CA1077430A - Electroplating bath for the electrodeposition of tin and tin/cadmium deposits - Google Patents
Electroplating bath for the electrodeposition of tin and tin/cadmium depositsInfo
- Publication number
- CA1077430A CA1077430A CA266,279A CA266279A CA1077430A CA 1077430 A CA1077430 A CA 1077430A CA 266279 A CA266279 A CA 266279A CA 1077430 A CA1077430 A CA 1077430A
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- CA
- Canada
- Prior art keywords
- group
- per liter
- zero
- lower alkyl
- grams per
- 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.)
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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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
-
- 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
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Abstract
ABSTRACT
An acidic electroplating bath for providing a bright tin or tin/cadmium deposit containing stannous ions or mixtures of stannous and cadmium ions, a free acid, a non-ionic surfactant and as a brightener system a ring-halogenated aryl aldehyde, formaldehyde, and at least one compound of the formula:
where n is zero or 1, m is zero or 1, and when n is 1, m is zero, and when m is 1, n is zero, R1 is hydrogen or a lower alkyl group, and when both m and n are zero, R2 and R3 are hydrogen or lower alkyl groups and R4 is a formyl, alkyl carbonyl, carboxamido, or carboxy group or mixtures thereof, and R4 is a formyl or alkyl carbonyl group or mixtures thereof, R1 or R2 is a lower alkyl group; when n is 1, the combination of R2 and ?
represent ethenylene and R3 is an oxygen or sulfur radical, and R4 is as above; when m is 1, the combination of R2 and ?1 represent alkylene, R3 is hydrogen or a lower alkyl group and R4 is a carbonyl group.
An acidic electroplating bath for providing a bright tin or tin/cadmium deposit containing stannous ions or mixtures of stannous and cadmium ions, a free acid, a non-ionic surfactant and as a brightener system a ring-halogenated aryl aldehyde, formaldehyde, and at least one compound of the formula:
where n is zero or 1, m is zero or 1, and when n is 1, m is zero, and when m is 1, n is zero, R1 is hydrogen or a lower alkyl group, and when both m and n are zero, R2 and R3 are hydrogen or lower alkyl groups and R4 is a formyl, alkyl carbonyl, carboxamido, or carboxy group or mixtures thereof, and R4 is a formyl or alkyl carbonyl group or mixtures thereof, R1 or R2 is a lower alkyl group; when n is 1, the combination of R2 and ?
represent ethenylene and R3 is an oxygen or sulfur radical, and R4 is as above; when m is 1, the combination of R2 and ?1 represent alkylene, R3 is hydrogen or a lower alkyl group and R4 is a carbonyl group.
Description
F.N. 912,566 lQ77430 ELECTROPLATING BATH FOR THE ELECTRODEPOSITION OF
TIN AND TIN/CADMIUM DEPOSITS
A variety of electroplating baths have been disclosed for the electrodeposition of brlght tln upon metallic substrates. These baths have been substantlally acidlc and have been utllized in many industrial appllca-tions. Typical of such disclosed baths include thosedescrlbed in U.S. Patent Nos. 3,361,652; 3,471,379 and 3,875,029.
Many of these aforementloned baths contain as surface active agents imidazoline derlvatives, whlch tend to provide instability to the bath. Furthermore, the baths aforementloned typically contain a single carbonyl compound as a brightener. While these baths have proven generally satisfactory, and have been widely utlllzed ln a commercial setting, they are usually deficlent in one or more desirable operating characteristics, and the deposits produced thereby frequently fail to provide a balance of characteristics such as smoothness, brlghtness, adherence, solderability and stability to reslst agingO
Furthermore, these baths typlcally do not exhibit the aforementioned characteristics over the entlre operable range of current densities and do not avold step platlng and shadowing when holes and deep recessed areas are present in the metallic work plece utillzed in the bathO
Therefore, while various of the baths described in the literature are operable with varying degrees of effectiveness, there has remained a need to provlde a bath capable of producing smooth adherent deposits exhibiting ~X~.
-1077~30 spectral brlghtness over a wide current denslty range andwherein the components of the bath provlde substantial stability thereto.
It has now been determined that by utilizing a specifically defined combination of organic brighteners, an acid tin or tin-cadmium alloy electroplating bath is provided which is substantially stable and is capable of producing brlght, smooth, fine-grained deposits over a wide cathode current density range upon continued electrolysisO Further-more, superior bright throwing power in recessed areas ofthe cathode is exhibited. Since the bath is free of ammon-ium ion and cyanide/or chelating compounds, simplification of waste treatment procedures necessary for removal of the metals from the bath is exhibied.
In accordance with the invention, there is pro-vided an aqueous acidic bath for the electrodeposition of tin or tin/cadmium comprising from about 7.5 to about 75 grams per liter of stannous or a mixture of stannous and cadmium lons, from about 70 to about 400 grams per liter of a free acid selected from the group consisting of sulfuric acid, fluoboric acid or mixtures thereof, from about 3 to about 30 grams per liter Or a non-ionic polyoxyalkylated surfactant and a brightener combination consisting of from about 0.01 to about 0.5 gram per liter of a ring-halogenated aryl aldehyde, from about 2 to about 30 milliliters per liter of an aqueous formaldehyde solution and about Ool to about 2.0 grams per liter of at least one compound of the formula:
- . . ~ . . ~ , .
10774;~0 ] ~2 (I)n(~)m 13 ¦ I
Rl - C - C R4 wherein n is zero or 1, m is zero or 1 and when n is 1, m is zero and when m ls 1, n ls zero, Rl is hydrogen or a lower alkyl group and when n and m are zero, R2 and R3 are hydrogen or lower alkyl groups and R4 is a formyl, alkyl carbonyl, carboxamido, or carboxy group or mlxture thereof, and when R4 is a formyl or alkyl carbonyl group or mixture thereof, Rl or R2 is a lower alkyl group; when n ls 1, the combination of R2 and g represent ethenylene, R3 is an oxygen or sulfur radical, and R4 is a formyl, alkyl car-bonyl, carboxamido, or carboxy group or mixture thereof;
when m is 1, the combination of R2 and ~1 represent alkylene, R3 is hydrogen or a lower alkyl group, and R4 is a carbonyl group.
A second brightener combination useful here~n consists of from about 0.01 to about 0.5 grams per liter of a ring-halogenated aryl aldehyde, about Ool to about 2.0 grams per llter of a compound defined by the above formula wherein m is zero and R4 is formyl or alkyl carbonyl group or mixture thereof, and from about 0.1 to about 2=0 grams per liter of a compound defined by the above formula wherein m is zero and R4 is a carboxamldo or carboxy group or mixture thereof Such can be represented by the formula:
. . .
