CA1046976A - Naphthalene monocarboxaldehyde bath for electrolytically plating tin - Google Patents
Naphthalene monocarboxaldehyde bath for electrolytically plating tinInfo
- Publication number
- CA1046976A CA1046976A CA217,157A CA217157A CA1046976A CA 1046976 A CA1046976 A CA 1046976A CA 217157 A CA217157 A CA 217157A CA 1046976 A CA1046976 A CA 1046976A
- Authority
- CA
- Canada
- Prior art keywords
- bath
- acid
- naphthalene
- carboxylate
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention disclosed herein relates to the electrolytic deposition of bright tin and tin-lead alloy.
This invention is embodied in a new plating bath and a plating bath additive. The new plating bath includes tin or tin and lead ions, sulfuric acid or fluoboric acid, and the new additive.
The new additive is an emulsified or dissolved naphthalene monocarboxaldehyde with or without a substituted olefin, having the general formula:
The invention disclosed herein relates to the electrolytic deposition of bright tin and tin-lead alloy.
This invention is embodied in a new plating bath and a plating bath additive. The new plating bath includes tin or tin and lead ions, sulfuric acid or fluoboric acid, and the new additive.
The new additive is an emulsified or dissolved naphthalene monocarboxaldehyde with or without a substituted olefin, having the general formula:
Description
The invention pertains to aqueous acid platiny baths and additives for producing semi-bright electrodeyosits of tin and tin-lead alloy.
Prior to this invention recently introd-~ced commercially usable acid tin baths have been composed of multi-component brightening agents to produce acceptably bright electrodeposits.
The essential ingredients of these baths are various combina-tions of certain aldehydes and ketones r imidazoline surfactants, nonionic surfactants, and amines. While these baths produce significantly bright deposits, many of them lack sufficient broad bright current density ranges. This means careful control of current and time consuming racking procedures are required to avoid dull or coarse deposi~s on parts that due to their irreg-ular shapes promote uneven current distribution.
The one thing common to all of these combinations is that the ingredients depend on one another to ~roduce bright de-posits. Being essential ingredients the lack or absence of any one of them nullifies the effect of the others.
What makes our invention unique is that the naphthalene monocarboxaldehyde produces a brightness without dependence on distinct types of emulsifiers and amines. The only essential requirement is that the naphthalene monocarboxaldehyde be made soluble in the plating bath. This can be achieved by use of ~ --~oupling solvents as well as emulsifiers in general. Prior brightener systems require specific surfactants to he used since their brightening ability is essential in the performance of the .~ ~ystem as a whole.
While it is true that the addition of compounds of the general fo~nula:
R3 R2 `
!
R4 - C - C R~
are required fo~ extreme luster, semi~bright to bright, uniform deposits c~n be obtained without th~n. ~lso with the
Prior to this invention recently introd-~ced commercially usable acid tin baths have been composed of multi-component brightening agents to produce acceptably bright electrodeposits.
The essential ingredients of these baths are various combina-tions of certain aldehydes and ketones r imidazoline surfactants, nonionic surfactants, and amines. While these baths produce significantly bright deposits, many of them lack sufficient broad bright current density ranges. This means careful control of current and time consuming racking procedures are required to avoid dull or coarse deposi~s on parts that due to their irreg-ular shapes promote uneven current distribution.
The one thing common to all of these combinations is that the ingredients depend on one another to ~roduce bright de-posits. Being essential ingredients the lack or absence of any one of them nullifies the effect of the others.
What makes our invention unique is that the naphthalene monocarboxaldehyde produces a brightness without dependence on distinct types of emulsifiers and amines. The only essential requirement is that the naphthalene monocarboxaldehyde be made soluble in the plating bath. This can be achieved by use of ~ --~oupling solvents as well as emulsifiers in general. Prior brightener systems require specific surfactants to he used since their brightening ability is essential in the performance of the .~ ~ystem as a whole.
While it is true that the addition of compounds of the general fo~nula:
R3 R2 `
!
