Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1 333377
24133-643
BACKGROUND OF THE INVENTION
This lnvention relates to an electroplatlng bath, an
electroplatlng cell and a method for the electrodeposltlon of a
wlde range of tln-blsmuth alloys onto a conductlve substrate.
Alloys of tin and lead have been used ln a wlde varlety
of appllcatlons such as platlng for clrcult boards, as rust lnhlb-
ltlng coatlngs on metals and as solder. Increased awareness of
health and envlronmental hazards posed by lead has requlred hand-
llng and dlsposal precautlons that often escalate the cost of
handllng or dlsposlng of lead-contalnlng materlals lncludlng tln-
lead alloys. In some sltuatlons, therefore, lt would be deslrable
to replace tln-lead wlth alloys havlng acceptable characterlstlcs
but that do not present health and envlronmental rlsks attendant
to tln-lead alloys.
Moreover, tln-lead alloys have not proven entlrely
satlsfactory ln some temperature sensltlve appllcatlons where heat
ls undeslrable. Tln-lead alloys have conventlonally been used,
for lnstance, as platlng for multllayer clrcult boards and as a
eutectlc solder used to bond together the layers of tln-lead pla-
ted clrcult boards. The heat requlred to melt eutectlc tln-lead
alloy solder, however, ls so hlgh that lt can damage the compo-
nents of the clrcult board or lmpalr the conductlvlty character-
lstlcs of the clrcult board.
Tln-blsmuth alloys have characterlstlcs that make them
attractlve replacements for tln-lead alloys for many purposes.
Tln-blsmuth alloys, for lnstance, do not present the health and
envlronmental problems assoclated wlth lead contalnlng alloys.
Moreover, a tln-blsmuth eutectlc alloy has a meltlng polnt about
50C lower than a tln-lead eutectlc alloy, maklng the tln-blsmuth
eutectlc alloy an attractlve materlal for platlng and solderlng
~F
1 333377
24133-643
layered clrcult boards. Indeed, the broad range of potentlal uses
for tln-blsmuth alloys may warrant productlon of tln-blsmuth
alloys havlng a blsmuth content ranglng from nearly 0% to nearly
100% blsmuth. It ls therefore deslrable to develop a commerclally
acceptable electrolytlc bath, cell and process capable of provl-
dlng tln-blsmuth alloys whlch may have any deslred blsmuth content
ranglng from ~ust above 0% to ~ust below 100% blsmuth.
Conventlonal blsmuth salts used ln conventlonal electro-
lytes often are unstable and undergo undeslrable hydrolytlc pre-
clpltatlon. To prevent or mlnlmlze thls problem, addltlves whlchlnhlblt hydrolytlc preclpltatlon of blsmuth ln electrolyte baths
are ordlnarlly used. Cltrlc acld and chelatlng agents are
examples of addltlves commonly used for thls purpose. Conven-
tlonal baths contalnlng such addltlves, however, may be dlfflcult
to malntaln and do not provlde versatlle commerclally satlsfactory
baths and cells for deposltlng blsmuth-contalnlng alloys of any
deslred blsmuth content.
In some electroplatlng processes, small quantltles of
blsmuth have been added to tln plate to retard the formatlon of
tln pest and tln whlskers. From about 1% to 2% blsmuth ln the co-
plate ls ordlnarlly adequate for thls purpose. U.S. Patent No.
4,331,518 dlscloses an electroplatlng process whlch produces tln-
blsmuth alloys whlch may have as much as 10-14% blsmuth ln the co-
plate. Soluble blsmuth ls provlded ln the electroplatlng bath as
a chelated acld blsmuth sulfate gluconate.
Optlonal use of small quantltles of blsmuth nltrate as
an addltlve compound, ln an electroplatlng bath contalnlng alkyl
sulfonlc acld electrolyte, to ald ln the deposltlon of tln-lead
alloy onto a substrate ls dlsclosed ln U.S. Patent No. 4,565,610.
1 3~3377
24133-643
The bismuth nitrate is said to lower current density of the bath
or, when added in conjunction with an aromatic aldehyde and/or an
alkylene oxide, to improve brightness of the tin-lead deposits.
The present invention provides a method, bath and cell
for the electrodeposition of tin-bismuth alloys onto a conductive
substrate so that the bismuth content of the coplate may range
from greater than zero to less than 100% bismuth by weight of the
electrodeposited alloy with the balance of the alloy being tin.
Practising the present invention permits the electrodeposition of
a fine grained alloy coating of bismuth and tin of any desired
thickness and percent composition upon the immersed portion of a
conductive substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
The Figure is a correlation curve of percent bismuth in
the coplate as a function of the weight ratio of bismuth to tin in
an electroplating bath containing methane sulfonic acid
electrolyte. Soluble bismuth was provided by bismuth methane
sulfonate concentrate and a soluble bismuth anode while soluble
tin was provided by stannous methane sulfonate concentrate.
