CA1172599A - Method and apparatus for the electro-deposition of lead alloys - Google Patents

Method and apparatus for the electro-deposition of lead alloys

Info

Publication number
CA1172599A
CA1172599A CA000386328A CA386328A CA1172599A CA 1172599 A CA1172599 A CA 1172599A CA 000386328 A CA000386328 A CA 000386328A CA 386328 A CA386328 A CA 386328A CA 1172599 A CA1172599 A CA 1172599A
Authority
CA
Canada
Prior art keywords
lead
tin
solution
anode
cathode
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
CA000386328A
Other languages
French (fr)
Inventor
William J. Waterman
Michael G. Brook
Lita E. Jenni
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.)
Dana Inc
Original Assignee
GKN Vandervell 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 GKN Vandervell Ltd filed Critical GKN Vandervell Ltd
Application granted granted Critical
Publication of CA1172599A publication Critical patent/CA1172599A/en
Expired 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
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002Cell separation, e.g. membranes, diaphragms

Abstract

ABSTRACT

Apparatus and method for the electro-deposition of a ternary alloy on to a cathode comprises an anolyte containing chamber 14 and a catholyte containing chamber 10 in communi-cation with one another only through the medium of a cation exchange membrane 16. The apparatus is used for depositing a teruary bearing alloy, such as lead-antimony-tin or lead-tin-copper on to the bronze substrate of a steel backed bearing member; the bearing member comprising the cathode 12.
Use of the method and apparatus prevents undesirable immer-sion plating of the lead-containing anode 20 by metals from the plating solution which are more noble than lead.

Description

~7;~599 79.023/BT

Method and ~pparatus ~or the Elec'cro--Deposition of Lead Alloys This invention relates to a method and apparatus for the electro-deposition of an alloy coating on to a backing member, such a process being of particular intcrest to the coating of a load carrying bearing surface on to the backing member of a plain bearing.

Such a bearing may comprise for example a half shell backing member of steel with a bronze substrate bonded there--to and on to which is electro-deposited a bearing surface coating of lead~indium or lead-antimony-tin. ~inary and ternary alloys can be co-deposited electrolytically as is described for example in British Patents 577335 and 628L~59 and in U.S.A Patent 2605149. In British Patent 577335 it is stated, and has been verified in tests, that coatings of ternary alloys such as lead-antimony-tin or lead-tin-copper can replace the more usual lead-tin or lead indium binary alloy coatings as bearing surfaces.

However in the electro-deposition of ternary alloys containing antimony or copper, there is a displacement reaction when a soluble metal anode is used. For example in British Patent 628459 it is stated that antimony will immer sion plate on to a lead, lead-tin or lead-tin~antimony anode.
In Patent 628459 it is stated that this immersion plating is adherent eno~gh so that the anode may be used two or three times and then the antimony may be scrubbed off and reclaimed and~ whereas such a procedure may be acceptable for small scale operation, it would not be feasible tG operate a continuous production plating process wherein anodes were required to be removed many times durlng the working opera tion for scrubbing.
$~

~ 7~599 Simi.larly if a lead-tin--copper electrolyte is utilised, the copper .in the plating solution immersion p].ates out on to metal anodes such as lead or lead-tin and, although such an electrolyte has been in prodv.ction use f'or many years, the removal of~ al] the anodes frorn the bath during idle periods is required, and frequent additions of copper fluorobvrate are necessary to replace losses from the electrolyte.

It is the object of the present invention to provide an improved method and apparatus which will prevent the undesir-able immersion plating of a soluble metal anode containi.nglead by metals from the plating solution which are more noble than lead.