R4 - C - C R~
are required fo~ extreme luster, semi~bright to bright, uniform deposits c~n be obtained without th~n. ~lso with the
2~
u~e of this invention a ver~ brocld, brigh~ curren~ clensity ran~e is achieved ~xoviding a means for elec~roplcltinc3 e~.tremcly i~re-gular shapes without strlngent cGntrols on current or rackiny of parts. In addition, higher current-densities can be achieved S without obtaining coarse deposits, allowincJ an electropldter to obtain more plate thickness in a shorter time.
- This invention is embodied in an aqueous acid electro-plating bath containing a dissolved tin salt, together with a lead salt, if an alloy is desired, an acid selected from the group consisting of sulfuric ~cid and 1uoborlc acid and a sol-; ubilized or dissolved naphthalene monocarbo~aldehyde.
~hen compounds of the general formula: -~3 R2 lS where Rl is carboxyl,carboxamido, alkali carboxylate, ammonium carboxylate, amine carboxylate, or alkyl carboxylate, and R2, R3: and R4, are hydrogen - or lower alXyl are also added to the plating bath, they act synergistically with the naphtha-lene monocarboxaldehyde to give significantly brighter deposits than obtained ~ith the dissolved naphthalene ~onocarboxaldeh~de alone.
This invention is also directed to a brighter~ng aa,ent for theaqueous acid electroplatingbat~s described above which is ~prised of about 1 to 9~% naphthalene-monocarboxaldehyde, about 0 to 99%
emulsifier, 0 to 99% of a compound of the general formula:
~3 ~2 ~4 - ~ = C - Rl -where Rl, R2, R3, and R4 are defined as above, and the remaining percentage being a suitable solvent.
The aqueous acid electroplating baths of the present invention generally contain stannous ion, sulfate or fl~o~orate ions and dissolved naphthalene monocarbo~aldehyde for proper
u~e of this invention a ver~ brocld, brigh~ curren~ clensity ran~e is achieved ~xoviding a means for elec~roplcltinc3 e~.tremcly i~re-gular shapes without strlngent cGntrols on current or rackiny of parts. In addition, higher current-densities can be achieved S without obtaining coarse deposits, allowincJ an electropldter to obtain more plate thickness in a shorter time.
- This invention is embodied in an aqueous acid electro-plating bath containing a dissolved tin salt, together with a lead salt, if an alloy is desired, an acid selected from the group consisting of sulfuric ~cid and 1uoborlc acid and a sol-; ubilized or dissolved naphthalene monocarbo~aldehyde.
~hen compounds of the general formula: -~3 R2 lS where Rl is carboxyl,carboxamido, alkali carboxylate, ammonium carboxylate, amine carboxylate, or alkyl carboxylate, and R2, R3: and R4, are hydrogen - or lower alXyl are also added to the plating bath, they act synergistically with the naphtha-lene monocarboxaldehyde to give significantly brighter deposits than obtained ~ith the dissolved naphthalene ~onocarboxaldeh~de alone.
This invention is also directed to a brighter~ng aa,ent for theaqueous acid electroplatingbat~s described above which is ~prised of about 1 to 9~% naphthalene-monocarboxaldehyde, about 0 to 99%
emulsifier, 0 to 99% of a compound of the general formula:
~3 ~2 ~4 - ~ = C - Rl -where Rl, R2, R3, and R4 are defined as above, and the remaining percentage being a suitable solvent.
The aqueous acid electroplating baths of the present invention generally contain stannous ion, sulfate or fl~o~orate ions and dissolved naphthalene monocarbo~aldehyde for proper
3.
69~6 ~.p~ration. The s-tannous ion is introduced usually as stannous sulfate and the lead salt, when an alloy is desir~d, is intro-dùced as lead fluoborate.
The naphthalene monocarboxaldehydes are readily available in commerce and their uniqueness as brightening agents compared to other aldehydes and ketones can be partially explained by a close study of their chemical structure.
Three resonance bond structures for naphthalene are possible, the symmetrical structure I and the two unsymmetrical, equivalent structures II and IIa. In formulations of the un-symme~rical structures, one of the two rings is indicated as quinoid (q) because the arrangement of double bonds corresponds to that of o-benzoquinone.
I II IIa " Various chemical reactions of naphthalene show that the bond structure of the naphthalene nucleus is not so mobile as that `~ of benzene and that there is a relative fixation of bonds in at least part of the molecule at which substitution occurs. This is generally described as an enhanced 1,2-double bond character.