~ 10'~'74;~0 R2 (~)n ¦ 13 II
Rl - C = C4 R4 wherein n, Rl, R2 and R3 are as shown above By utilizing one of these brlghtener comblna-tions, bright tin or tin/cadmium deposits can be obtained over a wide current density range upon continued operation of the bath.
The acid bath of the present invention requires stannous ions or mlxtures of the stannous and cadmium ions, a free acid selected from the group consisting of sul~uric, fluoboric or mixtures thereof, a non-ionic polyoxyalkylated sur~actant, and a specific combination or organic br~ghten-ers as derined herein below.
Typically, the bath may contain from about 7O5 to about 75 grams per liter Or stannous ion or a mixture of stannous and cadmium ions furnished individually as soluble salts such as stannous sulphate, stannous ~luo-borate, cadmlum sulphate, cadmlum ~luoborate or materials such as cadmium oxide which are capable of forming a metallic salt with anions normally introduced with the bath. Metalllc ion concentrations greater than about 75 grams per liter may tend to produce coarse, grainy and dull deposits at low cathode current density areas, iOe less than about 0.5 amperes per square decimeterO Metal ion concentrations lower than about 7O5 grams per llter may tend to provide low cathode current eff~cienc~ to the b~th and burning and pitting of the cathode at high cathode .
1(~77430 current density areasO Preferably, the bath contains from about 12.0 to about 40.0 grams per llter of metaLllc ion.
The free acid concentration may range from about 70 to about 400 grams per liter wlth from about 100 to about 200 grams per liter being preferred. At concentra-tions of less than about 70 grams per liter, the bath may exhibit poor conductlvlty and therefore be operative only a narrow range of current densities producing coatlngs of marginal quality. Increasing the acld concentratlon beyond about 400 grams per liter produces a minimal additional increase in current density and tends to reduce the cathode current efficiencyO
As to the non-ionic surfactant~ vlrtually any surface active polyoxyalkylated compound which is soluble in the bath may be employed, and a wide variety of such materials are commercially avallable under a number of different tradenamesO However, lt has been found that the polyethoxylated fatty acld monoalkylolamldes and the polyethyoxylated alkyl phenols have performed particularly effectively in the baths of the inventionO Exemplary of the polyethoxylated fatty acld monoethanolamides that are advantageously used in the bath are the coconut fatty acld and lauric acid derivatives which are commercially aYailable from the Stepan Chemical Company under the traden~mes Amidox C-5 and Amidox L-5, respectively. Exemplary of a polyethoxylated alkyl phenol surfactant ls the ethoxyl~ted nonyl phenol derlvative commerclally availabl~ from the Millmaster Onyx Corporation under the tradename Neutronyx 656.
. : ~ . .
~:
' ~ ' ' - ~ , ~ .
.
.
Substitutlon of simllar surfactants ~or those enumerated above is contemplated and encompassed within the scope of the invention herein, and specific alternati~e non-ionic surfactants will be apparent to those skilled ln the art in view of the disclosure herein.
The surfactant concentration may range from about 3 to about 30 grams per llter with from about 4 to about 15 grams per liter being preferred. Utillzation of less than about 3 grams per llter may tend to produce a thln deposit, especially at low current density areas, lOeG
less than about 1.0 ampere per square decimeterO At sur-factant concentrations greater than about 30 grams per llter, :
little additional beneflt is gained and the deposit may tend to be dull at low current denslty areasO
It has been determined that a specific combina-tion of organic brighteners in con~unction with the non-ionic surfactant defined above, are capable of providing brlght specular deposits over the entire useful cathode current density range, l.e from about 0.02 to about 25 amperes per square decimeterO There are in essence two combinations of brighteners whlch have been found to func~ion satisfactorily to provide the aforementioned ch~racteristics to the tin or tin/cadmium plateO The flrst brightener -combination contalns therein a rlng-halogenated aryl aldehyde, formaldehyde and at least one compound o~ .t~e formula: ~
(~)n(l )m R
Rl - C = C ~ '4 ~ 0774~0 wherein n is zero or l, m is zero or l, and when n is l, m is zero and when m is 1, n is zero, Rl is hydrogen or a lower alkyl group, and when n and m are zero, R2 and R3 are hydrogen or lower alkyl groups and R4 ls a formyl (lOeO
OCH-), alkyl carbonyl (i.e. RCO-), carboxamido (i.eO R2NCO-), or carboxy (i.e. HOOC-) group or mixture thereof, and when R4 is a formyl or alkyl carbonyl group or a mixture thereof, Rl or R2 is a lower alkyl group; such can be depicted:
10 Rl - C = C - R4 when n is l, the comblnatlon of R2 and ~ represent ethenyl-ene (l.e. -CH=CH-), R3 ls an oxygen or sulfur radical, and R4 is a formyl, alkyl carbonyl, carboxamldo, or carboxy group or mixture thereof; such can be depicted:
1 ll3 Rl - = C - R4 when m is l, the combinatlon of R2 and gl represent alkylene, (i.e. -R-), R3 is hydrogen or a lower alkyl group, and R4 is a carbonyl group, (l.e. OC=); such can be represented:
~ 13 ¦
Rl - = C - 4 By the term "lower alkyl group" is meant an alkyl group of less than 4 carbon atoms.
-Examples of ring-halogenated aryl aldehydes include ortho-chlorobenzaldehyde, para-chlorobenzaldehyde,
TIN AND TIN/CADMIUM DEPOSITS
A variety of electroplating baths have been disclosed for the electrodeposition of brlght tln upon metallic substrates. These baths have been substantlally acidlc and have been utllized in many industrial appllca-tions. Typical of such disclosed baths include thosedescrlbed in U.S. Patent Nos. 3,361,652; 3,471,379 and 3,875,029.
Many of these aforementloned baths contain as surface active agents imidazoline derlvatives, whlch tend to provide instability to the bath. Furthermore, the baths aforementloned typically contain a single carbonyl compound as a brightener. While these baths have proven generally satisfactory, and have been widely utlllzed ln a commercial setting, they are usually deficlent in one or more desirable operating characteristics, and the deposits produced thereby frequently fail to provide a balance of characteristics such as smoothness, brlghtness, adherence, solderability and stability to reslst agingO
Furthermore, these baths typlcally do not exhibit the aforementioned characteristics over the entlre operable range of current densities and do not avold step platlng and shadowing when holes and deep recessed areas are present in the metallic work plece utillzed in the bathO
Therefore, while various of the baths described in the literature are operable with varying degrees of effectiveness, there has remained a need to provlde a bath capable of producing smooth adherent deposits exhibiting ~X~.
-1077~30 spectral brlghtness over a wide current denslty range andwherein the components of the bath provlde substantial stability thereto.