In accordance with one aspect of the invention there is provided apparatus for the electro~deposition of an alloy on to a cathode comprising a first cham'oer within which the cat.hode is located and which contains a catholyte solution; a second charr.ber w.ithin which the anode is located and wh.ich contains an anolyte solution, and said fir~t and second chambers communicating with one another only through the medium of a cation exchange membrane~

In accordance with a further aspect of the invention there is provided a method of electro-depositing an alloy on to a metal cathode comprising the steps of immersing the cathode in a first chamber containing a catholyte solution, immersing a metal anode in a second chamber contai.r,ing an anolyte solution communicating with said catholyte solution only through the medium of a cation exchange membrane and applying a direct current between the anode and cathode.

ln use of the apparatus and method according to the invention the anolyte will not contain elements capable of immersion plating on 'o the anode. Thus if the catholyte comprises a lead-antimony tin plating soluti.on then the anolyte ~ili not contair. any antimony. Sirni.larly i.f the ~7;~5~9 catholyte comprises a lead--tin--copper plating solution then the anolyte will not contain copper.

When the apparatus is in use, metal ions arising from the anode pass through the cation exchange membrane towards the cathode under the influence of the plating potential.
Since the anolyte contains ro metal capable of immersion plating on to the anode the anode will remain clean. A~ the end of a plating operation, when the plating potential is disconnected, the antimony or copper or arssnic in the catholyte (depending on what alloy is being co-deposited) is prevented f`rom entering the anolyte by the physical barrier of the cation exchange membrane. That is to say, metal ion~
can pass in one direction only, i.e towards the cathode, and then only under the influence of the plating potential applied between the anode and cathode. Thus the anolyte solution in the second chamber remains free of ions capable of immersion plating on to the anode.

A further advantage of the use of a cation exchange membrane tc physically separate the catholyte and anolyte solutions is that the composition of the catholyte may be controlled more readily since metal is not lost therefrom by immersion plating which in turn means that the electro-deposited alloys have more consistent compositions.

Other features of the in~Jention will become apparent from the following description given herein solely by way of exampla and with reference to the accompanying drawing which shows, in diagrammatic form, a plan view of a plating bath in accordance wlth the invention.

Referring to the drawings there is shown a first chan.ber 10 within which is locatable a member 12 to be p]ated and which comprises the cathode; such member may comprise a steel bac!cing member with a bronze substrate bonded thereto and on to which is to b- co-~-po~ited a ternary ~lloy as a ~7?rJ5~

bearing surfacc. This first chamber 10 is capable of being filled with the catholyte solution.

At the end of the first charnber lO remote f`ro~, the cathode 12 there is provided a second chamber 14 wholely contained within the ~irst chamber and communicating 'chere-with only through the medium of a cation exchange membrane 16. This second chamber 1L~ is conveniently of box like rectangular configuration having an open top and an open front across which is secured the exchange membrane 16 by means of detachable clamping plates and gaskets. To provide support and protection for the exchange membrane 16 a sheet 18 of porous polyethylene may be sealingly located by the gaskets on one or both sides of the membrane 16 the polye~
thylene sheeting 18 being provided to prevent physical damage to the exchange membrane 16 and also providing support against sag or swelling of the exchange membrane whieh may occur in use.

The cation exchange membrane is a proprietary item and may be of the type available from Permutit-Boby of Brentford, 1 ~0 Middlesex, England.

The anode 20 is locatable within the second chamber 14 ¦ and the chamber 14 is capable of being filled with an anolyte solution to at least the same level as that of the catholyte solution in the first chamber 10. It may be preferable for the level of the anolyte solution to be above that of the catholyte solution to provide a slight hydrostatic pressure I in favour of the anolyte.

The following examples of use of the apparatus will serve to illustrate the inventi~n:-:1~ 7~1~5 _x~le 1 The apparatus was used for the electro deposition of aternary alloy of lead-antimony-tin to give a coating having a basis of lead and containing between 9.5~ and 10.5% by wei.ght of antimony and between 5.5% and 6.5~ by weight of tin in the deposited alloy. The anode was a lead-tin anode containing 5% to 25% by weight of tin The cathode comprised a steel backing member on to which was bonded a bronze substra'ce. It is preferab].e to electro-plate a base coating of cobalt or nickel on to the bronzesubstrate thereby to give a better surface for the deposition of the required ternary alloy particularly for the preventior of dispersal of tin into the bronze.

