EP0255558A1 - Bains à base d'une solution comportant un sulfonate organique pour le dépôt de bismuth et des alliages de bismuth - Google Patents

Bains à base d'une solution comportant un sulfonate organique pour le dépôt de bismuth et des alliages de bismuth Download PDF

Info

Publication number
EP0255558A1
EP0255558A1 EP86113044A EP86113044A EP0255558A1 EP 0255558 A1 EP0255558 A1 EP 0255558A1 EP 86113044 A EP86113044 A EP 86113044A EP 86113044 A EP86113044 A EP 86113044A EP 0255558 A1 EP0255558 A1 EP 0255558A1
Authority
EP
European Patent Office
Prior art keywords
bismuth
acid
radical
baths
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.)
Granted
Application number
EP86113044A
Other languages
German (de)
English (en)
Other versions
EP0255558B1 (fr
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/fr
Application granted granted Critical
Publication of EP0255558B1 publication Critical patent/EP0255558B1/fr
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.
  • Examples are Bi-Sn, Bi-In, Bi-Pb, Bi-Co, Bi-Ni, Bi-Sb, Bi-In-Sn, and Bi-Sn-Pb alloys. Since the standard electrode potential of bismuth is far nobler than those of tin, indium, and lead, there occurs practically no codeposition of these alloying elements from their simple solution. To make their deposition potentials as close to one another as possible, a complex salt bath must be used instead.
  • 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 (I) wherein R is a C 1-5 alkyl radical, X 1 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, and aromatic sulfonic acids having various substituents of the formula (II) wherein X 2 is a halogen atom or hydroxyl, alkyl, aryl, alkylary, aldehyde, carboxyl, nitro, mercapto, sulfonyl, or amino radical, or two X 2 's which may combine with a benzene ring to form a naphthalene ring, and m is an integer of 0 to 3.
  • R is a
  • organic sulfonic acids examples include methanesulfonic, ethanesulfonic, propanesulfonic, 2-propanesulfonic, butanesulfonic, 2-butanesulfonic, pentanesulfonic, chloropropanesulfonic, 2-hydroxyethane-l-sulfonic, 2-hydroxypropane-l-sulfonic, 2-hydroxybutane-l-sulfonic, 2-hydroxypentanesulfonic, allylsulfonic, 2-sulfoacetic, 2- or 3-sulfopropionic, sulfosuccinic, sulfo- maleic, sulfofumaric, benzenesulfonic, toluenesulfonic, xylenesulfonic, nitrobenzenesulfonic, sulfobenzoic, sulfosalicylic, and benzaldehydesulfonic acids. These acids are used alone or as
  • 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/f.
  • the concentration of the free organic sulfonic acid to be present in the plating bath is stoichiomet- r ically 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).
  • plating was carried out by 600-coulomb constant current electrolysis, using a stainless steel plate (0.3 x 3 x 5 cm) as the cathode, with cathode rocking at a rate of 2 m/min, while varying the current density over a range of 0.5 - 3 A/dm 2 .
  • the electrodeposit formed was scraped off by a knife and dissolved in 6N-HNO 3 with the application of heat. Tin was separated and the bismuth in the solution was determined by the atomic absorption-spectroscopy. The results are given in Table 1.

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)
EP19860113044 1986-07-04 1986-09-22 Bains à base d'une solution comportant un sulfonate organique pour le dépôt de bismuth et des alliages de bismuth Expired - Lifetime EP0255558B1 (fr)

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 true EP0255558A1 (fr) 1988-02-10
EP0255558B1 EP0255558B1 (fr) 1991-11-27

Family

ID=15626076

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860113044 Expired - Lifetime EP0255558B1 (fr) 1986-07-04 1986-09-22 Bains à base d'une solution comportant un sulfonate organique pour le dépôt de bismuth et des alliages de bismuth

Country Status (4)

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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397663A1 (fr) * 1988-10-14 1990-11-22 Atochem North America Electrodeposition d'alliages d'etain-bismuth.
AU632464B2 (en) * 1988-10-14 1993-01-07 Atochem North America, Inc. A method, bath and cell for the electrodeposition of tin-bismuth alloys
WO1993007309A1 (fr) * 1991-10-07 1993-04-15 Unisys Corporation Systeme de galvanoplastie a basse temperature d'un alliage d'etain-bismuth
EP1308540A1 (fr) * 2001-10-02 2003-05-07 Shipley Co. L.L.C. Bain de placage et méthode de dépôt d'une couche métallique sur un substrat
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
US20220380921A1 (en) * 2021-05-28 2022-12-01 Central South University Compact and flat bismuth metal preparation by electrolysis method

