U.S. patent number 3,875,029 [Application Number 05/443,406] was granted by the patent office on 1975-04-01 for plating bath for electrodeposition of bright tin and tin-lead alloy.
This patent grant is currently assigned to R. O. Hull & Company, Inc.. Invention is credited to William E. Eckles, William E. Rosenberg.
United States Patent |
3,875,029 |
Rosenberg , et al. |
April 1, 1975 |
Plating bath for electrodeposition of bright tin and tin-lead
alloy
Abstract
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 includes an
emulsified naphthalene monocarboxaldehyde with or without a
substituted olefin, having the general formula: ##SPC1## In which
R.sub.1 is carboxy, carboxamido, alkali carboxylate, ammonium
carboxylate, amine carboxylate, or alkyl carboxylate, and R.sub.2,
R.sub.3, and R.sub.4 are hydrogen, methyl, or lower alkyl.
Inventors: |
Rosenberg; William E.
(Strongsville, OH), Eckles; William E. (Cleveland Heights,
OH) |
Assignee: |
R. O. Hull & Company, Inc.
(Cleveland, OH)
|
Family
ID: |
23760674 |
Appl.
No.: |
05/443,406 |
Filed: |
February 19, 1974 |
Current U.S.
Class: |
205/253; 205/302;
205/304 |
Current CPC
Class: |
C25D
3/32 (20130101); C25D 3/60 (20130101) |
Current International
Class: |
C25D
3/60 (20060101); C25D 3/30 (20060101); C25D
3/32 (20060101); C23b 005/14 (); C23b 005/38 ();
C23b 005/46 () |
Field of
Search: |
;204/43S,54R,53 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; G. L.
Attorney, Agent or Firm: Watts, Hoffmann, Fisher &
Heinke Co.
Claims
What we claim is:
1. An aqueous acid tin electroplating bath containing stannous
ions, at least one acid from the group consisting of sulfuric acid
and flouboric acid, and having dissolved 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 containing about 0.1 to 0.5 gms/liter of a
substituted olefin of the general formula: ##SPC7##
where R.sub.1 is carboxy, carboxamido, alkali carboxylate, ammonium
carboxylate, amine carboxylate, or alkyl carboxylate, and R.sub.2,
R.sub.3, and R.sub.4 are hydrogen, methyl, or lower alkyl.
4. The bath of claim 3 wherein R.sub.1 is carboxy, and R.sub.2,
R.sub.3, and R.sub.4 are hydrogen.
5. The bath of claim 4 wherein the emulsifying agent is an alkyl
phenol condensed with about 10 to 20 moles of ethylene oxide per
mole of alkyl phenol.
6. The bath of claim 3 wherein R.sub.1 is carboxy, R.sub.2 is
methyl, and R.sub.3 and R.sub.4 are hydrogen.
7. The bath of claim 6 wherein the emulsifying agent is an alkyl
phenol condensed with about 10 to 20 moles of ethylene oxide per
mole of alkyl phenol.
8. The bath of claim 3 wherein there is also present a dissolved
lead salt and the acid is flouboric acid.
9. The bath of claim 2 wherein the acid is sulfuric acid.
10. The bath of claim 2 wherein the acid is flouboric acid.
11. The bath of claim 2 wherein the emulsifying agent is selected
from the group consisting of cationic surfactants, nonionic
surfactants, and mixtures thereof.
12. 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.
13. The bath of claim 2 wherein the naphthalene monocarboxaldehyde
is 2-naphthalene monocarboxaldehyde.
14. The bath of claim 2 wherein the naphthalene monocarboxaldehyde
is 1-naphthalene carboxaldehyde.
15. The bath of claim 2 wherein there is also present a dissolved
lead salt and the acid is flouboric acid.
Description
BACKGROUND OF THE INVENTION
The invention pertains to aqueous acid plating baths and additives
for producing semi-bright or bright electrodeposits of tin and
tin-lead alloy.
Prior to this invention recently introduced 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 combinations of certain
aldehydes and ketones, 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
deposits on parts that due to their irregular shapes promote uneven
current distribution.
The one thing common to all of these combinations is that the
ingredients depend on one another to produce bright deposits. 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
coupling solvents as well as emulsifiers in general. Prior
brightener systems require specific surfactants to be used since
their brightening ability is essential in the performance of the
system as a whole.
While it is true that the addition of compounds of the general
formula: ##SPC2##
Are required also for extreme luster, semi-bright to bright,
uniform deposits can be obtained without them. Also with the use of
this invention a very broad, bright current density range is
achieved providing a means for electroplating extremely irregular
shapes without stringent controls on current or racking of parts.