SUMMARY OF THE INVENTION
The invention provides an article of manufacture
comprising at least one printed wireboard (PWB) with at least one
conductive surface, having a tin-bismuth alloy deposited on at
least a portion of the surface, the alloy being deposited from an
electroplating bath comprising bismuth and tin ion in aqueous
solution, wherein the bismuth and the tin ion are present in the
bath in amounts sufficient to deposit the tin-bismuth alloy onto
1 3J3377
24133-643
the conductive surface of the PWB in a weight ratio relative to
each other selected to provide a controlled bismuth content of the
tin-bismuth alloy on the conductive surface of the PWB in an
amount of greater than about 10 wt.% bismuth, the bath having an
electrolyte comprising at least one alkyl sulfonic acid or salt
thereof in an amount sufficient to inhibit hydrolytic
precipitation of the bismuth ion.
In preferred embodiments the bismuth content of
tin/bismuth alloy is greater than about 20 wt.%, preferably
between about 20 wt.% and about 80 wt.%. In a particular
embodiment the alloy comprises the tin/bismuth eutectic. The
article may comprise a plurality of PWBs or the alloy may be
deposited on a plurality of surfaces.
One embodiment of the present invention is an
electroplating bath for electrodeposition of tin-bismuth alloy
onto a conductive substrate comprising:
a) soluble bismuth in aqueous solution;
b) soluble tin in aqueous solution, wherein the soluble
bismuth and the soluble tin are present in the bath in amounts
sufficient to deposit a tin-bismuth alloy onto the conductive
substrate and in a weight ratio relative
3a
1 333377
24133-643
to each other selected to provlde a deslred blsmuth
content of the tln-blsmuth alloy on the conductlve
substrate; and
c) an alkyl sulfonlc acld electrolyte ln an amount
sufflclent to lnhlblt hydrolytlc preclpltatlon of
the soluble blsmuth.
A further embodlment of the present lnventlon ls an
electroplatlng cell for electrodeposltlon of tln-blsmuth alloy
onto a conductlve substrate comprlslng:
a) an electroplatlng bath comprlslng
1) soluble blsmuth ln aqueous solutlon;
2) soluble tln ln aqueous solutlon whereln the
soluble blsmuth and the soluble tln are pre-
sent ln the bath ln amounts sufflclent to
deposlt a tln-blsmuth alloy onto the conduc-
tlve substrate and ln a welght ratlo relatlve
to each other selected to provlde a deslred
blsmuth content of the tln-blsmuth alloy on
the conductlve substrate; and
3) a lower alkyl sulfonlc acld electrolyte ln an
amount sufflclent to lnhlblt hydrolytlc pre-
clpltatlon of the soluble blsmuth;
b) an anode lmmersed ln the bath;
c) a conductlve substrate cathode lmmersed ln the
bath; and
d) a supply of electrlclty for electrodepositlng tln
and blsmuth onto the conductlve substrate.
The present lnventlon also provldes a method for the
electrodeposltlon of a tin-blsmuth alloy onto a conductlve sub-
strate comprlslng:
.~ 4
1 333377
24133-643
a) provldlng an electroplatlng bath comprlslng:
1) soluble blsmuth ln aqueous solutlon;
2) soluble tln ln aqueous solutlon whereln the
soluble blsmuth and the soluble tln are
present ln the bath ln amounts sufflclent to
deposlt a tin-blsmuth alloy onto the conduc-
tlve substrate and ln a welght ratlo relatlve
to each other selected to provlde a deslred
blsmuth content of the tln-blsmuths alloy on
the conductlve substrate;
3~ a lower alkyl sulfonlc acld electrolyte ln an
amount sufflclent to lnhlblt hydrolytlc pre-
clpltatlon of the soluble blsmuth;
b) provldlng an anode lmmersed ln the bath;
c) supplylng sufflclent electrlclty to the bath to
electro deposlt tln-blsmuth alloy onto the conduc-
tlve substrate; and
d) lmmerslng the conductlve substrate lnto the
electroplatlng bath.
Addltlonal advantages and embodlments of the lnventlon
wlll be set forth ln part ln the descrlptlon whlch follows, and ln
part wlll be apparent from the descrlptlon, or may be learned by
practlce of the lnventlon. The advantages of the lnventlon may be
reallzed and attalned by processes, materlals and comblnatlons
partlcularly polnted out ln the appended clalms.
DESCRIPTION OF ~K~ KK~ EMBODIMENTS OF THE INVENTION
In the present appllcatlon, the phrase "tln-blsmuth
alloy" ls understood to mean an electroplated alloy coatlng of
greater than 0% and less than 100% blsmuth by total welght of the
1 333377
24133-643
electrodeposited alloy coating with the balance of the
electrodeposited alloy coating being tin. Ordinarily, tin-bismuth
alloy will have a minimum bismuth content of about 0.1% and a
maximum bismuth content of about 99.9%.
It has been found that tin-bismuth alloy having nearly
any desired bismuth content may be electroplated onto a conductive
substrate from a relatively simple versatile electroplating bath
which includes sufficient amounts of free alkyl sulfonic acid
electrolyte. The deposition of alloys having a wide range of
bismuth content from a bath of the present invention is possible,
in part, because bismuth has been found to be more hydrolytically
stable in the presence of sufficient amounts of free alkyl
sulfonic acid, particularly methane sulfonic acid, than in
conventional electrolyte solutions used for bismuth such as
sulfuric acid or chloride-citrate. Using a sufficient amount of
alkyl sulfonic acid electrolyte therefore is one aspect of the
present invention which makes possible the electrodeposition of
tin-bismuth alloys having virtually any desired bismuth content.