Families Citing this family (6)

* 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
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
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
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

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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 76, no. 14, 3rd April 1972, page 573, 80287f, Columbus, Ohio, US; SU-A-322 414 (KHARKOV CONSTRUCTION-ENGINEERING INSTITUTE) 30-11-1971 *
GALVANOTECHNIK, vol. 66, no. 7, 1975, page 50; S. SRIVEERARAGHAVAN: "Galvanische Abscheidung von Wismut" *
METAL FINISHING, vol. 61, no. 5, May 1963, pages 58,59; J.A. McCARTHY: "Bismuth plating on steel from alkaline electrolytes" *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0397663A1 (fr) * 1988-10-14 1990-11-22 Atochem North America Electrodeposition d'alliages d'etain-bismuth.
EP0397663A4 (en) * 1988-10-14 1991-01-09 Atochem North America, Inc. A method, bath and cell for the electrodeposition of tin-bismuth alloys
AU632464B2 (en) * 1988-10-14 1993-01-07 Atochem North America, Inc. A method, bath and cell for the electrodeposition of tin-bismuth alloys
WO1993007309A1 (fr) * 1991-10-07 1993-04-15 Unisys Corporation Systeme de galvanoplastie a basse temperature d'un alliage d'etain-bismuth
EP1308540A1 (fr) * 2001-10-02 2003-05-07 Shipley Co. L.L.C. Bain de placage et méthode de dépôt d'une couche métallique sur un substrat
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
US20220380921A1 (en) * 2021-05-28 2022-12-01 Central South University Compact and flat bismuth metal preparation by electrolysis method
US11913128B2 (en) * 2021-05-28 2024-02-27 Central South University Compact and flat bismuth metal preparation by electrolysis method

Also Published As

Publication number Publication date
JPH0781196B2 (ja) 1995-08-30
JPS6314887A (ja) 1988-01-22
EP0255558B1 (fr) 1991-11-27
DE3682679D1 (de) 1992-01-09
CA1311713C (fr) 1992-12-22

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
US3677909A (en) Palladium-nickel alloy plating bath
KR20040111564A (ko) 주석 전기증착물에서 위스커 성장의 최소화
CN101243210A (zh) 具有最小化锡晶须生长性能或特性的锡电沉积物
EP0255558B1 (fr) Bains à base d'une solution comportant un sulfonate organique pour le dépôt de bismuth et des alliages de bismuth
JPH0978285A (ja) Ｓｎ−Ｂｉ系合金めっき浴
US3149058A (en) Bright gold plating process
US6562221B2 (en) Process and composition for high speed plating of tin and tin alloys
Kondo et al. Bright tin-silver alloy electrodeposition from an organic sulfonate bath containing pyrophosphate, iodide & triethanolamine as chelating agents
US3692641A (en) Electrodeposition of low stress ruthenium alloy
CA1083078A (fr) Electrodeposition d'alliage
US3850765A (en) Bright solder plating
CA1162505A (fr) Methode et dispositif de deposition ultra-rapide du nickel et de l'or
JP3306768B2 (ja) 鉛及び鉛−錫合金めっき浴
GB2101634A (en) Process and composition for the electrodeposition of tin
US2986500A (en) Electrodeposition of bright nickel
JPH0663110B2 (ja) ビスマス―錫合金電気のめっき浴
US4440608A (en) Process and bath for the electrodeposition of tin-lead alloys
CA1180677A (fr) Bain et methode de nickelage electrolytique rapide
US5264112A (en) Acidic nickel baths containing 1-(2-sulfoethyl)-pyridiniumbetaine
US2763605A (en) Electrodepositing aluminum
US4207148A (en) Electroplating bath for the electrodeposition of tin and tin/cadmium deposits
US2854389A (en) Bright copper plating process
JP3292055B2 (ja) 錫−ビスマス合金電気めっき浴及びそれを使用するめっき方法

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