In addition, higher current-densities can be achieved without
obtaining coarse deposits, allowing an electroplater to obtain more
plate thickness in a shorter time.
SUMMARY OF THE INVENTION
This invention is embodied in an aqueous acid electroplating 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 acid and fluoboric acid and a solubilized or dissolved
naphthalene monocarboxaldehyde.
When compounds of the general formula: ##SPC3##
Where R.sub.1 is carboxy, carboxamido, alkali carboxylate, ammonium
carboxylate, amine carboxylate, or alkyl carboxylate, and R.sub.2,
R.sub.3, and R.sub.4, are hydrogen, methyl, or lower alkyl are also
added to the plating bath, they act synergistically with the
naphthalene monocarboxaldehyde to give significantly brighter
deposits than obtained with the dissolved naphthalene
monocarboxaldehyde alone.
This invention is also a brightening agent for the aqueous acid
electroplating baths described above comprised of about 1 to 99
percent naphthalene monocarboxaldehyde, about 0 to 99 percent
emulsifier, 0 to 99 percent of a compound of the general formula:
##SPC4##
where R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are defined as above,
and the remaining percentage being a suitable solvent.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The aqueous acid electroplating baths of the present invention
generally contain stannous ion, sulfate or flouborate ions and
dissolved naphthalene monocarboxaldehyde for proper operation. The
stannous ion is introduced usually as stannous sulfate and the lead
salt, when an alloy is desired, is introduced as lead
flouborate.
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 resinance bond structures for naphthalene are possible, the
symmetrical structure I and the two unsymmetrical, equivalent
structures II and IIa. In formulations of the unsymmetrical
structures, one of the two rings is indicated as quinoid (q)
because the arrangement of double bonds corresponds to that of
o-benzoquinone. ##SPC5##
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 naphthalene's
unique chemical behavior is given in "Advanced Organic Chemistry"
by Fieser and Fieser, page 880. As can be concluded from the above
discussion, monosubstituted binuclear aromatic aldehydes will show
distinctly different chemical properties such as electron donating
ability and reactivity when compared to aldehydes and ketones
derived from benzene, heterocyclic aromatic single ring compounds,
and certainly those of cyclic and straight chained aliphatic
compounds.
The naphthalene monocarboxaldehyde is used at a concentration of
about 0.05 to 0.5 gms/liter and the preferred concentration is 0.2
gms/liter.
Due to its low solubility, coupling agents or emulsifying agents
must be used to dissolve the naphthalene monocarboxaldehyde in the
plating bath. Some of the suitable coupling agents are diethylene
glycol monomethyl ether, diethylene glycol monobutylether, 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 tertiery heterocyclic amines and alkyl
imadazolinium salts, amphoterics such as the alkyl imidazoline
carboxylates, and nonionics such as the aliphatic alcohol ethylene
oxide condensates, sorbitan alkyl ester ethylene oxide condensates,
and alkyl phenol ethylene oxide condensates. The nonionics are
generally condensed with 10 to 20 moles of ethylene oxide per mole
of lipophilic group. Listed in Table I are the commercial names and
manufacturers of these emulsifiers. This invention is not limited
to the use of these emulsifiers only, it being pointed out that
this is merely a list of preferred types.
TABLE I ______________________________________ Trade name Type
Manufacturer ______________________________________ 1. Miranol HM
Amphoteric Miranol Chemical Co. 2. Miranol HS Amphoteric do. 3.
Amine C Cationic Ciba-Geigy 4. Amine S Cationic do. 5. Tween 40
Nonionic ICI America 6. Triton N-101 Nonionic Rohm & Haas Co.
7. Tergitol TMN Nonionic Union Carbide
______________________________________
The coupling agent concentration can be as low as about 3 percent
by volume of the plating bath to as high as 20 percent by volume, 5
percent being the optimum. The emulsifier concentration will depend
on its individual emulsifying ability, but a concentration of from
about 1 to 10 gms. per liter of plating bath is generally
sufficient.
An additional part of this invention is the combined brightening
effect of naphthalene monocarboxaldehyde and compounds of the
general formula: ##SPC6##
where R.sub.1 is carboxy, carboxamido, alkali carboxylate, ammonium
carboxylate, amine carboxylate, or alkyl carboxylate, and R.sub.2,
R.sub.3, R.sub.4 are hydrogen, methyl, or lower alkyl. The olefinic
compound as set forth above may be added to a plating bath using
the naphthalene monocarboxylate to obtain a much brighter deposit
than can be obtained with the naphthalene monocarboxaldehyde alone.