Aqueous acidic electroplating baths of the present
invention are therefore composed of alkyl sulfonic acids, and more
preferably lower alkyl sulfonic acids such as Cl 5 alkyl sulfonic
acids. Methane or ethane sulfonic acid are the most preferred
acids used in accordance with the present invention.
Lower alkyl sulfonic acid electrolytes useful may be
purchased commercially from Pennwalt Corporation. Alternatively,
alkyl sulfonic acids may be prepared by methods known to the art
such as the methods described in U.S. Patent Nos. 774,049 and
2,525,942.
1 333377
24133-643
Hydrolytlc preclpltatlon ln a multl-component electro-
lyte solutlon probably ls quite complex, but in the case of
blsmuth, the followlng formula, ln which soluble blsmuth is
provided by bismuth trimethane sulfonate, may represent the
mechanlsm of hydrolytic precipitation ln a simplistlc manner:
O O
Il 11
Bi(O-S-CH3)3 + 3 H2O ~ Bl(OH~3 + 3 HO-S-CH3
O O
Blsmuthtrimethane Insoluble white Methane sulfonic
sulfonate precipitate acid
Bismuth tri-
hydroxide
To maintain stablllty of the bath and prevent hydrolytic
precipitation of bismuth from the bath solution the amount of free
alkyl sulfonic acid electrolyte in the aqueous acidic electro-
platlng bath ordlnarlly ranges from about 100 grams per llter to
about 400 grams per liter, preferably from about 150 grams per
llter to about 300 grams per liter and more preferably 200 grams
per liter to about 250 grams per liter. Generally, when the free
MSA concentration ln the platlng bath ls below 200 grams per
liter, for example below about 150 grams per liter, the bath may
undergo undeslrable hydrolytic precipitation of bismuth after a
period of time. When concentrations of about 200 grams per liter
free MSA are maintained in the bath, hydrolytic precipitation
seldom occurs and the degree of precipitation is very moderate.
At concentrations of about 250 grams per liter free MSA, pre-
clpltatlon of blsmuth ordlnarily does not occur at observable
levels.
Soluble blsmuth avallable to form a tln-blsmuth alloy on
a conductlve substrate may be provlded ln a bath of the present
lnventlon by addlng a bismuth salt, preferably bismuth alkyl
~- 7
':
1 333377
24133-643
sulfonate, dlrectly to the bath or by a soluble blsmuth metal
anode. Elther source of soluble blsmuth may be used wlthout the
other but they are frequently used together.
For most appllcatlons of the present lnventlon, the
amount of soluble blsmuth ln the aqueous acldlc platlng bath ordl-
narlly ranges from about .05 grams per llter of the bath to about
150 grams per llter of the bath, preferably, from about .05 grams
per llter of the bath to about 80 grams per llter of the bath.
Soluble blsmuth ls preferably provlded ln bath solutlons of MSA
lnltlally ln the form of blsmuth trlmethane sulfonate concentrate
(alternatively referred to as blsmuth methane sulfonate concen-
trate).
Blsmuth trlmethane sulfonate concentrate may be prepared
by reactlng blsmuth trloxlde wlth 70% methane sulfonlc acld. It
has been found that a product bath solutlon of 200-225 grams of
blsmuth trlmethane sulfonate per llter blsmuth ls stable only when
there ls at least 200 grams per llter free methane sulfonlc acld
ln the solutlon. As the electroplatlng process proceeds, addl-
tlonal blsmuth trlmethane sulfonate concentrate may be added to
malntaln an adequate soluble blsmuth content ln the bath.
In one electroplatlng system of the present lnventlon, a
soluble blsmuth anode ls used to recharge the blsmuth platlng bath
so that further addltlons of blsmuth methane sulfonate are mlnl-
mlzed or not requlred durlng operatlon. The blsmuth anode prefer-
ably useful ln the present lnventlon ls constructed of soluble
blsmuth metal, typlcally cast hlgh purity blsmuth. It has been
found useful to bag the soluble blsmuth anode with polypropylene
cloth. Other components of cells, such as the contalner for the
electrolyte solutlon, are conventlonal. Those skllled in the art
1 333377
24133-643
are well acqualnted wlth electroplatlng cells and thelr assembly
and would therefore be able to provlde a cell ln accordance wlth
the teachlngs of the present lnventlon.
When blsmuth anodes are used to supply soluble blsmuth,
the lmmerslon area of the anodes wlll have to be regulated to con-
trol the solublllzatlon rate to meet platlng demand and malntaln
solutlon concentratlon. Blsmuth anodes generally produce tln-
blsmuth co-plates havlng clean graylsh whlte satln flnlshes.
It has been found that blsmuth anodes ln platlng baths
contalnlng about 250 grams per llter free methane sulfonlc acld
are very actlve and tend to lncrease the soluble blsmuth concen-
tration, thereby slowly upsettlng the blsmuth/tln ratlo ln the co-
plate to contaln about 5% blsmuth. Thls may be counteracted by
addlng addltlonal tln to the bath. However, the soluble blsmuth
bulld-up ls preferably mlnlmlzed by controlllng the lmmerslon area
of the blsmuth anode to provlde an anode current denslty near 110
amp/ft2 where the anode current efflclency probably becomes suffl-
clently low to inhlblt the solublllzatlon rate of blsmuth.