The catholyte solution in the first chamber was as follows:-Lead 150 grammes/litre added as lead fluoroborate Antimony 6 grammes/litre added as anti-mony trifluoride Tin (stannous) 22 grammes/litre added as tin f1uoroborate Resorcinol 7.5 grammes/litre Gelatin 0.75 grammes/litre Free fluoroboric acid 20 grammes/litre The tcmperatl1re of the catholyte was maintained at l'QC
and a cathode current density of 30 amperes per square -. foot ~as utilised for approximately 20 minutes to gi.~te a deposited alloy thickness of 25 um.

~7~5~9 The second chamber was fi.lled with an anolyte solution of the following composition Lead 150 gramMes/litre added as lead fluoroborate Tin 22 grammes/litre added as tin fluoroborate Resorcinol 7.5 grammes/litre Gelatin 0.75 grammes/litre ~ ree fluoroboric acid 20 grammes/litre The temperature of the anolyte solution was maintained at 40C

Example 2 In this example identical constructions of anode and cathode were utilised as in the preceding example but the electrolyte solutions were chosen to give a ternary alloy deposit on the cathode of iead tin-copper having a basis of lead and containing between 8% and 12% by weight of tin and between 2% and 3% by weight of copper in the deposited alloy.

A catholyte solution of the following composition was used:-Lead 100 grammes/litre added as lead fluoroborate Tin (Stannous) 10 grammes/lltre added as tin fluoroborate ~' 25 Copper 3 grammes/litre added as copper fluoroborate ~ ~7~dS9 9 Resorcinol 5 grammes/]itre Gelatin 0.5 grammes~litre Free fluoroboric acid 40 grammes/litre The temperature of the catholyte solution was maintained at 25C and cathode current density of 20 amperes per squarefoot was utilised for approximately 20 minutes to give a deposited ternary alloy of 25 um thickness.

The anolyte solution was identical in all respects with the catholyte solution with the exception that no copper fluoroborate was present in the anolyte.

In both examples it was found that the anode remained clean and that the platillg elemellts had been lost from the catholyte to the cathode at a controlled rate.

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of electro-depositing a lead alloy onto a metal cathode characterized by the steps of immersing the cathode in a first chamber containing a lead based catholyte solution;
immersing a soluble lead alloy anode in a second chamber containing a lead based anolyte solution which does not contain ions capable of immersion plating onto the anode; maintaining the anolyte solution and the catholyte solution separate from one another by the medium of a cation exchange membrane; and applying a direct current between the anode and the cathode.
2. A method according to Claim 1 wherein the catholyte solution is a lead-antimony-tin solution, the anolyte solution is a lead-tin solution and the anode is a lead-tin anode.
3. A method as claimed in Claim 1 wherein the catholyte solution is a lead-tin-copper solution, the anolyte solution is a lead-tin solution and the anode is a lead-tin anode.
4. A method according to claim 1, 2 or 3, wherein the cathode is a steel backed bearing member.
5. A method according to claim 1, 2 or 3, wherein said second chamber is located wholly within said first chamber.
CA000386328A 1980-09-23 1981-09-21 Method and apparatus for the electro-deposition of lead alloys Expired CA1172599A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8030638 1980-09-23
GB8030638A GB2084191A (en) 1980-09-23 1980-09-23 Electro-deposition of alloys

Publications (1)

Publication Number Publication Date
CA1172599A true CA1172599A (en) 1984-08-14

Family

ID=10516222

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000386328A Expired CA1172599A (en) 1980-09-23 1981-09-21 Method and apparatus for the electro-deposition of lead alloys

Country Status (6)