It has now been determined that by utilizing a specifically defined combination of organic brighteners, an acid tin or tin-cadmium alloy electroplating bath is provided which is substantially stable and is capable of producing brlght, smooth, fine-grained deposits over a wide cathode current density range upon continued electrolysisO Further-more, superior bright throwing power in recessed areas ofthe cathode is exhibited. Since the bath is free of ammon-ium ion and cyanide/or chelating compounds, simplification of waste treatment procedures necessary for removal of the metals from the bath is exhibied.
In accordance with the invention, there is pro-vided an aqueous acidic bath for the electrodeposition of tin or tin/cadmium comprising from about 7.5 to about 75 grams per liter of stannous or a mixture of stannous and cadmium lons, from about 70 to about 400 grams per liter of a free acid selected from the group consisting of sulfuric acid, fluoboric acid or mixtures thereof, from about 3 to about 30 grams per liter Or a non-ionic polyoxyalkylated surfactant and a brightener combination consisting of from about 0.01 to about 0.5 gram per liter of a ring-halogenated aryl aldehyde, from about 2 to about 30 milliliters per liter of an aqueous formaldehyde solution and about Ool to about 2.0 grams per liter of at least one compound of the formula:
- . . ~ . . ~ , .
10774;~0 ] ~2 (I)n(~)m 13 ¦ I
Rl - C - C R4 wherein n is zero or 1, m is zero or 1 and when n is 1, m is zero and when m ls 1, n ls zero, Rl is hydrogen or a lower alkyl group and when n and m are zero, R2 and R3 are hydrogen or lower alkyl groups and R4 is a formyl, alkyl carbonyl, carboxamido, or carboxy group or mlxture thereof, and when R4 is a formyl or alkyl carbonyl group or mixture thereof, Rl or R2 is a lower alkyl group; when n ls 1, the combination of R2 and g represent ethenylene, R3 is an oxygen or sulfur radical, and R4 is a formyl, alkyl car-bonyl, carboxamido, or carboxy group or mixture thereof;
when m is 1, the combination of R2 and ~1 represent alkylene, R3 is hydrogen or a lower alkyl group, and R4 is a carbonyl group.
A second brightener combination useful here~n consists of from about 0.01 to about 0.5 grams per liter of a ring-halogenated aryl aldehyde, about Ool to about 2.0 grams per llter of a compound defined by the above formula wherein m is zero and R4 is formyl or alkyl carbonyl group or mixture thereof, and from about 0.1 to about 2=0 grams per liter of a compound defined by the above formula wherein m is zero and R4 is a carboxamldo or carboxy group or mixture thereof Such can be represented by the formula:
. . .
~ 10'~'74;~0 R2 (~)n ¦ 13 II
Rl - C = C4 R4 wherein n, Rl, R2 and R3 are as shown above By utilizing one of these brlghtener comblna-tions, bright tin or tin/cadmium deposits can be obtained over a wide current density range upon continued operation of the bath.
The acid bath of the present invention requires stannous ions or mlxtures of the stannous and cadmium ions, a free acid selected from the group consisting of sul~uric, fluoboric or mixtures thereof, a non-ionic polyoxyalkylated sur~actant, and a specific combination or organic br~ghten-ers as derined herein below.
Typically, the bath may contain from about 7O5 to about 75 grams per liter Or stannous ion or a mixture of stannous and cadmium ions furnished individually as soluble salts such as stannous sulphate, stannous ~luo-borate, cadmlum sulphate, cadmlum ~luoborate or materials such as cadmium oxide which are capable of forming a metallic salt with anions normally introduced with the bath. Metalllc ion concentrations greater than about 75 grams per liter may tend to produce coarse, grainy and dull deposits at low cathode current density areas, iOe less than about 0.5 amperes per square decimeterO Metal ion concentrations lower than about 7O5 grams per llter may tend to provide low cathode current eff~cienc~ to the b~th and burning and pitting of the cathode at high cathode .
1(~77430 current density areasO Preferably, the bath contains from about 12.0 to about 40.0 grams per llter of metaLllc ion.
The free acid concentration may range from about 70 to about 400 grams per liter wlth from about 100 to about 200 grams per liter being preferred. At concentra-tions of less than about 70 grams per liter, the bath may exhibit poor conductlvlty and therefore be operative only a narrow range of current densities producing coatlngs of marginal quality. Increasing the acld concentratlon beyond about 400 grams per liter produces a minimal additional increase in current density and tends to reduce the cathode current efficiencyO
As to the non-ionic surfactant~ vlrtually any surface active polyoxyalkylated compound which is soluble in the bath may be employed, and a wide variety of such materials are commercially avallable under a number of different tradenamesO However, lt has been found that the polyethoxylated fatty acld monoalkylolamldes and the polyethyoxylated alkyl phenols have performed particularly effectively in the baths of the inventionO Exemplary of the polyethoxylated fatty acld monoethanolamides that are advantageously used in the bath are the coconut fatty acld and lauric acid derivatives which are commercially aYailable from the Stepan Chemical Company under the traden~mes Amidox C-5 and Amidox L-5, respectively. Exemplary of a polyethoxylated alkyl phenol surfactant ls the ethoxyl~ted nonyl phenol derlvative commerclally availabl~ from the Millmaster Onyx Corporation under the tradename Neutronyx 656.
. : ~ . .
~:
' ~ ' ' - ~ , ~ .
.
.
Substitutlon of simllar surfactants ~or those enumerated above is contemplated and encompassed within the scope of the invention herein, and specific alternati~e non-ionic surfactants will be apparent to those skilled ln the art in view of the disclosure herein.
The surfactant concentration may range from about 3 to about 30 grams per llter with from about 4 to about 15 grams per liter being preferred. Utillzation of less than about 3 grams per llter may tend to produce a thln deposit, especially at low current density areas, lOeG
less than about 1.0 ampere per square decimeterO At sur-factant concentrations greater than about 30 grams per llter, :
little additional beneflt is gained and the deposit may tend to be dull at low current denslty areasO
It has been determined that a specific combina-tion of organic brighteners in con~unction with the non-ionic surfactant defined above, are capable of providing brlght specular deposits over the entire useful cathode current density range, l.e from about 0.02 to about 25 amperes per square decimeterO There are in essence two combinations of brighteners whlch have been found to func~ion satisfactorily to provide the aforementioned ch~racteristics to the tin or tin/cadmium plateO The flrst brightener -combination contalns therein a rlng-halogenated aryl aldehyde, formaldehyde and at least one compound o~ .t~e formula: ~
(~)n(l )m R
Rl - C = C ~ '4 ~ 0774~0 wherein n is zero or l, m is zero or l, and when n is l, m is zero and when m is 1, n is zero, Rl is hydrogen or a lower alkyl group, and when n and m are zero, R2 and R3 are hydrogen or lower alkyl groups and R4 ls a formyl (lOeO
OCH-), alkyl carbonyl (i.e. RCO-), carboxamido (i.eO R2NCO-), or carboxy (i.e. HOOC-) group or mixture thereof, and when R4 is a formyl or alkyl carbonyl group or a mixture thereof, Rl or R2 is a lower alkyl group; such can be depicted:
10 Rl - C = C - R4 when n is l, the comblnatlon of R2 and ~ represent ethenyl-ene (l.e. -CH=CH-), R3 ls an oxygen or sulfur radical, and R4 is a formyl, alkyl carbonyl, carboxamldo, or carboxy group or mixture thereof; such can be depicted:
1 ll3 Rl - = C - R4 when m is l, the combinatlon of R2 and gl represent alkylene, (i.e. -R-), R3 is hydrogen or a lower alkyl group, and R4 is a carbonyl group, (l.e. OC=); such can be represented:
~ 13 ¦
Rl - = C - 4 By the term "lower alkyl group" is meant an alkyl group of less than 4 carbon atoms.