In the case of tln-blsmuth co-plates contalnlng 1-2%
blsmuth, useful for lnhlbltlng the growth of tln whlskers and tln
pest ~allotroplc transformatlon to alpha-tln, the gray cublc form,
at 12C to -70~C or lower) lt may be preferable to add blsmuth ln
chelated form to the bath rather than as a sulfonlc acld concen-
trate. When thls ls done lt ls ordlnarlly posslble to lower the
concentratlon of free methane sulfonlc acld to 150 or even 100
grams per llter.
When chelated blsmuth ls used ln the bath as the source
of blsmuth lons, lt also may be posslble to substltute tln anodes
for the blsmuth anodes.
1 333377
24133-643
The followlng three chelatlng compounds may be used to
provide chelated blsmuth to the electrolyte bath:
(1) Tetraammonlum blsmuth dlnltrllotrlacetate Chelate.
(approx. 26% blsmuth ln water soluble transparent
crystals)
(2) Dlammonlum blsmuth diethylene trlamlnopentaacetate
Chelate. (approx. 325 grams per llter blsmuth ln
concentrate)
(3) Trlmethane sulfonlc acld blsmuth trlmethane sulfo-
nate trlgluconate Chelate Complex. (approx. 200
grams per llter blsmuth ln concentrate)
The concentratlons of these blsmuth sources ln the bathare calculated ln the same manner as descrlbed for blsmuth
methane-sulfonate except that the free acld concentratlon may be
less (say approx. 100-150 grams per llter, preferably about 150
grams per llter). These chelated compounds, partlcularly chelate
No. 2, at hlgh concentratlons tend to saturate and cause a spon-
taneous breakdown preclpltatlon ln the MSA bath. The flrst
chelate llsted above ls ordlnarlly the preferred chelate ln MSA
electrolyte baths of the present lnventlon.
Processes for maklng the foregolng blsmuth chelates are
descrlbed ln the ensulng paragraphs.
Tetraammonlum blsmuth dlnltrllotrlacetate Chelate.
Reactlon Formulatlon
comPonent Amount
Blsmuth (Bl) 20.0 g
Blsmuth trloxlde (B1203) 22.2 g
Nltrllotrlacetlc acld (2m/m Bl) 36.6 g
Dlstllled Water 200 ml
Ammonlum hydroxlde (29% NH3) 25 ml
,~
~
1 333377
24133-643
A slurry of B12O3 and nltrllotrlacetate (NTA) ls aglta-
ted and heated at 80C for about one hour. The NH40H ls added
slowly to form a water clear solutlon. If crystals appear when
the solutlon ls cooled to room temperature a llttle dlstllled
water ls added to redlssolve them. The solutlon ls near satura-
tlon at about 200 grams per llter blsmuth. The pH of the solutlon
should be near 6.8 at 25C. Any resldue ls removed by flltratlon
through hardened ashless paper. The flltrate may be vacuum
evaporated at 26-29 ln. Hg and < 80C to recover the crystals.
The crystals may be vacuum drled at 29 ln. Hg and c 50C.
The blsmuth content of the crystals ls typlcally 26.4%
by analysls. The crystals dlssolve readlly ln water to form clear
solutlons that are stable at pH values at 7Ø Mlldly alkallne
(pH 7.5 - 10) solutlon are somewhat unstable. However, lncreased
alkallnlty (pH 10+) restores stablllty.
Dlammonlum blsmuth dlethylene trlamlnePentaacetate
Chelate (DTPA).
A typlcal procedure for synthesls the dlammonlum blsmuth
dlethylene trlamlnepentaacetate chelate ls descrlbed below:
Reactlon Formulatlon
Component Amount
Blsmuth (Bl) 60 g
Blsmuth trloxlde (B12O3), 98.5% 67.9 g
Dlethylene trlamlnepentaacetlc acld
(DTPA) (1 m/m Bl) 116.0 g
Distllled or D.I. Water 200 ml
Ammonlum hydroxlde (29% NH3) 39 ml
30% Hydrogen Peroxlde 0.5 ml
Reactlon Procedure
The reactor ls a 600 ml thlck-walled boroslllcate glass
(PYREX)~ beaker wlth a TEFLON~ encapsulated magnetlc stlrrer on a
11
, ~
1 333377
24133-643
THERMOLYNE STIR-PLATE~. A cover glass and a thermometer are
avallable.
The water ls added flrst and agltated. Then the DTPA ls
added to form a whlte slurry. The NH40H ls added to dlssolve the
DTPA. Heatlng ls started. When the solutlon ls practlcally clear
the blsmuth trloxlde ls added to form a yellow slurry. After
about 1.5 hours the solutlon temperature reaches about 90C and
the solutlon has a sllght haze and a volume of about 300 ml. Then
the cover glass ls removed to promote evaporatlon to about 200 ml.