A much more detailed explanation of monosubstituted naph- ;
thalene's unique chemical behavior is given in "Advanced Organic Chemistry" by Fieser and Fieser, paqe 880. As can be con-c`luded from the above discussion, monosubstituted binuclear axomatic aldehydes will show distinctly different chemical pro-perties such as electron donating ability and reactivity when compared to aldehydes and Xetones derived from benzene, hetero-: cyclic aromatic single ring compounds. and certainly those of cyclic and straight chained aliphatic compounds.
The naphthalene monocarboxaldeh-~de is used at a concentration of about 0.05 to 0O5 gms/liter and the preferred concentration is :~ ;
_ ~ _ ~ jrc~
- : ~ .. .
. . . . . .
002 gms/liter.
Coupling agents or emulsifying agents must be used in the plating bath to dissolve the naphthal~ne monocarboxaldehyde due to its low solubility. Some of the suitable coupling agents are diethylene glycol monomethyl ether, diethylene glycol monobutyl-ether, ethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.
The emulsifying agents that have been found to work best are cationics such as the alkyl tertiary heterocyclic amines and alkyl imidazolinium salts, amphoterics such as the alkyl imida-zoline carboxylates, and nonionics such as the aliphatic alcohol ethylene oxide condensates, sorbitan alkyl ester ethylene oxide condensates and alkyl phenol ethylene o~ide condensates. The nonionics are generally condensed with 10 to 20 moles of ethylene oxide per mole of lipophilic group. Listed in Table 1 are the commercial names and manufacturers of these emulsifiers. This inven~ion is not limited to the use of these emulsi~iers only, ; it being pointed out that this is merely a list of preferred types.
Trade Name Type Manufacturer -- ,:
1. Miranol ~ HM (dicarboxylic Amphoteric Miranol Chemical Co.
lauric acid sodium salt) 2. Miranol ~ HS (sodium salt Amphoteric Miranol Chemical Co.
of lauric acid) 3. Amine C (brand name for a Cationic Ciba-Geigy heterocyclic tertiary amine ,,~
alkylated with lauric acid)
69~6 ~.p~ration. The s-tannous ion is introduced usually as stannous sulfate and the lead salt, when an alloy is desir~d, is intro-dùced as lead fluoborate.
The naphthalene monocarboxaldehydes are readily available in commerce and their uniqueness as brightening agents compared to other aldehydes and ketones can be partially explained by a close study of their chemical structure.
Three resonance bond structures for naphthalene are possible, the symmetrical structure I and the two unsymmetrical, equivalent structures II and IIa. In formulations of the un-symme~rical structures, one of the two rings is indicated as quinoid (q) because the arrangement of double bonds corresponds to that of o-benzoquinone.
I II IIa " Various chemical reactions of naphthalene show that the bond structure of the naphthalene nucleus is not so mobile as that `~ of benzene and that there is a relative fixation of bonds in at least part of the molecule at which substitution occurs. This is generally described as an enhanced 1,2-double bond character.
A much more detailed explanation of monosubstituted naph- ;
thalene's unique chemical behavior is given in "Advanced Organic Chemistry" by Fieser and Fieser, paqe 880. As can be con-c`luded from the above discussion, monosubstituted binuclear axomatic aldehydes will show distinctly different chemical pro-perties such as electron donating ability and reactivity when compared to aldehydes and Xetones derived from benzene, hetero-: cyclic aromatic single ring compounds. and certainly those of cyclic and straight chained aliphatic compounds.
The naphthalene monocarboxaldeh-~de is used at a concentration of about 0.05 to 0O5 gms/liter and the preferred concentration is :~ ;
_ ~ _ ~ jrc~
- : ~ .. .
. . . . . .
002 gms/liter.
Coupling agents or emulsifying agents must be used in the plating bath to dissolve the naphthal~ne monocarboxaldehyde due to its low solubility. Some of the suitable coupling agents are diethylene glycol monomethyl ether, diethylene glycol monobutyl-ether, ethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.
