CA1311713C - Baths of organic sulfonate solution for bismuth and bismuth alloy plating - Google Patents

Baths of organic sulfonate solution for bismuth and bismuth alloy plating

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Publication number
CA1311713C
CA1311713C CA 519048 CA519048A CA1311713C CA 1311713 C CA1311713 C CA 1311713C CA 519048 CA519048 CA 519048 CA 519048 A CA519048 A CA 519048A CA 1311713 C CA1311713 C CA 1311713C
Authority
CA
Canada
Prior art keywords
bismuth
acid
baths
radical
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
CA 519048
Other languages
French (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
Application granted granted Critical
Publication of CA1311713C publication Critical patent/CA1311713C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

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

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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)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE

A bismuth or bismuth alloy plating bath comprises as essen-tial ingredients an organic sulfonic acid of the general formula (I) (X1)n-R-SO3H ------ (I) 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, or of the formula (II)

Description

c~ ~z~g ~,31~PI~'~
BATHS OF ORGANIC SULFONATE SOLUTION
FOR BISMUTH AND BISMUTH ALLOY PLATING

BACKGROUND OF T~, INVENTION
This invention relates to bismut;h 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` bismu~h and the ~etal other than bismuth and give smooth electroplated deposits without the emission of highly pollutlng matter.
Bismuth is extensively used as a lubricant in nuclear reactor construction as well as in such newly opened fields as the manu-facture of recti~ier 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 ~ree of trees dendrite are at best 10 ~m thick. Ordinary baths using no complex s~lt provide only coarse=
crystal films.
Fast progress of the electronic industry in recent years has created demands Lor various bismuth-base alloys of low-melting points. Increasing importance is being attached to these low=
melting solders because o~ the introduction o~ semiconductors with more and more dellcate thermal properties. Ordinary sol-ders, typi~ied by the Sn-Pb alloy, have the disadvanta~e of *Trademark v, ,., ,. , ; .~, 131~P3 so-called low-temperature brittleness. Component parts soldered with them become brittle when placed in environmcnts below ordi nary temperature, as are encountered by the soldered parts of devices and apparatus for use in superconductive and space development projects. For services in such severe environments, therefore, low-temperature resistant solders are desirable.
Examples are Bi-Sn, Bi-In, Bi-Pb, Bi-Co, Bi-Ni, Bi-Sb, Bi-In-Sn, and Bi-Sn-Pb alloys. Since the st;~ndard 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 camplex salt bath must be used instead!
Varied 8i-Sn alloy plating baths, for example, in the ~orm of sulfate, chloride, perchlorate, boro~luoride, and alkali baths, have hitherto been reported. Nevertheless, because o~
the electric potential difference, it is dlfficult to codeposit a relatively large proportion of bismuth to tin, and an electro-deposit of the low-~elting alloy can hardl~ be obtained. As for 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.
SU~ARY OF THE INVENTION
The present invention has resulted ~rom investigations made in view o~ the foregoine. It i9 ai~ed at providing a pl-tin~

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`"': ' :
~:

~3:1~ 7~

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 electrodepo-sits 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. Thus the investigations have led to the discovery of useful acids for the above purpose.
In the case of Bi-Sn alloy pl~ating, a major disadvantage is that, where the electric potential difference between tin and bismuth is too wide for the passage of current, bismuth can be lost by its contact deposition on the anode tin surface. It has now been found that the plating bath of the invention character-istically inhibits to a large measure the unwanted bismuth deposition on the anode tin surface.
DETAILED D~SCRIPTION OF THE INVENTION
The organic sulfon~c acids to be used in accordance with the invention are sulfonic acids as aliphatic or nonbenzene alicyclic compounds of the general formula ~I) (Xl) n ~ ~ -S Os~
wherein R is a Cl 5 alkyl radical, Xl is a halogen atom or hydroxyl 9 aryl, alkylaryl, carboxyl, or sulfonyl radical which may be in any optional position of the alkyl radical, and n is an integer of O to 3, and aromatic sulfonic acids having various substituen~s o~ The formula (I.) .' ' ~ .. ' ' ~ . .
.

