alloy plating bath
CA1083078A (en) Alloy plating
US3850765A (en) Bright solder plating
JP4547583B2 (ja) スズ合金メッキを施した表面被覆材料、並びに当該被覆材料を利用した電子部品
CA1162505A (en) Process for high speed nickel and gold electroplate system
JP3306768B2 (ja) 鉛及び鉛−錫合金めっき浴
GB2101634A (en) Process and composition for the electrodeposition of tin
US4440608A (en) Process and bath for the electrodeposition of tin-lead alloys
US2734025A (en) Twatktnw att
US3408272A (en) Electrodeposition of chromium
CA1180677A (en) Bath and process for high speed nickel electroplating
US4207148A (en) Electroplating bath for the electrodeposition of tin and tin/cadmium deposits
JPH0663110B2 (ja) ビスマス―錫合金電気のめっき浴
US2474092A (en) Composition for and method of electrodeposition of lead

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19880212

17Q First examination report despatched

Effective date: 19890320

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19911127

Ref country code: FR

Effective date: 19911127

Ref country code: NL

Effective date: 19911127

REF Corresponds to:

Ref document number: 3682679

Country of ref document: DE

Date of ref document: 19920109

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20050905

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050914

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20060921

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20