The emulsifying agents that have been found to work best are cationics such as the alkyl tertiary heterocyclic amines and alkyl imidazolinium salts, amphoterics such as the alkyl imida-zoline carboxylates, and nonionics such as the aliphatic alcohol ethylene oxide condensates, sorbitan alkyl ester ethylene oxide condensates and alkyl phenol ethylene o~ide condensates. The nonionics are generally condensed with 10 to 20 moles of ethylene oxide per mole of lipophilic group. Listed in Table 1 are the commercial names and manufacturers of these emulsifiers. This inven~ion is not limited to the use of these emulsi~iers only, ; it being pointed out that this is merely a list of preferred types.
Trade Name Type Manufacturer -- ,:
1. Miranol ~ HM (dicarboxylic Amphoteric Miranol Chemical Co.
lauric acid sodium salt) 2. Miranol ~ HS (sodium salt Amphoteric Miranol Chemical Co.
of lauric acid) 3. Amine C (brand name for a Cationic Ciba-Geigy heterocyclic tertiary amine ,,~
alkylated with lauric acid)
4. Amine S (brand name for a Cationic Ciba-Geigy heterocyclic tertiary amine alkylated with stearic acid)
5. Tween ~ 40 tPolyoxyethyi- Nonionic ICI America ene sorbitan monopalmitate) ~i 6. Triton ~ N-101 ~nonylphen- Nonionic Rohm & Haas Co.
oxy polyethoxy ethanol) 7. Tergitol ~ TMN ~trimethyl Nonionic Union Carbide ;~
nonyl polyethylene glycol ether) The coupling agent concentration can be as low as about ' ~:
'; :
:,, ,k",:,' ~ 5 ~
~ by volum~ of ~hc plating bath to as hiyll a5 20~ by volurn~,S~
being the optimum. The emulsificr conccntr~tion will depend on its individual emulsifying ability, but a CGnCentra-tiOn of ~rorn about 1 to 10 gms. per litcr of plating batl~ cJenerally suf ficient.
An additional part of this invention is the combined brightening effect of naphthalene monocarbo~.ald~hyde and com-pounds of the general formula:
1'3 ~2 R4 - C = C R1 where Rl is carbo~yl,carboxamido, alXali carbo~ylate, ammonium carboxylate, amine carboxylate, or alkyl carboxylate, and R2, . R3, R4 are hydrogen or lower alkyl. The olefinic com-; pound as set forth above may be added to a plating bath using the naphthalene monocarboxylate to obtain a much brighter de- ~.
posit than can be obtained with the naphthalene monocarboxalde hyde alone. The olefinic compound has no b~ightening abili'y ;
when used by itself, and acts as a brightener only when used in , i the above mentioned comhination.
. 20 Examples of some`of the preferred ol~finic compounds are listed in Table II.
TABLE II
Acrylic Acid Acrylamide 25. Methacrylamide ./ Methacrylic acid .~.
' .
Crotonic acid Ethyl acrylate .
The required concentration of the olefinic compound is about 0.1 30 to 5 yms/liter, the preferxed amount be.ing 0.5 gms/liter. The required amount o~ the naphtllalene monocarbo~aldehyde. in this ~ynergistic combination is the same as when it is uscd alone.
.. 6 .... .
~, - . . .
Other known a(ldition ~gents may be use~ in combination with the additlon a~ents o~ this invention such as other arorllclt-ic and aliphatic al~hydes and ~.etones, ~ut it has be~n ~ener-ally found that the~ are not necessary. Antio~.idants such as pyrocatechol and cresol sulfonic acids may ~e used ~ith this in-vention as well as chelating agents to prevent metal sludge build up on anodes.
The brighteniny agents of this invention are gencrally added as aqueous, or methyl alcohol solutions, but other suit-able solvents can be used as long as they do~'t cause detrimen-tal results during electrodeposition. In some cases the addi-tion agents may be added in their concentrated form, provided the plating bath is thoroughly stirred.
While the brightening agents of this invention are effective in many aqueous, acid tin plating bath formulations, it is preferred to use any of the basic baths described in the following examples. It will be understood tha~ the following examples are just illustrations and are not meant to li~it the use of the invention to these bath formulations only.