-Examples of ring-halogenated aryl aldehydes include ortho-chlorobenzaldehyde, para-chlorobenzaldehyde,
2,4-dichlorobenzaldehyde and 2,6-dichlorobenzaldehydeO
Exemplary compounds falling under the scope of Formula I when both m and n are zero, i.e. non-cyclic compounds, include:
mesityl oxide CH3-C = CH - ~ - CH3 croton aldehyde CH3 - CH = CH - C - H
acrylic acid CH2 = CH = - OH
dlacetone ~ ¦ 3 acrylamide CH2 = CH _ - NH - C - CH2 - C - CH3 Exemplary compounds of the Formula when n is 1 and m is zero include:
alpha-thiophene CH~ CH
aldehyde ¦ O ~
CH.~ ._ C/ - CH
furfural CH~ _CH
CH ~ C/ S ~
Exemplary compounds when n is zero and m ls 1 include:
-~077430 isophorone\ /
C CH
CH2/ \C = O
\1. C/
2-cyclopentenone CH / / C = O
The second brightener comblnation found to provide the aforementioned characteristics contains a ring-halogenated aryl aldehyde, at least one compound of Formula:
R2- (I)n ~R3 II
Rl - C = 4 wherein n, Rl, R2 and R3 are as defined above and R4 is a carboxamido or carboxy group, and at least one compound of Formula II wherein R4 is a formyl or alkyl carbonyl group.
Either Rl or R2 must be a lower alkyl group in the latter compound. (It should be noted that in this instance dlace-tone acrylamide functions as a ketone as opposed to an ~
amlde.) ~-The concentration of the ring-halogenated aryl aldehyde may typically range from about OoOl to about 0,5 gram per liter, with from about 0.03 to about 0O3 gram per liter being preferred. The concentration of formaldehyde (as 37 percent by weight formaldehyde in an aqueous solution~
..: . . ~ . . .
. . : . . .
'' '' : - ' ~ ' , ' 1~:)77430 may range from about 2 to about 30 mllliliters per liter with about 4 to about 15 mllliliters per liter being pre- ¦-ferred. Concentration of compounds deplcted by Formula I
or Formula II may range from about 0.1 to about 2.0 grams per liter with from about 0O15 to about loO gram per liter being preferred.
Brightener concentrations below those recommended above may produce no plating at all or may tend to produce frostlness, dullness, non-uniformity or roughness in the deposlt. Concentrations exceeding the upper llmit are wasteful, may tend to cause insolubility o~ the brighten-ers in the bath, and may tend to produce thln or even non-exlstent deposlt at low current density areas, i.e. below about 1.0 amperes per square decimeter.
Although it has been generally determined that the bath of the present invention characteristically functions without necessity of addltional additives therein, such may deslrably be lncluded to modify the operation of the present bath. Additives such as pyrocatechol, resor-cinol, beta-naphthol, and cresyllc acld, as are reported useful as antloxldants ln the llterature relatlng to acid tln baths may typlcally be lncluded.
The electroplating bath of the present inventlon may characterlstically be operated over a wide range of plating conditlons, and more partlcularly at temperatures ranging from about 60F (16C) to about 90F (32C) with from about 68F (20C) to 85F (30C) being preferred, and at cathode current densities of from about 0O02 to 25 amperes per square decimeter.
The invention wlll now be more speclfically illustrated by the use of the following non-limiting examples wherein all parts are by weight unless otherwlse indicated. In each Or the baths of the following examples, unless otherwise noted, testing thereof was undertaken utilizing a conventional 267 milliliter Hull cell under
Exemplary compounds falling under the scope of Formula I when both m and n are zero, i.e. non-cyclic compounds, include:
mesityl oxide CH3-C = CH - ~ - CH3 croton aldehyde CH3 - CH = CH - C - H
acrylic acid CH2 = CH = - OH
dlacetone ~ ¦ 3 acrylamide CH2 = CH _ - NH - C - CH2 - C - CH3 Exemplary compounds of the Formula when n is 1 and m is zero include:
alpha-thiophene CH~ CH
aldehyde ¦ O ~
CH.~ ._ C/ - CH
furfural CH~ _CH
CH ~ C/ S ~
Exemplary compounds when n is zero and m ls 1 include:
-~077430 isophorone\ /
C CH
CH2/ \C = O
\1. C/
2-cyclopentenone CH / / C = O
The second brightener comblnation found to provide the aforementioned characteristics contains a ring-halogenated aryl aldehyde, at least one compound of Formula:
R2- (I)n ~R3 II
Rl - C = 4 wherein n, Rl, R2 and R3 are as defined above and R4 is a carboxamido or carboxy group, and at least one compound of Formula II wherein R4 is a formyl or alkyl carbonyl group.
Either Rl or R2 must be a lower alkyl group in the latter compound. (It should be noted that in this instance dlace-tone acrylamide functions as a ketone as opposed to an ~
amlde.) ~-The concentration of the ring-halogenated aryl aldehyde may typically range from about OoOl to about 0,5 gram per liter, with from about 0.03 to about 0O3 gram per liter being preferred. The concentration of formaldehyde (as 37 percent by weight formaldehyde in an aqueous solution~
..: . . ~ . . .
. . : . . .
'' '' : - ' ~ ' , ' 1~:)77430 may range from about 2 to about 30 mllliliters per liter with about 4 to about 15 mllliliters per liter being pre- ¦-ferred. Concentration of compounds deplcted by Formula I
or Formula II may range from about 0.1 to about 2.0 grams per liter with from about 0O15 to about loO gram per liter being preferred.
Brightener concentrations below those recommended above may produce no plating at all or may tend to produce frostlness, dullness, non-uniformity or roughness in the deposlt. Concentrations exceeding the upper llmit are wasteful, may tend to cause insolubility o~ the brighten-ers in the bath, and may tend to produce thln or even non-exlstent deposlt at low current density areas, i.e. below about 1.0 amperes per square decimeter.