The olefinic compound has no brightening ability when used by
itself, and acts as a brightener only when used in the above
mentioned combination.
Examples of some of the preferred olefinic compounds are listed in
Table II.
TABLE II
Acrylic Acid
Acrylamide
Methacrylamide
Methacrylic acid
Crotonic acid
Ethyl acrylate
The required concentration of the olefinic compound is about 0.1 to
5 gms/liter, the preferred amount being 0.5 gms/liter. The required
amount of the naphthalene monocarboxaldehyde in this synergistic
combination is the same as when it is used alone.
Other known addition agents may be used in combination with the
addition agents of this invention such as other aromatic and
aliphatic aldehydes and ketones, but it has been generally found
that they are not necessary. Antioxidants such as pyrocatechol and
cresol sulfonic acids may be used with this invention as well as
chelating agents to prevent metal sludge build-up on anodes.
The brightening agents of this invention are generally added as
aqueous, or methyl alcohol solutions, but other suitable solvents
can be used as long as they don't cause detrimental results during
electrodeposition. In some cases the addition 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 that the following examples are just
illustrations and are not meant to limit the use of the invention
to these bath formulations only.
EXAMPLE I ______________________________________ Bath Composition
Concentration in gms/liter ______________________________________
Stannous Sulfate 30 Sulfuric Acid 200 1-naphthalene carboxaldehyde
0.2 diethyleneglycol monomethyl ether 40 EXAMPLE II
______________________________________ Bath Composition
Concentration in gms/liter Stannous Sulfate 45 Sulfuric Acid 150
2-naphthalene carboxaldehyde 0.2 Triton N-101 8 EXAMPLE III
______________________________________ Bath Composition
Concentration in gms/liter Stannous Sulfate 20 Sulfuric Acid 200
1-naphthalene carboxaldehyde 0.1 Miranol HM 4 EXAMPLE IV
______________________________________ Bath Composition
Concentration in gms/liter Stannous Sulfate 30 Sulfuric Acid 200
2-naphthalene carboxaldehyde 0.2 Methacrylic acid 0.5 Triton N-101
8 EXAMPLE V ______________________________________ Bath Composition
Concentration in gms/liter Stannous Sulfate 30 Sulfuric Acid 200
1-naphthalene carboxaldehyde 0.2 Acrylic acid 0.4 Triton N-101 10
EXAMPLE VI ______________________________________ Bath Composition
Concentration in gms/liter Lead Flouborate 4.5 Boric Acid 10 Tin
Flouborate 14 Flouboric Acid 90 2-naphthalene carboxaldehyde 0.2
Methacrylic acid 0.5 Tergitol TMN 10
______________________________________
All testing 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 minutes at temperatures ranging from 70.degree. to
85.degree.F. with mechanical agitation of the electrolyte. Table
III indicates the type combinations run, the various basic baths
used, and the results obtained.
TABLE III
__________________________________________________________________________
Basic bath as described Position of aldehyde Olefinic compound
Emulsifier or Results in examples but no addition group on
naphthalene coupling agent agent, emulsifiers, or ring coupling
agent
__________________________________________________________________________
1. Bath of Example I 1 -- Triton N-101 Semi-bright to bright from 1
to 100 amps/ft..sup.2 2. Bath of Example I 1 Methacrylic acid
Miranol HM Very bright from 1 to 80 amps/ft..sup.2 3. Bath of
Example I 2 -- Amine C Semi-bright from 1 to 80 amps/ft..sup.2 4.
Bath of Example I 1 Acrylic Acid Tween 40 Very bright from 5 to 60
amps/ft..sup.2 5. Bath of Example I 2 Methacrylic Acid Tergitol TMN
Very bright from 5 to 80 amps/ft..sup.2 6. Bath of Example VI 1
Methacrylamide Triton N-101 Very bright deposit from 10 to 80
amps/ft..sup.2 of an alloy composed of about 60% tin and 40% lead
7. Bath of Example I -- Acrylic Acid -- Very dull at all current
densities 8. Bath of Example VI -- Methacrylic acid -- Very dull at
all current densities 9. Bath of Example I 1 -- diethyleneglycol
Bright from 1 to 100 monomethyl amps/ft..sup.2 ether 10. Bath of
Example II 1 Crotonic acid Tergitol TMN Bright from 10 to 100
amps/ft..sup.2
__________________________________________________________________________
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 invention, we state that the
subject matter which we regard as being our invention is
particularly pointed out and distinctly claimed in what is claimed,
it being understood that equivalents or modifications of, or
substituitions for, parts of the above specifically described
imbodiment of the invention may be made without departing from the
scope of the invention as set forth in what is claimed.
* * * * *