~ E ~PLE I -~
Bath Composi~ion Concentration in ~ms/lit~r .
Stannous Sulfate 30 Sulfuric Acid 200 l-naphthalene carboxaldehyde 0.2 diethyleneglycol monomethyl ether 40 EXh~5PLE II
Bath Compositiononcentration in gms~liter . .
Stannous Sulfate 45 Sulf~ric ~cid lS0 2~naph~halene carbo~al~ehyde 0.2 ~riton N-101 8 .
... ....
,:
.
oxy polyethoxy ethanol) 7. Tergitol ~ TMN ~trimethyl Nonionic Union Carbide ;~
nonyl polyethylene glycol ether) The coupling agent concentration can be as low as about ' ~:
'; :
:,, ,k",:,' ~ 5 ~
~ by volum~ of ~hc plating bath to as hiyll a5 20~ by volurn~,S~
being the optimum. The emulsificr conccntr~tion will depend on its individual emulsifying ability, but a CGnCentra-tiOn of ~rorn about 1 to 10 gms. per litcr of plating batl~ cJenerally suf ficient.
An additional part of this invention is the combined brightening effect of naphthalene monocarbo~.ald~hyde and com-pounds of the general formula:
1'3 ~2 R4 - C = C R1 where Rl is carbo~yl,carboxamido, alXali carbo~ylate, ammonium carboxylate, amine carboxylate, or alkyl carboxylate, and R2, . R3, R4 are hydrogen or lower alkyl. The olefinic com-; pound as set forth above may be added to a plating bath using the naphthalene monocarboxylate to obtain a much brighter de- ~.
posit than can be obtained with the naphthalene monocarboxalde hyde alone. The olefinic compound has no b~ightening abili'y ;
when used by itself, and acts as a brightener only when used in , i the above mentioned comhination.
. 20 Examples of some`of the preferred ol~finic compounds are listed in Table II.
TABLE II
Acrylic Acid Acrylamide 25. Methacrylamide ./ Methacrylic acid .~.
' .
Crotonic acid Ethyl acrylate .
The required concentration of the olefinic compound is about 0.1 30 to 5 yms/liter, the preferxed amount be.ing 0.5 gms/liter. The required amount o~ the naphtllalene monocarbo~aldehyde. in this ~ynergistic combination is the same as when it is uscd alone.
.. 6 .... .
~, - . . .
Other known a(ldition ~gents may be use~ in combination with the additlon a~ents o~ this invention such as other arorllclt-ic and aliphatic al~hydes and ~.etones, ~ut it has be~n ~ener-ally found that the~ are not necessary. Antio~.idants such as pyrocatechol and cresol sulfonic acids may ~e used ~ith this in-vention as well as chelating agents to prevent metal sludge build up on anodes.
The brighteniny agents of this invention are gencrally added as aqueous, or methyl alcohol solutions, but other suit-able solvents can be used as long as they do~'t cause detrimen-tal results during electrodeposition. In some cases the addi-tion agents may be added in their concentrated form, provided the plating bath is thoroughly stirred.
While the brightening agents of this invention are effective in many aqueous, acid tin plating bath formulations, it is preferred to use any of the basic baths described in the following examples. It will be understood tha~ the following examples are just illustrations and are not meant to li~it the use of the invention to these bath formulations only.
~ E ~PLE I -~
Bath Composi~ion Concentration in ~ms/lit~r .
Stannous Sulfate 30 Sulfuric Acid 200 l-naphthalene carboxaldehyde 0.2 diethyleneglycol monomethyl ether 40 EXh~5PLE II
Bath Compositiononcentration in gms~liter . .
Stannous Sulfate 45 Sulf~ric ~cid lS0 2~naph~halene carbo~al~ehyde 0.2 ~riton N-101 8 .
... ....
,:
.
6~7~i E;~r~PLE III
-Bath Composition Concent~ation in cJms/lit~r Stannous Sulfate 20 Sulfuric Acid 200 l-naph ~ alene carboxaldehyde 0.1 Miranol HM 4 EXA~PLE IV
Bath CompositionConcentration in gms/liter - ' ,.