Although it has been generally determined that the bath of the present invention characteristically functions without necessity of addltional additives therein, such may deslrably be lncluded to modify the operation of the present bath. Additives such as pyrocatechol, resor-cinol, beta-naphthol, and cresyllc acld, as are reported useful as antloxldants ln the llterature relatlng to acid tln baths may typlcally be lncluded.
The electroplating bath of the present inventlon may characterlstically be operated over a wide range of plating conditlons, and more partlcularly at temperatures ranging from about 60F (16C) to about 90F (32C) with from about 68F (20C) to 85F (30C) being preferred, and at cathode current densities of from about 0O02 to 25 amperes per square decimeter.
The invention wlll now be more speclfically illustrated by the use of the following non-limiting examples wherein all parts are by weight unless otherwlse indicated. In each Or the baths of the following examples, unless otherwise noted, testing thereof was undertaken utilizing a conventional 267 milliliter Hull cell under
3 ampere~ of current for 3 minutes. Furthermore, the bath was not agitated and temperatures were maintained at from 22C to 24C therein. The examples were prepared utilizing a stock solution of 30 grams per liter of stannous sulfate and 105 milliliters per liter of 66 Baume sulfurlc acid unless otherwise indicated.
A bath was prepared utilizing the aforementioned ;
stock solution and, on a per liter basis, 10 grams of Amidox C-5 (tradename for a polyethoxylated, coconut fatty acid monoethanolamide), 7.5 milliliters of 37 percent by -welght aqueous formaldehyde and 0.4 gram of mesityl oxide were added thereto. Testing in the Hull cell indicated a 20 dull plate from 0.01 to 0,2 amperes per square decimeter, a semi bright plate from 0.2 to lo 5 amperes per square decimeter, a dull band was visible from 1.5 to 2.5 amperes per square decimeter, the panel was semi bright from 2.5 to 8.0 amperes per square decimeter and was fully bright at densities greater than 8.o amperes per square decimeter~
To the above bath was added 0.15 gram per liter of 2,4-dichlorobenzaldehyde. The Hull Cell panel indicated a fully bright deposit over the entire density range of from 0.01 to 15.0 amperes per square decimeterO
. . . .
~'` 1077430 A bath was prepared utilizing the stock solu~lon, and addlng thereto on a per liter basis, 10 grams of Amidox C-5, 705 milliliters of 37 percent by weight aqueous form-aldehyde and 0.15 gram of 2,4-dichlorobenzaldehydeO The Hull cell panel indicated a dull and thin plating from 0.01 to 0.15 amperes per square decimeter, frostiness was noted at from 0015 to 3.5 amperes per square decimeter, a bright plate with some striation or streak~ng was noted from 3.5 to 7.0 amperes per square decimeter and at densities greater than 7.0 amperes per square decimeter, the plate was gray and appeared burned.
To the above bath was added 0.4 gram per liter o~
mesltyl oxide whereupon a panel simllar to that disclosed in Example 1 was providedO
A bath was prepared utilizing the stock solution, and on a per liter basis were added thereto 10 grams of Amidox C-5, 0.15 gram of 2,4-dichlorobenzaldehyde, and 004 gram of mesltyl oxideO From 0.01 to 205 amperes per square decimeter the plate was very thin or nonexistent. At densities greater than 2.5 amperes per square decimeter, a thin, rough, black deposlt appeared on the test panel~
When 705 millillters of the 37 percent by weight formaldehyde was added to the bath, and retested, a fully bright panel was obtained as in the second solution of - ~ -Example 1.
The above examples illustrate that the specific organlc brightener comblnation~ together with the non-ionic . . - .
. . -` 1077430 surfactant provide a bright, deslrable and commerclally usable electroplated tin depositO
To the basic stock solution were added, per liter, 10 grams of Amidox C-5, 0.15 gram of 2,4-dichloro-benzaldehyde, 7.5 milliliters o~ 37 percent by weight formaldehyde and 0.16 gram of alpha-thiophene aldehyde.
The Hull test panel provided a bright deposit ~rom 0~05 :;-to 4~0 amperes per square decimeter with some pitting noted at densities greater than 1.8 amperes per square decimeter. From 4.0 to 12.0 amperes per square decimeter, the panel illustrated a brlght plating with some pitting ~ -:
and striation noted.
An electroplating bath was prepared utilizlng the stock solution in con~unction with, on a per liter basis, 10 grams of Amidox C-5, 0.15 gram of 2,4-dichloro-benzaldehyde~ 7.5 milllliters of 37 percent by welght :
formaldehyde and 0O3 gram of 2-furyl methyl ketoneO The Hull panel had a bright plate thereon from 0.05 to 6 0 amperes per square decimeter with some pitting noted at denslties greater than 2.4 amperes per square decimeter, and waæ fully brlght with some strlation and pitting noted at from 6Oo to 12.0 amperes per square decimeterO
When the 2-furyl methyl ketone of Example 5 wa~
replaced by 0O5 grams of dlacetone acrylamide, a panel -was fully bright from 0O05 to 12.0 amperes per square decimeter was obtained.
When the ketone of Example 5 was replaced by 0O3 gram of acrylic acid, a test panel which was fully bright was obtained at current densities from 0O05 to 1.2 amperes per square decimeter, and from 1.2 to 12~0 amperes per square decimeter the plate was fully brlght with some striation noted and some pitting was observed at denslties greater than 2O0 amperes per square decimeterO
A bath was prepared utillzing the stock solution in con~unction with, on a per liter basis, 10 grams of Neutronyx 656 (tradename for an ethoxylated nonly phenol), 8 milllliters of 37 percent by weight formaldehyde and 0O4 gram of mesltyl oxlde. At current densitles of from 0.05 to 3.0 amperes per square decimeter, the plate was dully, and up to 12.0 amperes per square decimeter was semi bright~
To this solution was added 0.15 gram of 2,4- -dlchlorobenzaldehyde whereupon a fully bright panel was obtalned from 0.01 to 15.0 amperes per square declmeter wlth some pittlng being noted at densities greater than 5.0 amperes per square decimeterO
To the stock solution was added, on a per liter basis, 2 grams of Neutronyx 656, 8 milliliters of 37 percent by weight formaldehyde and 0.03 gram of 1~77430 parachlorobenzaldehydeO The Hull test panel indicated nonexistent or a very thin bright plate at densities of from 0.01 to 102 amperes per square decimeter and ~rostiness was noted at current densitles greater than 1c2 amperes per square decimeterO
An additional 8 grams Or Neutronyx 656 was added to the bath whereupon the panel provlded bright plating with some haziness from 0.01 to 1.2 amperes per square decimeter,frostlness at densities of from 1.2 to 3O5 amperes per square decimter, a bright panel with some striation and pitting from 3O5 to 8 0 amperes per square decimter and bur~ing of the panel at densitles greater than 8~o amperes per square decimeter.