~3~7 ~ 3 I~(X2)m ~

wherein X2 is a halogen atom or hydroxyl, alkyl, aryl, alkylaryl, aldehyde, carboxyl, nitro, mercapto, sulfonyl, or amino radical, or two Xz's which may combine with a benzene ring to form a naphthalene ring, and m is an lnteger of 0 to 3.
Examples of these organic sulfonic aclds are methanesulfonic, ethanesulfonic, propanesul~onic, 2-propanesulfonic, butanesulfon-ic, 2-butanesulfonic, pentanesulfonlc, chloropropanesulfonic, 2-hydroxyethane-l-sulfonic, 2-hydroxypropane-l-sulfonic, 2-hy-droxybutane-l-sul~onic, 2-hydroxypentanesulfonic, allylsulfonic, ~-sulfoacetic, 2- or 3-sulfopropionic, sul~osuccinic, sulfo-maleic, sulfofumaric, benzenesulfonic, toluenesulfonic~ xylene-sulfonic, nitrobenzenesulfonic, sulfobenzoic, sulfosalicylic, 2nd benzaldehydesuifonlc 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 sul~onic acid and its bismuth salt. In the case o~ 2 bismuth alloy plating ~ath, such an organic sulfonic acid, its bismuth salt, and ano~her or two ar more metal salts are contained.

The total concentration of bi6muth and another metal salt of the organic sul~onic acid is, in terms of the metals, from 0.5 to 200 gJ~t preferably from lO to lO0 g/~. The concentration of the free organic .... :
-. .
. .

~ 3 ~

sulfonic acid to be pre~ent in the plating bath is stoichiometrically at least an equivalent to the concentration of the bismuth and other metal salts in the bath. Preferably, the concentration of the free organic sulfonic acid is 30-400 g/Q.
The plating bath of the invention may contain peptone, gela-tin, nonionic surfactant, or other additive effective in avoiding burnt deposits due to exeessive current lntensity and in inhibit-ing dendritic growth. The concentration of the additive usually ranges from 0.01 to 50 g~l, preferably from 0.05 to 20 g/l.

*
Among typical nonionic surfactants for this use are "Epon 740", "Liponox N-105", and "Neugen EN".
~ X A M P L E S
While the present invention is illustrated by the following several examples in which certain plating bath compositions and operating conditions are used, it should be noted that the inven~
tion is not limited thereto but may be ~ariously embodied with changes in the compositions and conditions to realize the objects of obtaining uniform, smooth plated deposits.
Throughout the examples, the outward appearance of the plate obtained was e~aluated by the Hull cell test.
Example 1 Bismuth (as bismuth methanesulfonate) 20 g/l Free methanesul~onic acid 150 "
Gelatin 5 "
Temperature 25C
Current density range 0.5-S A/dm *Trademark j!

. . .

' ' '. ', ' . ' ' ~3~7~3 Example 2 Bismuth tas bismuth 2-hydroxypropanesulfonate) 15 g/~
Free 2-hydroxypropanesulfonic acid 100 "
"Epon 740"
Temperature 30C
Current density range 0.2-3 A/dm2 Example 3 Bismuth (as bismuth sulfosuccinate) 30 g/2 Free sulfosuccinic acid . 200 Peptone 5 "
Temperature 20C
Current density range 1-6 A/dm2 Example 4 Bismuth (as bismuth p-phenolsulfonate) 25 g/~
Free p-phenolsulfonic acid 120 Peptone 2 Temperature 25C
Current density range 1-5 A/dm2 Example 5 Bismuth (as bismuth p-toluenesulfonate) 6 g/~
Free p-toluenesulfonic acid 150 Gelatin 3 "
Temperature 30C
Current density range 0.2-S A/dm2 , .
. ~ . ... .

13~7~3 Bismuth (as bismuth sulfosalicylate) 10 g/Q
Free sulfosalicylic acld 200 "
"Liponox N-105"
Temperature 30C
Current densit~ range 0.5-5 A/dm2 With the platin~ baths of Examples 1 to 6, Hull cell tests were conducted under the conditions of 1 A and 5 min. Each example gave a grayish white smooth electrodeposit.
Example 7 Bismuth ~as bismuth methanesulfonate) 2 g/Q
Divalent tin (as stannous methanesulfonate) 18 "
Free methanesulfonic acid 150 "
"Neugen EN" ` 5 "
Temperature 25C
Current density range 0.5-3 A/dm2 Example 8 Bismuth (as bismuth benzenesulfonate) 12 g/2 Divalent tin (as tin benzenesulfonate) 8 "
Free benzenesulfonic acid 120 "
Peptone 2 "
Temperature 30C
Current density range 0.2-5 A/dm2 Example 9 Bismuth (as bismuth 2-hydroxypropanesulfonate) 10 g/~
Divalent tin (as stannous 2-hydrox~propanesulfonate) : - 7 -.