Stannous Sulfate 30 Sulfuric Acid 200 ~:
2-naphthalene carboxaldehyde0.2 Methacrylic acid 0.5 Triton N-101 8 EX~MPLE V .
:_th CompositionConcentration in gms/liter Stannous Sulfate 30 . Sulfuric Acid 200 l~naphthalene carboxaldehyde0.2 Acrylic acid 0.4 ~' (~,~ , ..
' 20 Triton N-101 10 EXAMPLE VI
Bath CompositionConcentration in ~ms/liter ;~
Lead FlUoborate 4,5 Boric Acid 10 ~ luRborate . 14 FlUo~boric Acid 90 ~, ~ 2-naphthalene carboxaldehyde0.2 ethacr~lic acid 0.5 ~R) T~3rgitorTMN 10 ~ , - All ~esting was done in a conventional 267 ml. Hull Cell, using steel cathode panels and tin anodes. A current of two -- amperes was used for 5 ~inutes at temperatures ranging from 70 r~
, ~ . . ~ . . I
-Bath Composition Concent~ation in cJms/lit~r Stannous Sulfate 20 Sulfuric Acid 200 l-naph ~ alene carboxaldehyde 0.1 Miranol HM 4 EXA~PLE IV
Bath CompositionConcentration in gms/liter - ' ,.
Stannous Sulfate 30 Sulfuric Acid 200 ~:
2-naphthalene carboxaldehyde0.2 Methacrylic acid 0.5 Triton N-101 8 EX~MPLE V .
:_th CompositionConcentration in gms/liter Stannous Sulfate 30 . Sulfuric Acid 200 l~naphthalene carboxaldehyde0.2 Acrylic acid 0.4 ~' (~,~ , ..
' 20 Triton N-101 10 EXAMPLE VI
Bath CompositionConcentration in ~ms/liter ;~
Lead FlUoborate 4,5 Boric Acid 10 ~ luRborate . 14 FlUo~boric Acid 90 ~, ~ 2-naphthalene carboxaldehyde0.2 ethacr~lic acid 0.5 ~R) T~3rgitorTMN 10 ~ , - All ~esting was done in a conventional 267 ml. Hull Cell, using steel cathode panels and tin anodes. A current of two -- amperes was used for 5 ~inutes at temperatures ranging from 70 r~
, ~ . . ~ . . I
7~
to 85F. with mechanical agitation of the electrolyte. Table III indicates the type combinations run, the various basic baths used, and the results obtained.
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Having thus described this invention in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains to make and use the same, and having set forth the best mode contemplated of carrying out this inven-tion, we state that the subject matter which we regard as beingour invention is particularly pointed out and distinctly claimed in what is claimed, it being understood that equivalents or mod-ifications of, or substitutions for, parts of the above specif- .
ically described imbodiment of the invention may be made without departing from the scope of the invention as set forth in what is claimed.
' ~, ' ,.
~ .
~ 12.
: . ~ : :, .. . ..
to 85F. with mechanical agitation of the electrolyte. Table III indicates the type combinations run, the various basic baths used, and the results obtained.
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Having thus described this invention in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains to make and use the same, and having set forth the best mode contemplated of carrying out this inven-tion, we state that the subject matter which we regard as beingour invention is particularly pointed out and distinctly claimed in what is claimed, it being understood that equivalents or mod-ifications of, or substitutions for, parts of the above specif- .
ically described imbodiment of the invention may be made without departing from the scope of the invention as set forth in what is claimed.
' ~, ' ,.
~ .
~ 12.
: . ~ : :, .. . ..
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous acid tin electroplating bath containing sta nous ions, at least one acid from the group consisting of sulfuric acid and fluoboric acid, and having dissolved or emulsified therein as a brightening agent about 0.05 to 0.5 gms/liter of a naphthalene monocarboxaldehyde.
2. The bath of claim 1 wherein about 1 to 10 gms/liter of an emulsifying agent is added to solubilize the naphthalene monocarboxaldehyde.
3. The bath of claim 2 wherein the acid is sulfuric acid.
4. The bath of claim 2 wherein the acid is fluoboric acid.
5. The bath of claim 2 wherein the emulsifying agent is selected from the group consisting of cationic surfactants, nonionic surfactants, and mixtures thereof.