To this solution was added 0.3 gram per liter of mesityl oxide whereupon the test panel provided a bright plate from 0.05 to 15.0 amperes per square decimeter, some pitting being noted at densities greater than ~.0 amperes per square decimeter~
A bath was prepared utlllzlng the stock solutlon in con~unction with, on a per liter basis, 10.0 grams of Amidox C-5, 0~15 grams Or 2,4-dichlorobenzaldehyde, 0O3 gram of mesityl oxide and 0O15 gram of acylic acidO The test panel was fully bright over a current density range 25 of from 0.1 to 12.0 amperes per square decimeter.
A bath was prepared utilizing the stock solut~on in conJunction with, on a per llter basis, lOo O grams of Amidox C-5, 0O15 gr~m o~ 2,4-dichlorobenzaldehyde, 0O4 gr~m . -of diacetone acrylamide and 0.15 gram of acrylic acidO
The test panel was fully bright over a current density range of from 0.05 to 15.0 amperes per square decimeterO
A bath was prepared by mixing, on a per liter basis, 45 milliliters of a 49.6 percent by weight aqueous stannous fluoborate solution, 140 milliliters of a 49 percent by weight aqueous fluoboric acid, 4 grams of Amidox C-5, 0.15 grams of 2,4-dichlorobenzaldehyde and 7.5 milliliters of 37 percent by weight formaldehyde. The test panel provided a very thin, or in some instances, non-existent plating at current densities of from 0.01 to 0O2 amperes per square decimeter, a frosty plate at from 0.2 to 8.o amperes per square decimeter, and a fully bright plate with some striation and pitting noted at from 8.o to 12.0 amperes per square decimeter.
To this solution was added 0.45 gram of mesityl oxlde whereupon the test panel illustrated a relatively thln plate at current densities of from 0.01 to 0.15 amperes per square decimeter and a fully bright plate fromØ15 to 12.0 amperes per square decimeter wlth some pltting noted at densities greater than 6Ø
EXA~PLE 13 A bath was prepared by combinlng, on a per llter basis, 90 millillters of a 49.6 percent by welght aqueous stannous ~luoborate solution, 140 milliliters of 4~ percent by welght aqueous fluoborlc acld, 10.0 grams of Amldox C-5, 0.15 gram of 2,4-dichlorobenzaldehyde, 0.6 gram of mesityl oxide and 15 mllliliters of 37 percent by weight aqueous formaldehyde. A Hull cell panel tested under 5 amperes sf current for 2 minutes with fast agitation lndicated a brightness range over from 2.0 to 23.0 amperes per square decimeter with some pitting Or the plate being noted at densities above 12.5 amperes per square decimeter.
An electroplating bath was prepared by combining, on a per liter basis, 25.7 grams of cadmium oxide, 15 grams of stannous sulfate, 105 millillters of 66 Baume sulfurlc acid, 12.0 grams of Amidox C-5, 0.15 gram of 2,4-dlchloro-benzaldehyde and 7.5 milliliters of 37 percent by weight aqueous formaldehyde. A ~ull test panel indicated a frosty plate at current denslties of from 0.01 to 3 0 amperes per square decimeter with the plating being ~ully bright wlth heavy pitting noted at densities of from 3.0 to 15.0 amperes per square decimeter.
To thls solution was added 0.22 gram per llter of mesityl oxide. The test panel indicated a fully bright range over densities Or from 0.05 to 15.0 amperes per square decimeter.
A bath was prepared utilizing the aforementioned ;
stock solution and, on a per liter basis, 10 grams of Amidox C-5 (tradename for a polyethoxylated, coconut fatty acid monoethanolamide), 7.5 milliliters of 37 percent by -welght aqueous formaldehyde and 0.4 gram of mesityl oxide were added thereto. Testing in the Hull cell indicated a 20 dull plate from 0.01 to 0,2 amperes per square decimeter, a semi bright plate from 0.2 to lo 5 amperes per square decimeter, a dull band was visible from 1.5 to 2.5 amperes per square decimeter, the panel was semi bright from 2.5 to 8.0 amperes per square decimeter and was fully bright at densities greater than 8.o amperes per square decimeter~
To the above bath was added 0.15 gram per liter of 2,4-dichlorobenzaldehyde. The Hull Cell panel indicated a fully bright deposit over the entire density range of from 0.01 to 15.0 amperes per square decimeterO
. . . .
~'` 1077430 A bath was prepared utilizing the stock solu~lon, and addlng thereto on a per liter basis, 10 grams of Amidox C-5, 705 milliliters of 37 percent by weight aqueous form-aldehyde and 0.15 gram of 2,4-dichlorobenzaldehydeO The Hull cell panel indicated a dull and thin plating from 0.01 to 0.15 amperes per square decimeter, frostiness was noted at from 0015 to 3.5 amperes per square decimeter, a bright plate with some striation or streak~ng was noted from 3.5 to 7.0 amperes per square decimeter and at densities greater than 7.0 amperes per square decimeter, the plate was gray and appeared burned.
To the above bath was added 0.4 gram per liter o~
mesltyl oxide whereupon a panel simllar to that disclosed in Example 1 was providedO
A bath was prepared utilizing the stock solution, and on a per liter basis were added thereto 10 grams of Amidox C-5, 0.15 gram of 2,4-dichlorobenzaldehyde, and 004 gram of mesltyl oxideO From 0.01 to 205 amperes per square decimeter the plate was very thin or nonexistent. At densities greater than 2.5 amperes per square decimeter, a thin, rough, black deposlt appeared on the test panel~
When 705 millillters of the 37 percent by weight formaldehyde was added to the bath, and retested, a fully bright panel was obtained as in the second solution of - ~ -Example 1.
The above examples illustrate that the specific organlc brightener comblnation~ together with the non-ionic . . - .
. . -` 1077430 surfactant provide a bright, deslrable and commerclally usable electroplated tin depositO
To the basic stock solution were added, per liter, 10 grams of Amidox C-5, 0.15 gram of 2,4-dichloro-benzaldehyde, 7.5 milliliters o~ 37 percent by weight formaldehyde and 0.16 gram of alpha-thiophene aldehyde.
The Hull test panel provided a bright deposit ~rom 0~05 :;-to 4~0 amperes per square decimeter with some pitting noted at densities greater than 1.8 amperes per square decimeter. From 4.0 to 12.0 amperes per square decimeter, the panel illustrated a brlght plating with some pitting ~ -:
and striation noted.