The solutlon ls cooled to room temperature and flltered at low
vacuum through REEVE ANGEL 934 AH glass fibre paper to yleld 175
ml clear yellow flltrate typlcally havlng a denslty of 1.54 g/ml
at room temperature and analyzlng 328 grams per llter blsmuth.
The product concentrate generally has a pH at room temperature of
at least 6Ø
Trlmethane sulfonlc acld blsmuth trlmethane sulfonate
Trlglutonate Chelate Complex.
O O
Il 11
3 CH3-SI-OH Bl (O-S-CH3)3 (gluconate)3
Reactlon Formulatlon
Components Amount
Blsmuth (Bl) 20 g
Blsmuth trloxlde (B12O3), 98.5% 22.3 g
50% Gluconlc Acid (3 m.gl.ac./m.Bl) 91.3 ml
Dlstllled or D.I. Water 30 ml
70% Methane Sulfonlc Acld 58.1 ml
Reactlon Procedure
The reactor ls a 250 ml thlck-walled boroslllcate glass
beaker wlth a magnetlc stlrrer on a THERMOLYNE STIR-PLAT~ . A
cover glass and thermometer are avallable.
Trade-mark
12
1 333377
24133-643
The water ls added flrst, followed by the gluconlc acld.
The solutlon ls agltated and heatlng starts as the blsmuth trl-
oxlde ls added to form a slurry. The slurry ls heated at about
94C for nearly 3 hours. 70% MSA ls then added ln lncrements for
another hour. When all of the MSA ls added at 86.5C the solutlon
becomes clear dark red. Over another 2 hours the hydrogen per-
oxlde ls added drop wlse to oxldlze any blsmuthlte formed and the
product solutlon ls cooled to room temperature to yleld about 125
ml of sllghtly vlscous dark red solutlon. About 0.5 ml of the
product solutlon ls dlluted 500/1 with D.I. water and shows no
slgns of hydrolysls or preclpltatlon. Typlcally the product solu-
tlon analyzes 174 grams per llter blsmuth at a denslty of 1.518
g/ml at 25C.
Soluble tln may be provlded to a bath of the present
lnventlon by a salt of a tln compound or a tln soluble anode.
Elther source of tln may be used alone or they may be used to-
gether.
The preferred salts of a tln compound useful ln the
aqueous acldlc electroplatlng bath of the present lnventlon tln
salts of alkyl sulfonlc aclds, preferably lower alkylsulfonlc
aclds havlng 1-5 carbon atoms. The most preferred salt ls stan-
nous methane sulfonate.
The preferred amount of a tln salt, ln terms of tln
content ln the bath of the present lnventlon, ranges from about
.05 grams of soluble tln per llter of the bath to about 80 grams
of soluble tln per llter of the bath, preferably from about .05
grams of soluble tln per llter of the bath to about 50 grams of
soluble tln per llter of the bath. A preferred range of stannous
methane sulfonate ls from about .13 grams per llter to about 208
13
1 333377
24133-643
grams per llter, more preferably from about 0.13 grams per llter
to about 104 grams per llter. These amounts of stannous methane
sulfonate provlde, respectlvely, from about .05 grams to about 80
grams of soluble tln per llter of bath and from about .05 grams to
about 50 grams of soluble tln per llter of bath. Generally, for
most commerclal purposes, soluble tln concentrations ln the bath
below about 5 grams per llter wlll seldom be practlcal.
Stannous methane sulfonate ls preferably supplled ln a
concentrate contalnlng about 300 grams per llter stannous tln and
10-30 grams per llter free methane sulfonlc acld. Stannous
methane sulfonate concentrate may be made by reactlng stannous
oxlde wlth methane sulfonlc acld. The concentrate may also be
formed electrolytlcally uslng a tln anode ln a membrane cell
contalnlng MSA.
As lllustrated ln the Flgure, a correlatlon curve of
percent blsmuth ln satln electroplate (tln-blsmuth co-plate,
sometlmes referred to as alloy plate) as a functlon of the welght
ratlo of blsmuth to total tln ln the bath was derlved from analy-
ses of slmultaneous samples of tln-blsmuth co-plates and the
platlng bath over a wlde range of alloys from about 10% blsmuth to
about 90% blsmuth. The blsmuth content of the tln-blsmuth electro
co-plates on the cathode panels range from about 3.38% to about
98.48%. The welght ratlo of blsmuth to tln ln the baths ranged
from about 0.30 to about 9.50 and the welght concentratlon of
total tln plus blsmuth spanned about 27 to about 66.5 grams per
llter. The correlatlon curve of percent blsmuth ln the tln-
blsmuth electro co-plate as a functlon of the welght ratlo of
blsmuth to total tln ln the bath ls based on chemlcal analyses of
samples taken through the above mentloned ranges. Platlng
14
~ 333377
24133-643
variables other than soluble blsmuth and tin content, of course,
may be ad~usted to provlde a deslred co-plate composltlon at the
deslred rate of electrodeposltlon. The plater could, for
lnstance, ad~ust current denslty to affect the deslred average
percent blsmuth in the co-plate. Making such ad~ustments is
withln the ablllty of a person of ordlnary sklll ln the art. The
lllustrated correlatlon curve ls therefore an accurate gulde for
calculatlng both concentratlons of tln and blsmuth for the full
range of tln-blsmuth alloys and partlcularly for alloys havlng 10-
90% blsmuth ln the co-plate.