6. The bath of claim 2 wherein the emulsifying agent is an alkyl phenol condensed with about 10 to 20 moles of ethylene oxide per mole of alkyl phenol.
7. The bath of claim 2 wherein the naphthalene mono-carboxaldehyde is 2-naphthalene monocarboxaldehyde.
8. The bath of claim 2 wherein the naphthalene mono-carboxaldehyde is 1-naphthalene carboxaldehyde.
9. The bath of claim 2 containing about 0.1 to 0.5 gms/
liter of a substituted olefin of the general formula:
where R1 is carboxyl, carboxamido, alkali carboxylate, ammonium carboxylate, amine carboxylate, or alkyl carboxylate, and R2, R3, and R4 are hydrogen or lower alkyl.
liter of a substituted olefin of the general formula:
where R1 is carboxyl, carboxamido, alkali carboxylate, ammonium carboxylate, amine carboxylate, or alkyl carboxylate, and R2, R3, and R4 are hydrogen or lower alkyl.
10. The bath of claim 9 wherein R1 is carboxyl, and R2, R3, and R4 are hydrogen.
11. The bath of claim 9 wherein R1 is carboxyl,R2 is methyl, and R3 and R4 are hydrogen.
12. The bath of claim 10 wherein the emulsifying agent is an alkyl phenol condensed with about 10 to 20 moles of ethylene oxide per mole of alkyl phenol.
13. The bath of claim 11 wherein the emulsifying agent is an alkyl phenol condensed with about 10 to 20 moles of ethylene oxide per mole of alkyl phenol.
14. The bath of claim 2 wherein there is also present a dissolved lead salt and the acid is fluoboric acid.
15. The bath of claim 9 wherein there is also present a dissolved lead salt and the acid is fluoboric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA282,821A CA1046977A (en) | 1974-02-19 | 1977-07-15 | Naphthalene monocarboxaldehyde brightening agents for electrolytically plating tin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US443406A US3875029A (en) | 1974-02-19 | 1974-02-19 | Plating bath for electrodeposition of bright tin and tin-lead alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1046976A true CA1046976A (en) | 1979-01-23 |
Family
ID=23760674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA217,157A Expired CA1046976A (en) | 1974-02-19 | 1974-12-31 | Naphthalene monocarboxaldehyde bath for electrolytically plating tin |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3875029A (en) |
| JP (1) | JPS581195B2 (en) |
| BR (1) | BR7500985A (en) |
| CA (1) | CA1046976A (en) |
| ES (1) | ES434856A1 (en) |
| FR (1) | FR2261351B1 (en) |
| SE (1) | SE419104B (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3977949A (en) * | 1975-07-07 | 1976-08-31 | Columbia Chemical Corporation | Acidic plating bath and additives for electrodeposition of bright tin |
| US4207148A (en) * | 1975-11-28 | 1980-06-10 | Minnesota Mining And Manufacturing Company | Electroplating bath for the electrodeposition of tin and tin/cadmium deposits |
| US4135991A (en) * | 1977-08-12 | 1979-01-23 | R. O. Hull & Company, Inc. | Bath and method for electroplating tin and/or lead |
| US4376018A (en) * | 1979-12-31 | 1983-03-08 | Bell Telephone Laboratories, Incorporated | Electrodeposition of nickel |
| US4379738A (en) * | 1979-12-31 | 1983-04-12 | Bell Telephone Laboratories, Incorporated | Electroplating zinc |
| US4263106A (en) * | 1979-12-31 | 1981-04-21 | Bell Telephone Laboratories, Incorporated | Solder plating process |
| US4377449A (en) * | 1979-12-31 | 1983-03-22 | Bell Telephone Laboratories, Incorporated | Electrolytic silver plating |
| US4377448A (en) * | 1979-12-31 | 1983-03-22 | Bell Telephone Laboratories, Incorporated | Electrolytic gold plating |
| SE8204505L (en) * | 1981-09-08 | 1983-03-09 | Occidental Chem Co | ELECTROPLETING FOR PROVISION OF TIN LEAD ALLOYS ON DIFFERENT SUBSTRACTS |