An electroplating bath was prepared utilizlng the stock solution in con~unction with, on a per liter basis, 10 grams of Amidox C-5, 0.15 gram of 2,4-dichloro-benzaldehyde~ 7.5 milllliters of 37 percent by welght :
formaldehyde and 0O3 gram of 2-furyl methyl ketoneO The Hull panel had a bright plate thereon from 0.05 to 6 0 amperes per square decimeter with some pitting noted at denslties greater than 2.4 amperes per square decimeter, and waæ fully brlght with some strlation and pitting noted at from 6Oo to 12.0 amperes per square decimeterO
When the 2-furyl methyl ketone of Example 5 wa~
replaced by 0O5 grams of dlacetone acrylamide, a panel -was fully bright from 0O05 to 12.0 amperes per square decimeter was obtained.
When the ketone of Example 5 was replaced by 0O3 gram of acrylic acid, a test panel which was fully bright was obtained at current densities from 0O05 to 1.2 amperes per square decimeter, and from 1.2 to 12~0 amperes per square decimeter the plate was fully brlght with some striation noted and some pitting was observed at denslties greater than 2O0 amperes per square decimeterO
A bath was prepared utillzing the stock solution in con~unction with, on a per liter basis, 10 grams of Neutronyx 656 (tradename for an ethoxylated nonly phenol), 8 milllliters of 37 percent by weight formaldehyde and 0O4 gram of mesltyl oxlde. At current densitles of from 0.05 to 3.0 amperes per square decimeter, the plate was dully, and up to 12.0 amperes per square decimeter was semi bright~
To this solution was added 0.15 gram of 2,4- -dlchlorobenzaldehyde whereupon a fully bright panel was obtalned from 0.01 to 15.0 amperes per square declmeter wlth some pittlng being noted at densities greater than 5.0 amperes per square decimeterO
To the stock solution was added, on a per liter basis, 2 grams of Neutronyx 656, 8 milliliters of 37 percent by weight formaldehyde and 0.03 gram of 1~77430 parachlorobenzaldehydeO The Hull test panel indicated nonexistent or a very thin bright plate at densities of from 0.01 to 102 amperes per square decimeter and ~rostiness was noted at current densitles greater than 1c2 amperes per square decimeterO
An additional 8 grams Or Neutronyx 656 was added to the bath whereupon the panel provlded bright plating with some haziness from 0.01 to 1.2 amperes per square decimeter,frostlness at densities of from 1.2 to 3O5 amperes per square decimter, a bright panel with some striation and pitting from 3O5 to 8 0 amperes per square decimter and bur~ing of the panel at densitles greater than 8~o amperes per square decimeter.
To this solution was added 0.3 gram per liter of mesityl oxide whereupon the test panel provided a bright plate from 0.05 to 15.0 amperes per square decimeter, some pitting being noted at densities greater than ~.0 amperes per square decimeter~
A bath was prepared utlllzlng the stock solutlon in con~unction with, on a per liter basis, 10.0 grams of Amidox C-5, 0~15 grams Or 2,4-dichlorobenzaldehyde, 0O3 gram of mesityl oxide and 0O15 gram of acylic acidO The test panel was fully bright over a current density range 25 of from 0.1 to 12.0 amperes per square decimeter.
A bath was prepared utilizing the stock solut~on in conJunction with, on a per llter basis, lOo O grams of Amidox C-5, 0O15 gr~m o~ 2,4-dichlorobenzaldehyde, 0O4 gr~m . -of diacetone acrylamide and 0.15 gram of acrylic acidO
The test panel was fully bright over a current density range of from 0.05 to 15.0 amperes per square decimeterO
A bath was prepared by mixing, on a per liter basis, 45 milliliters of a 49.6 percent by weight aqueous stannous fluoborate solution, 140 milliliters of a 49 percent by weight aqueous fluoboric acid, 4 grams of Amidox C-5, 0.15 grams of 2,4-dichlorobenzaldehyde and 7.5 milliliters of 37 percent by weight formaldehyde. The test panel provided a very thin, or in some instances, non-existent plating at current densities of from 0.01 to 0O2 amperes per square decimeter, a frosty plate at from 0.2 to 8.o amperes per square decimeter, and a fully bright plate with some striation and pitting noted at from 8.o to 12.0 amperes per square decimeter.
To this solution was added 0.45 gram of mesityl oxlde whereupon the test panel illustrated a relatively thln plate at current densities of from 0.01 to 0.15 amperes per square decimeter and a fully bright plate fromØ15 to 12.0 amperes per square decimeter wlth some pltting noted at densities greater than 6Ø
EXA~PLE 13 A bath was prepared by combinlng, on a per llter basis, 90 millillters of a 49.6 percent by welght aqueous stannous ~luoborate solution, 140 milliliters of 4~ percent by welght aqueous fluoborlc acld, 10.0 grams of Amldox C-5, 0.15 gram of 2,4-dichlorobenzaldehyde, 0.6 gram of mesityl oxide and 15 mllliliters of 37 percent by weight aqueous formaldehyde. A Hull cell panel tested under 5 amperes sf current for 2 minutes with fast agitation lndicated a brightness range over from 2.0 to 23.0 amperes per square decimeter with some pitting Or the plate being noted at densities above 12.5 amperes per square decimeter.
An electroplating bath was prepared by combining, on a per liter basis, 25.7 grams of cadmium oxide, 15 grams of stannous sulfate, 105 millillters of 66 Baume sulfurlc acid, 12.0 grams of Amidox C-5, 0.15 gram of 2,4-dlchloro-benzaldehyde and 7.5 milliliters of 37 percent by weight aqueous formaldehyde. A ~ull test panel indicated a frosty plate at current denslties of from 0.01 to 3 0 amperes per square decimeter with the plating being ~ully bright wlth heavy pitting noted at densities of from 3.0 to 15.0 amperes per square decimeter.
To thls solution was added 0.22 gram per llter of mesityl oxide. The test panel indicated a fully bright range over densities Or from 0.05 to 15.0 amperes per square decimeter.