A stralght-llne correlatlon of percent bismuth as a
function of the weight ratio of bismuth to total tin in the bath
has been found in the range 0-15% bismuth in the co-plate. In the
range of 1-2% bismuth in the co-plate there may be another
straight-line correlation with a higher slope than the slope
appearing in the Figure as shown in U.S. Patent No. 4,331,518.
The lllustrated correctlonal curve, however, ls a useful gulde for
both composltlon even at the lowest and hlghest ranges of blsmuth
content.
The method for calculatlng the bath formulatlon of the
present invention is based on the desired percentage blsmuth in
the tin-bismuth co-plate. The desired total bismuth content of
the co-plate are selected. The correlation curve may be used to
find the weight ratio of blsmuth to tin corresponding to the
percentage bismuth in the co-plate. A soluble tin concentration
for the bath is selected and is multiplied by the weight ratio of
blsmuth to tln to provlde the blsmuth concentratlon needed for the
bath. The volumes of blsmuth methane sulfonate concentrate and
stannous methane sulfonate concentrate for one llter of the bath
1 333377
24133-643
may then be calculated accordlng to the respectlve blsmuth and tln
analyses of the concentrates. Ordlnarlly, the free methane sul-
fonlc acld contrlbuted by the concentrates ls subtracted from 250
grams per llter free methane sulfonlc acld and the balance ls used
to calculate the volume of 70% methane sulfonlc acld (say at 938
grams per llter 100% MSA) to add before the concentrates.
The blsmuth content of the electroplate, of course, ls
determlned by the welght ratlo of blsmuth to tln ln the platlng
bath. If a broad range of tln concentratlon of 1-6 oz/gal or 7.5-
45 grams per llter ls selected then the blsmuth ln the bath should
range from 0.8-44 oz/gal or 6-330 grams per llter for 5-58% bls-
muth ln the co-plate. It ls preferable to determlne the best
dlstrlbutlon of tln and blsmuth concentratlons ln the platlng bath
for a glven blsmuth content ln the electroplate accordlng to the
correlatlon curve.
For optlmum bath stablllty and lnhlbltlon of hydrolytlc
preclpltatlon of blsmuth, when blsmuth anodes are used and tln ln
the co-plate ls replaced by addlng acld stannous methane sulfonate
concentrate to the bath at frequent lntervals, the mlnlmum free
methane sulfonlc acld concentratlon ls from about 200-250 grams
per llter and the preferred concentratlon ls near 250 grams per
llter. The broad range of free methane sulfonlc acld concentra-
tlon however ls about 100-400 grams per llter.
Electroplatlng baths of the present lnventlon may con-
taln conventlonal amounts of addltlves such as surfactants, graln
reflners, prlmary and/or secondary brlghteners. Modlfled aromatlc
aldehydes (or ketones) and/or modlfled alkylene oxldes or thelr
analogs. These addltlves may be components of a brlghtenlng and
levellng system such as ~RI-TIN~ and ULTRA STAN-100O produced by
16
.~,.
1 373377
24133-643
M & T Chemlcals, Inc., formerly the Vulcan Materials Company.
The BRI-TIN~ addltlve system lmparts a mlrror brlght
finlsh to the tln-blsmuth co-plate. ULTRA STAN-100~ ls a system
for promotlng satln whlte tln plates havlng excellent reflowlng
and solderabillty characterlstlcs ln acld platlng baths. It
conslsts of two solutlons, a Prlmary Addltlon Solutlon whlch ls
used malnly to make up the bath, and an Actlvator Solutlon whlch
ls added malnly to satlsfy platlng demand. These solutlons con-
taln the surfactants, brlghtness, levelers and enhancers necessary
for promotlng the deslred satln whlte flnlsh to the electro co-
plate of tln-blsmuth. The partlcular levellng and brlghtenlng
system ls an not essentlal feature, however, of the lnventlon.
Dlfferent levellng and brlghtenlng systems may result ln
some alteratlon of the correlatlon of percentage blsmuth ln the
co-plate as a functlon of the welght ratlo of blsmuth to total tln
ln the bath or cell. Thus, ULTRA STAN-100~ and BRI-TIN~ may
result ln correlatlon curves slmllar ln form but dlfferent ln
curvature and havlng dlfferent correlatlon equatlon constants.
Such alteratlons, however, may readlly be antlclpated by and
accounted for by a person skllled ln the art.
The conductlve substrate or cathode of electroplatlng
cells of the present lnventlon may be any ob~ect whlch ls conduc-
tlve of electrlclty. Frequently, such ob~ects are composed of
metals such as lron, nlckel, stalnless steel, zlnc, copper, or
comblnatlons of metals. The foregolng metals are examples of
conventlonal conductlve substrates but the spectrum of conductlve
substrates whlch may be plated ln accordance wlth the present
lnventlon ls not llmlted to the llsted metals.