| US5066367B1 (en) * | 1981-09-11 | 1993-12-21 | I. Nobel Fred | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
| US5094726B1 (en) * | 1981-09-11 | 1993-12-21 | I. Nobel Fred | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
| US4871429A (en) * | 1981-09-11 | 1989-10-03 | Learonal, Inc | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
| AU1517383A (en) * | 1982-03-15 | 1983-10-24 | Gsp Metals & Chemicals Corp. | Chelating metals |
| US4586990A (en) * | 1982-03-15 | 1986-05-06 | Gsp Metals & Chemicals Corporation | Chelating metals |
| US4530741A (en) * | 1984-07-12 | 1985-07-23 | Columbia Chemical Corporation | Aqueous acid plating bath and brightener composition for producing bright electrodeposits of tin |
| US4582576A (en) * | 1985-03-26 | 1986-04-15 | Mcgean-Rohco, Inc. | Plating bath and method for electroplating tin and/or lead |
| US4816070A (en) * | 1985-08-29 | 1989-03-28 | Techo Instruments Investments Ltd. | Use of immersion tin and alloys as a bonding medium for multilayer circuits |
| US4715894A (en) * | 1985-08-29 | 1987-12-29 | Techno Instruments Investments 1983 Ltd. | Use of immersion tin and tin alloys as a bonding medium for multilayer circuits |
| DE3856429T2 (en) * | 1987-12-10 | 2001-03-08 | Learonal Inc | Tin, lead or tin-lead alloy electrolytes for high speed electroplating |
| US5174887A (en) * | 1987-12-10 | 1992-12-29 | Learonal, Inc. | High speed electroplating of tinplate |
| EP0499638B1 (en) * | 1989-04-20 | 1998-12-02 | Tokin Corporation | Method for Plating a Permanent Magnet of a R2T14B Intermetallic Compound |
| US4885064A (en) * | 1989-05-22 | 1989-12-05 | Mcgean-Rohco, Inc. | Additive composition, plating bath and method for electroplating tin and/or lead |
| US5698087A (en) * | 1992-03-11 | 1997-12-16 | Mcgean-Rohco, Inc. | Plating bath and method for electroplating tin and/or lead |
| US5545440A (en) * | 1994-12-05 | 1996-08-13 | At&T Global Information Solutions Company (Aka Ncr Corporation) | Method and apparatus for polymer coating of substrates |
| US5597469A (en) * | 1995-02-13 | 1997-01-28 | International Business Machines Corporation | Process for selective application of solder to circuit packages |
| US5814202A (en) * | 1997-10-14 | 1998-09-29 | Usx Corporation | Electrolytic tin plating process with reduced sludge production |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL124247C (en) * | 1963-08-28 | |||
| NL128321C (en) * | 1965-02-13 | |||
| US3785939A (en) * | 1970-10-22 | 1974-01-15 | Conversion Chem Corp | Tin/lead plating bath and method |
-
1974
- 1974-02-19 US US443406A patent/US3875029A/en not_active Expired - Lifetime
- 1974-12-31 CA CA217,157A patent/CA1046976A/en not_active Expired
-
1975
- 1975-01-22 FR FR7501951A patent/FR2261351B1/fr not_active Expired
- 1975-02-17 SE SE7501711A patent/SE419104B/en not_active IP Right Cessation
- 1975-02-18 BR BR985/75A patent/BR7500985A/en unknown
- 1975-02-19 JP JP50019994A patent/JPS581195B2/en not_active Expired
- 1975-02-19 ES ES434856A patent/ES434856A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| SE419104B (en) | 1981-07-13 |
| DE2506158A1 (en) | 1975-08-21 |
| JPS581195B2 (en) | 1983-01-10 |
| ES434856A1 (en) | 1976-12-01 |
| JPS50118934A (en) | 1975-09-18 |
| US3875029A (en) | 1975-04-01 |
| FR2261351A1 (en) | 1975-09-12 |
| FR2261351B1 (en) | 1979-09-28 |
| SE7501711L (en) | 1975-08-20 |
| DE2506158B2 (en) | 1976-12-02 |
| BR7500985A (en) | 1976-11-16 |
| AU7620874A (en) | 1976-06-10 |
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