Claims (6)
1. An aqueous acid plating bath for the electro-deposition of bright tin and tin/cadmium alloys comprising about 7.5 to 75 grams per liter of a metal ion selected from the group consisting of stannous ion, cadmium ion and mixtures thereof; about 70 to 400 grams per liter of a free acid selected from the group consisting of fluoboric acid, sulfuric acid and mixtures thereof; about 3 to 30 grams per liter of a non-ionic polyoxyalkylated surfactant;
about 0.01 to 0.5 grams per liter of a ring-halogenated aryl aldehyde; about 2 to 30 milliliters per liter of an aqueous formaldehyde solution; and about 0.1 to 2.0 grams per liter of at least one compound of the formula:
where n is zero or 1, m is zero or 1, and when n is 1, m is zero, and when m is 1, n is zero, R1 is hydrogen or a lower alkyl group, and when n and m are zero, R2 and R3 are hydrogen or lower alkyl groups, and R4 is a formyl, alkyl carbonyl, carboxamido or carboxy group or mixtures thereof, and when R4 is a formyl or alkyl carbonyl group or mixture thereof, R1 or R2 is a lower alkyl group; when n is 1, the combination of R2 and Z represent ethenylene, R3 is an oxygen or sulfur radical, and R4 is a formyl, alkyl carbonyl, carboxamido or carboxy group or mixture thereof; when m is 1, the combination of R2 and Z1 represent alkylene, R3 is hydrogen or a lower alkyl group and R4 is a carbonyl group.
about 0.01 to 0.5 grams per liter of a ring-halogenated aryl aldehyde; about 2 to 30 milliliters per liter of an aqueous formaldehyde solution; and about 0.1 to 2.0 grams per liter of at least one compound of the formula:
where n is zero or 1, m is zero or 1, and when n is 1, m is zero, and when m is 1, n is zero, R1 is hydrogen or a lower alkyl group, and when n and m are zero, R2 and R3 are hydrogen or lower alkyl groups, and R4 is a formyl, alkyl carbonyl, carboxamido or carboxy group or mixtures thereof, and when R4 is a formyl or alkyl carbonyl group or mixture thereof, R1 or R2 is a lower alkyl group; when n is 1, the combination of R2 and Z represent ethenylene, R3 is an oxygen or sulfur radical, and R4 is a formyl, alkyl carbonyl, carboxamido or carboxy group or mixture thereof; when m is 1, the combination of R2 and Z1 represent alkylene, R3 is hydrogen or a lower alkyl group and R4 is a carbonyl group.
2. The bath of claim 1 wherein said compound is selected from the group consisting of mesityl oxide, crotonaldehyde, acrylic acid, diacetone acrylamide, alphathiophene aldehyde, furfural, 2-furyl methyl ketone, isophorone and 2-cyclopentenone.
3. The bath of claim 1 wherein said surfactant is selected from the group consisting of polyethoxylated fatty acid monoalkylolamides and polyethoxylated alkyl phenols.
4. An aqueous acidic bath for the electro-deposition of tin and tin/cadmium alloys comprising from 7.5 to 75 grams per liter of a metallic ion selected from the group consisting of stannous ion, cadmium ion and mixtures thereof; about 70 to 400 grams per liter of a free acid selected from the group consisting of fluo-boric acid, sulfuric acid and mixtures thereof; about 3 to 30 grams per liter of a nonionic polyoxyalkylated surfactant; about 0.01 to 0.5 gram per liter of a ring-halogenated aryl aldehyde; about 0.1 to 2.0 grams per liter of a first compound of the formula:
wherein n is zero or 1, R1 is hydrogen or a lower alkyl group; and when n is zero, R2 and R3 are hydrogen or a lower alkyl group, wheren R1 or R2 is a lower alkyl group and R4 is a formyl or alkyl carbonyl group or mixtures thereof; and when n is 1, the combination of R2 and ? represent ethenylene, R3 is an oxygen or sulfur radical and R4 is a formyl or alkyl carbonyl group or mixture thereof; and about 0.1 to about 2.0 grams per liter of a second compound of the formula:
wherein n is zero or 1, R1 is hydrogen or a lower alkyl group; and when n is zero, R2 and R3 are hydrogen or a lower alkyl group, and where R4 is a carboxy or carbox-amido group or mixture thereof; and when n is 1, the combination of R2 and ? represent ethenylene, R3 is an oxygen or sulfur radical, and R4 is a carboxy or carbox-amido group or mixture thereof.
wherein n is zero or 1, R1 is hydrogen or a lower alkyl group; and when n is zero, R2 and R3 are hydrogen or a lower alkyl group, wheren R1 or R2 is a lower alkyl group and R4 is a formyl or alkyl carbonyl group or mixtures thereof; and when n is 1, the combination of R2 and ? represent ethenylene, R3 is an oxygen or sulfur radical and R4 is a formyl or alkyl carbonyl group or mixture thereof; and about 0.1 to about 2.0 grams per liter of a second compound of the formula:
wherein n is zero or 1, R1 is hydrogen or a lower alkyl group; and when n is zero, R2 and R3 are hydrogen or a lower alkyl group, and where R4 is a carboxy or carbox-amido group or mixture thereof; and when n is 1, the combination of R2 and ? represent ethenylene, R3 is an oxygen or sulfur radical, and R4 is a carboxy or carbox-amido group or mixture thereof.
5. The bath of claim 4 wherein said first compound is selected from the group consisting of mesityl oxide, crotonaldehyde, diacetone acrylamide, alpha-thiophene aldehyde, furfural or 2-furyl methyl ketone and said second compound is acrylic acid.
6. The bath of claim 4 wherein said surfactant is selected from the group consisting of polyethoxylated fatty acid monoalkylolamides and polyethoxylated alkyl phenols.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63606875A | 1975-11-28 | 1975-11-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1077430A true CA1077430A (en) | 1980-05-13 |
Family
ID=24550290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA266,279A Expired CA1077430A (en) | 1975-11-28 | 1976-11-22 | Electroplating bath for the electrodeposition of tin and tin/cadmium deposits |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS52110231A (en) |
| AU (1) | AU508244B2 (en) |
| CA (1) | CA1077430A (en) |
| DE (1) | DE2654344C3 (en) |
| FR (1) | FR2333061A1 (en) |
| GB (1) | GB1549679A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0433775Y2 (en) * | 1986-08-04 | 1992-08-12 | ||
| JP6133056B2 (en) * | 2012-12-27 | 2017-05-24 | ローム・アンド・ハース電子材料株式会社 | Tin or tin alloy plating solution |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3785939A (en) * | 1970-10-22 | 1974-01-15 | Conversion Chem Corp | Tin/lead plating bath and method |
-
1976
- 1976-11-22 CA CA266,279A patent/CA1077430A/en not_active Expired
- 1976-11-25 AU AU20006/76A patent/AU508244B2/en not_active Expired
- 1976-11-26 DE DE19762654344 patent/DE2654344C3/en not_active Expired
- 1976-11-26 FR FR7635689A patent/FR2333061A1/en active Granted
- 1976-11-26 GB GB4944076A patent/GB1549679A/en not_active Expired
- 1976-11-29 JP JP14327876A patent/JPS52110231A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52110231A (en) | 1977-09-16 |
| DE2654344A1 (en) | 1977-06-02 |
| AU508244B2 (en) | 1980-03-13 |
| DE2654344B2 (en) | 1978-10-19 |
| FR2333061B1 (en) | 1980-08-01 |
| GB1549679A (en) | 1979-08-08 |
| DE2654344C3 (en) | 1979-06-07 |
| FR2333061A1 (en) | 1977-06-24 |
| AU2000676A (en) | 1978-06-08 |
| JPS5646560B2 (en) | 1981-11-04 |
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| MKEX | Expiry |