''' ' , ' . . . ~

,. .
' ' : ' ' "

.
.
~' :. .

1 3 ~

5.6 "
Lead (as lead 2-hydroxypropanesulfonate) 4.4 "
Free 2-hydroxypropanesulfonic acid 180 "
Gelatin 7 "
Temperature 20C
Current density ran~e 0.1-3 A/dm2 The plating baths of Examples 7 to 9 were subjected to Hull cell tests under the conditions of 1 A and 5 minO All gave gray-ish white smooth electrodeposits.
In order to con~irm the composition of the electrodeposit formed by the bismuth alloy plating, 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 ~arying the current density over a range of 0.5 - 3 A/dm2. After each run the electrodeposit formed was scraped off by a knife and dissolved in 6N-HN03 with the ~pplication 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.
T a b 1 e Dk (Ajdm2) 0.5 1.0 2.0 3.0 Bi in electrodeposit, % 26,0 20.4 13,8 15.3 Current efficiency, % 89.2gO.3 73.2 56.4 .
~ 8 ---

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A bismuth or bismuth alloy plating bath comprising as essential ingredients an or-ganic sulfonic acid of the general formula (X1)n - R - SO3H
wherein R is a C1-5 allyl radical, X1 is a halogen atom or hydroxyl, 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 a bismuth salt of the acid or a mixture of the bismuth salt of the acid and one or more other metal salts of the acid, said bismuth or bismuth alloy salts of the organic acid being used at a concentration, in terms of the respective metallic elements, of 0.5 to 200 g per liter of the bath, and the concen-tration of free organic sulfonic acid being 30 to 400 g per liter of the bath.
CA 519048 1986-07-04 1986-09-25 Baths of organic sulfonate solution for bismuth and bismuth alloy plating Expired - Lifetime CA1311713C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61156361A JPH0781196B2 (en) 1986-07-04 1986-07-04 Bismuth and bismuth alloy plating baths from organic sulfonates
JP156361/1986 1986-07-04

Publications (1)

Publication Number Publication Date
CA1311713C true CA1311713C (en) 1992-12-22

Family

ID=15626076

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 519048 Expired - Lifetime CA1311713C (en) 1986-07-04 1986-09-25 Baths of organic sulfonate solution for bismuth and bismuth alloy plating

Country Status (4)

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

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0765206B2 (en) * 1988-09-22 1995-07-12 上村工業株式会社 Bismuth-tin alloy electroplating method
JPH0765207B2 (en) * 1988-09-22 1995-07-12 上村工業株式会社 Bismuth-tin alloy electroplating method
DE3889667T2 (en) * 1988-10-14 1994-10-13 Atochem North America, Inc., Philadelphia, Pa. ELECTRIC DEPOSITION OF TIN-BISMUT 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
JP2819180B2 (en) * 1990-02-22 1998-10-30 信康 土肥 Tin-lead-bismuth alloy plating bath
US5227046A (en) * 1991-10-07 1993-07-13 Unisys Corporation Low temperature tin-bismuth electroplating system
JP3274232B2 (en) * 1993-06-01 2002-04-15 ディップソール株式会社 Tin-bismuth alloy plating bath and plating method using the same
JP4728462B2 (en) * 2000-02-29 2011-07-20 日本リーロナール有限会社 Tin electroplating solution and plating method
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 (en) * 2005-04-12 2009-10-01 Dr.-Ing. Max Schlötter GmbH & Co KG Electrolyte, process for the deposition of tin-bismuth alloy layers and use of the electrolyte
JP7508077B2 (en) * 2019-04-03 2024-07-01 奥野製薬工業株式会社 Bi-Sb alloy plating solution for electroplating
CN113293409B (en) * 2021-05-28 2022-06-24 中南大学 Method for preparing compact and flat bismuth metal through electrolysis

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5967387A (en) * 1982-10-08 1984-04-17 Hiyougoken Tin, lead and tin-lead alloy plating bath
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
JPS6314887A (en) 1988-01-22
JPH0781196B2 (en) 1995-08-30
DE3682679D1 (en) 1992-01-09
EP0255558B1 (en) 1991-11-27
EP0255558A1 (en) 1988-02-10

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