17
1 333377
24133-643
The anode of electroplatlng cells of the present lnven-
tion ls preferably a soluble blsmuth metal anode that functlons as
a source of soluble blsmuth. However, other anodes useful ln the
present lnventlon lnclude tln metal anodes. Insoluble anodes,
such as zlrcalloy, pyrolltlc graphlte and platlnum, could be used
ln the present lnventlon but are not preferred slnce they often
provlde poor quallty ln tln-blsmuth electroplates and excesslve
oxldatlon of stannous tln.
The ratlo of anode area to cathode area needs to be
regulated for the proper anode current denslty to control the rate
of anode solublllzatlon to meet the platlng requlrement and to
prevent bulld-up of the soluble blsmuth concentratlon ln the bath.
Soluble blsmuth bulld-up upsets the welght ratlo of blsmuth to tln
to change the blsmuth content of the co-plate. For 5% blsmuth ln
the co-plate the ratlo of blsmuth anode area to cathode area prob-
ably would be about 1/7-8. For 58% blsmuth ln the co-plate the
ratlo of blsmuth anode area to cathode area probably would be in
the order of about 0.5/1. For hlgher blsmuth content the ratlo
probably would be on the order of 2/1. Blsmuth ln the range of
1-2% ln the tln-blsmuth co-plate probably would requlre a ratlo of
blsmuth anode area to cathode area ln the order of 1/10. In that
case platlng performance mlght be better lf hlgh grade tln anodes
are substltuted for blsmuth anodes, wlth blsmuth added ln concen-
trates accordlng to platlng demand and the concentratlon of free
acld ln the bath lowered to subtend anode actlvlty.
In a typlcal process of the present lnventlon, an aque-
ous acldlc electroplatlng bath ls prepared ln an electroplatlng
vessel known to the art and ls clrculated vlgorously at room
temperature (15C to 25C). An anode, preferably soluble blsmuth
18
1 333377
24133-643
metal anode, which can be wrapped or bagged ln polypropylene, ls
lmmersed or placed lnto the bath and the current ls turned on. A
cathode current denslty from about 2 to about 40 amp/ft2 should
ordlnarlly be malntalned. The conductlve substrate wlth an anode
area/cathode area ratlo ad~usted accordlng to deslred blsmuth
content of the tln-blsmuth co-plate ls then lmmersed lnto the
aqueous acldlc electroplatlng bath and reclprocated moderately.
The conductlve substrate ls lmmersed ln the bath and
remalns lmmersed for a tlme sufflclent to deposlt a varlable alloy
coatlng of tln-blsmuth of the deslred thlckness upon the conduc-
tive substrate. The conductlve substrate ls subsequently wlth-
drawn from the aqueous acldlc electroplatlng bath.
It ls beneflclal to malntaln the current ln the bath
untll the conductlve substrate has been completely wlthdrawn.
Thls mlnlmlzes smuttlng of the plate caused by dlsplacement of
blsmuth from the solutlon at hlgh concentratlon by the substrate.
The plated conductlve substrate should be washed
thoroughly as qulckly as posslble to mlnlmlze stalnlng.
Thls lnventlon ls further lllustrated ln the followlng
Examples. It should be understood, however, that the lnventlon ls
not llmlted to the speclflc detalls of the Examples.
PREPARATION OF THE CONDUCTIVE SUBSTRATE
Conductlve substrates used for the electrodeposltlon of
blsmuth ln Examples 1-4 were steel panels (25 cm2 platlng area)
from Hull cell panels strlpped of zlnc electrocoat ln 1:1 HCl and
actlvated ln 10% methanesulfonlc acld at room temperature, wlth
thorough washlng wlth demlnerallzed water after each treatment.
The strlpped panels then were electroplated wlth 0.15 - 0.25 ml
19
1 3J3377
24133-643
copper in an acld cuprlc methane sulfonate bath as descrlbed ln
Table 1 before belng electroplated wlth 0.1 to 1.0 ml blsmuth. It
was found that the adheslon of the electro copper plate to the
steel panel was very much lmproved by a very short dlp (e.g. 5-10
seconds) of the strlpped panel ln 20-50 grams per llter HN03 at
room temperature and by very thorough washlng before actlvatlon ln
10% methanesulfonlc acld.
Table 1 contalns a llstlng of the bath composltlon for
the electroplatlng of the Hull cell panels wlth copper and Table 2
contalns a llstlng of the platlng condltlons and solutlon charac-
terlstlcs for the bath used to plate the panels wlth copper.
Table 3 llsts the platlng condltlons and solutlon characterlstlcs
that were common throughout Examples 1-4.
1 3~3377
24133-643
TABLE 1
Component Concentratlon (qtl)
Copper 25
Free Methanesulfonlc Acld 40
Cuprlc Methane Sulfonate
Concentrate
(129 gtl Cu, 11 gtl Free MSA) 193.8 ml/l
69.5% Methanesulfonlc Acld
(938 g/l 100% MSA) 40.4 ml/l
TABLE 2
Platlng Condltions
Temperature 20C-25C (Room Temp.)