Country Link
EP (1) EP0048579B1 (en)
AT (1) ATE10862T1 (en)
BR (1) BR8106041A (en)
CA (1) CA1172599A (en)
DE (1) DE3167841D1 (en)
GB (1) GB2084191A (en)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3335716A1 (en) * 1983-10-01 1985-05-02 Glyco-Metall-Werke Daelen & Loos Gmbh, 6200 Wiesbaden SLIDING BEARING AND METHOD FOR THE PRODUCTION THEREOF
DE3430945A1 (en) * 1984-08-22 1986-03-06 Miba Gleitlager Ag, Laakirchen Electrodeposited bearing layer for a sliding bearing
CA2034568C (en) * 1990-01-19 1995-08-29 Yoshikazu Fujisawa Slide member
CA2069988C (en) * 1991-05-31 1997-03-04 Yoshikazu Fujisawa Slide member with surface composed of pyramidal microprojections
CA2070932C (en) * 1991-06-11 1995-11-07 Yoshikazu Fujisawa Slide bearing
FR2685012B1 (en) * 1991-07-18 1995-11-17 Honda Motor Co Ltd SLIDING BODY.
DE19606993C1 (en) * 1996-02-24 1997-04-03 Glyco Metall Werke Prodn. of layered material for friction bearing
GB2324805A (en) * 1997-04-30 1998-11-04 Platt Electromeck Limited Electroplating
US6740221B2 (en) 2001-03-15 2004-05-25 Applied Materials Inc. Method of forming copper interconnects
WO2003063067A1 (en) 2002-01-24 2003-07-31 Chatterbox Systems, Inc. Method and system for locating positions in printed texts and delivering multimedia information
US7195702B2 (en) * 2003-06-06 2007-03-27 Taskem, Inc. Tin alloy electroplating system
FR2864553B1 (en) * 2003-12-31 2006-09-01 Coventya INSTALLATION OF ZINC DEPOSITION OR ZINC ALLOYS
US20110226613A1 (en) 2010-03-19 2011-09-22 Robert Rash Electrolyte loop with pressure regulation for separated anode chamber of electroplating system
US9404194B2 (en) 2010-12-01 2016-08-02 Novellus Systems, Inc. Electroplating apparatus and process for wafer level packaging
US9534308B2 (en) 2012-06-05 2017-01-03 Novellus Systems, Inc. Protecting anodes from passivation in alloy plating systems
CN103849915B (en) * 2012-12-06 2016-08-31 北大方正集团有限公司 Electroplanting device and pcb board via copper coating
CN105350063B (en) * 2015-11-09 2018-10-30 科文特亚环保电镀技术(江苏)有限公司 A kind of anode system of electroplate liquid separation
KR102568350B1 (en) 2017-11-01 2023-08-21 램 리써치 코포레이션 Plating electrolyte concentration control on electrochemical plating equipment
JP6750186B1 (en) * 2019-11-28 2020-09-02 ユケン工業株式会社 Method for suppressing increase in zinc concentration of plating solution and method for producing zinc-based plated member
RU2739899C1 (en) * 2020-07-27 2020-12-29 Алексей Игоревич Буянов Acid electrolyte for application of antifriction coating with lead-tin-copper alloy

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB577335A (en) * 1944-02-10 1946-05-14 Vandervell Products Ltd Improvements in and relating to bearings and bearing surfaces
GB628459A (en) * 1945-07-10 1949-08-30 Cleveland Graphite Bronze Co Electrodeposition of lead-antimony-tin alloys
GB679947A (en) * 1950-06-09 1952-09-24 Cleveland Graphite Bronze Co Improvements in bearings
GB741864A (en) * 1952-06-04 1955-12-14 Silvercrown Ltd Improvements in the electrodeposition of alloys containing copper and tin
FR1508573A (en) * 1967-01-18 1968-01-05 Eugene Arbez Ets Process for depositing a lead coating on solid plates, in particular with a view to their printing by stamping, as well as the plates conforming to those obtained by the present process or similar process
JPS6015716B2 (en) * 1977-10-21 1985-04-20 デイツプソ−ル株式会社 Method for stabilizing tin or tin alloy electroplating baths
US4217198A (en) * 1979-03-23 1980-08-12 Olin Corporation Coated perfluorosulfonic acid resin membranes and a method for their preparation

Also Published As

Publication number Publication date
BR8106041A (en) 1982-06-08
EP0048579B1 (en) 1984-12-19
EP0048579A1 (en) 1982-03-31
DE3167841D1 (en) 1985-01-31
GB2084191A (en) 1982-04-07
ATE10862T1 (en) 1985-01-15

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