Agltatlon None
Anode Rolled Electrolytlc Cu
Ratlo Anode Area to
Cathode Area 2:1
Cathode Current Denslty
Amp/ft2 2-25
Cathode Current Efflclency 100%
Solutlon Characterlstlcs:
Clarlty Water clear
Color Sllght yellow tlnt
Resldue Practlcally none
21
1 333377
24133-643
TABLE 3
Platlnq Conditlons:
Temperature, C Room (20C-25C)
Agitatlon
solutlon clrculatlon Vlgorous
cathode reclprocatlon Moderate
Anodes Cast hlgh purlty
blsmuth bagged wlth
polypropylene
Ratlo anode area to cathode area ad~usted accordlng
to the deslred
percentage of
blsmuth ln the tln-
blsmuth co-plate.
Solutlon Characterlstlcs:
Clarlty Water clear
Color Sllght yellow tlnt
Resldue Practlcally none
EXAMPLE 1
The panels electroplated ln the electroplatlng bath of
Table 4 resulted ln a conductlve substrate wlth an electro-
deposlted alloy coatlng comprlsed of 95% Tln/5% Blsmuth.
22
.
1 333377
24133-643
TABLE 4
ml/l q/l
Total Tln 15.0
Stannous Methane Sulfonate Concentrate48.7
Blsmuth 12.0
Blsmuth Methane Sulfonate Concentrate54.4
Free Methane Sulfonlc Acld 250.0
69.5% Methane Sulfonlc Acld 253.0
ULTRA STAN-1000 Prlmary Additlon
Solutlon (3-1/2% v/v) 35
ULTRA STAN-100~ Actlvator Solutlon
(2-1/2% v/v) 25
Worklng Range of Cathode Current
Denslty 2-40 amp/ft2
Cathode Current Efflclency 95+%
EXAMPLE 2
The panels electroplated ln the electroplatlng bath of
Table 5 resulted ln a conductlve substrate wlth an electro-
deposlted alloy coatlng comprlsed of 90% tln/10% blsmuth.
23
1 333377
24133-643
TABLE 5
ml/l q/l
Total Tln 15.0
Stannous Methane Sulfonate Concentrate48.7
Blsmuth 24.0
Blsmuth Methane Sulfonate Concentrate 109.0
Free Methane sulfonlc Acld 250.0
69.5% Methane Sulfonlc Acld 241
ULTRA STAN-100~ Prlmary Addltlon
Solutlon t3-1/2% v/v) 35
ULTRA STAN-100~ Actlvator Solutlon
(2-1/2% v/v) 25
Worklng Range of Cathode Current
Denslty 2-40 amp/ft2
Cathode Current Efflclency 95+%
EXAMPLE 3
The panels electroplated ln the electroplatlng bath of
Table 6 resulted ln a conductlve substrate wlth an electro-
deposlted alloy coatlng comprised of 42% tln/58% blsmuth. Thls
proportlon of blsmuth to tln comprlses a eutectlc coatlng.
24
, .
~,
1 333377
24133-643
TABLE 6
ml/l q/l
Total Tln 7.5
Stannous Methane Sulfonate Concentrate24.4
Bismuth 55.0
Blsmuth Methane Sulfonate Concentrate275.0
Free Methane Sulfonlc Acld 250.0
69.5% Methane Sulfonlc Acld 200.0
ULTRA STAN-100~ Prlmary Addltlon
Solutlon (3-1/2% v/v) 35.0
ULTRA STAN-100~ Actlvator Solutlon
(4% v/v) 40 0
Worklng Range of Cathode Current
Denslty 2-20 amp/ft
Cathode Current Efflclency 80%
EXAMPLE 4
The panels electroplated ln the electroplatlng bath of
Table 7 resulted ln a conductlve substrate wlth an electro-
deposlted alloy coatlng comprlsed of 14.5% tln/85.5% blsmuth.
~ 3J~377
24133-643
TABLE 7
ml/l q/l
Total Tln 6.4
Stannous Methane Sulfonate Concentrate 20.8
Blsmuth 49.6
Blsmuth Methane Sulfonate Concentrate 228.0
Free Methane Sulfonlc Acld 250
69.5% Methane Sulfonlc Acld 200
ULTRA STAN-100~ Primary Addition Solution 35.0
(3-1/2% v/v)
ULTRA STAN-100~ Actlvator Solution 40.0
(4% v/v)
Worklng Range of Cathode Current Density 2-20 amp/ft2
Cathode Current Efficiency 80%
Ratlo of Anode Area to Cathode Area 2:1
Tln-bismuth alloys that may be made in accordance wlth
the present lnventlon lnclude: 1) 42% tln/58% blsmuth whlch forms
a eutectic material having a melting point of about 138C, approx-
imately 50C lower than tin-lead eutectic compositlon, and 2)
25/75 or 16/84 tin-bismuth alloys sandwiched in plastic sheets to
make formable metalllzed plastic. Other tln-blsmuth alloys may be
expected to flnd utility in many applications prevlously filled by
tin/lead alloys.
The princlples, preferred embodlments and modes of
operation of the present invention have been described in the
foregoing specification. The invention which is intended to be
protected, however, ls not limlted to the partlcular embodlments
dlsclosed, slnce these are to be regarded as lllustratlve rather
26
1 333377
24133-643
than restrlctlve. Varlatlons and changes may be made by those
skilled ln the art wlthout departlng from the splrlt of the
lnventlon.
27
