U.S. patent number 3,769,182 [Application Number 05/160,109] was granted by the patent office on 1973-10-30 for bath and method for electrodepositing tin and/or lead.
This patent grant is currently assigned to Conversion Chemical Corporation. Invention is credited to Merton M. Beckwith, Grace F. Hsu.
United States Patent |
3,769,182 |
Beckwith , et al. |
October 30, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
BATH AND METHOD FOR ELECTRODEPOSITING TIN AND/OR LEAD
Abstract
A plating bath for electrodepositing tin and/or lead contains
stannous ion, lead ion, or a mixture thereof, together with a
fluoborate, fluosilicate and/or sulfamate electrolyte and a
polyoxyalkylated fatty acid alkylolamide surfactant. The bath
operates at pH values of less than about 3.0, and very desirable
deposits are produced over wide ranges of current densities and
under a variety of plating conditions.
Inventors: |
Beckwith; Merton M. (Rockville,
CT), Hsu; Grace F. (Vernon, CT) |
Assignee: |
Conversion Chemical Corporation
(Rockville, CT)
|
Family
ID: |
26769076 |
Appl.
No.: |
05/160,109 |
Filed: |
July 6, 1971 |
Current U.S.
Class: |
205/253; 205/299;
205/303; 205/301; 205/304 |
Current CPC
Class: |
C25D
3/56 (20130101); C25D 3/36 (20130101); C25D
3/60 (20130101); C25D 3/32 (20130101) |
Current International
Class: |
C25D
3/60 (20060101); C25D 3/30 (20060101); C25D
3/36 (20060101); C25D 3/56 (20060101); C25D
3/32 (20060101); C25D 3/02 (20060101); C23b
005/14 (); C23b 005/16 (); C23b 005/38 () |
Field of
Search: |
;204/43,53,54R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1,151,460 |
|
May 1969 |
|
GB |
|
652,405 |
|
Dec 1964 |
|
BE |
|
Primary Examiner: Kaplan; G. L.
Claims
Having thus described the invention, I claim:
1. An aqueous acid plating bath for the electrodeposition of tin,
lead and alloys thereof comprising about 15.0 to 350.0 grams per
liter of a metal ion selected from the group consisting of stannous
ion, lead ion, and mixtures thereof; about 100.0 to 500.0 grams per
liter of a radical selected from the group consisting of
fluoborate, fluosilicate sulfamate, and mixtures thereof; and about
10.0 - 25.0 grams per liter of an alkoxylated fatty acid
alkylolamide surfactant, said bath having a pH less than about
3.0., said alkylolamide surfactant having the formula ##SPC2##
wherein R.sub.1 is a fatty acid alkyl group containing eight to 22
carbon atoms, R.sub.2 is selected from the group ethylene,
propylene and mixtures thereof, m is an integer from 0 to 15, n is
an integer from 1 to 30, and the sum of m plus n is an integer from
2 to 30.
2. The bath of claim 1 additionally containing about 0.1 to 10.0
grams per liter of a ring halogenated aromatic aldehyde.
3. The bath of claim 1 additionally containing about 2.0 to 15.0
grams per liter of an aromatic amine.
4. The bath of claim 3 wherein said aromatic amine is selected from
the group consisting of toluidines and aniline.
5. The bath of claim 3 additionally containing about 0.1 to 10.0
grams per liter of a carbonyl containing compound selected from the
group consisting of benzylidene acetone, 3-hydroxybutanal,
thiophene aldehyde, benzaldehyde, dimethoxybenzaldehyde,
tolualdehyde, cinnamaldehyde, and anisaldehyde.
6. The bath of claim 1 additionally containing about 2.0 to 25.0
grams per liter of a lower aliphatic aldehyde containing 1 to 4
carbon atoms.
7. The bath of claim 1 additionally containing about 0.5 to 3.0
grams per liter of a trichlorinated benzene derivative.
8. The bath of claim 1 wherein said radical of said group is
fluoborate, and wherein said pH is about 0.1 to 1.5.
9. The bath of claim 1 wherein said metal ion is lead ion in an
amount of at least about 75.0 grams per liter, said bath being
substantially free of tin ions.
10. The bath of claim 9 wherein the amount of said lead ion is at
least 150.0 grams per liter, wherein said pH is about 0.1 to 1.5,
and wherein said bath additionally contains about 0.5 to 5.0 grams
per liter of a polyethoxylated alkylphenol secondary
surfactant.
11. The bath of claim 1 wherein said metal ion is stannous ion in
an amount of at least about 75.0 grams per liter, said bath being
substantially free of lead ion.
12. The bath of claim 11 wherein the amount of said stannous ion is
about 100.0 to 150.0 grams per liter, and wherein the pH of said
bath is about 0.1 to 1.5.
13. The bath of claim 12 additionally including about 0.5 to 3.0
grams per liter of a trichlorinated benzene derivative.
14. The bath of claim 1 wherein said metal ion is a mixture of
stannous and lead ions, wherein the amount of said stannous ion is
about 10.0 to 180.0 grams per liter and wherein the amount of said
lead ion is about 90.0 to 6.0 grams per liter.
15. The bath of claim 14 wherein said radical is fluoborate in an
amount of at least about 150.0 grams per liter, wherein said bath
contains at least about 50.0 grams per liter of free fluoboric acid
and from at least about 10.0 grams per liter of free boric acid to
saturation therewith, and wherein said pH is about 0.1 to 1.5.
16. The bath of claim 15 additionally including an aromatic
aldehyde selected from the group consisting of
2,4-dichlorobenzaldehyde and 2,6-dichlorobenzaldehyde present in an
amount of about 0.3 to 2.0 grams per liter.
17. The bath of claim 15 additionally including about 0.5 to 3.0
grams per liter of a trichlorinated benzene derivative.
18. The bath of claim 15 additionally including about 0.3 to 2.0
grams per liter of an aromatic aldehyde selected from the group
consisting of 2,4-dichlorobenzaldehyde and
2,6-dichlorobenzaldehyde, and about 0.5 to 3.0 grams per liter of
1,2,4-trichlorobenzene.
19. The bath of claim 15 additionally including about 2.0 to 15.0
grams per liter of an aromatic amine selected from the group
consisting of toluidines and aniline.
20. The bath of claim 19 additionally including about 0.1 to 10.0
grams per liter of a carbonyl-containing compound selected from the
group consisting of benzylidene acetone, acetaldol, thiophene
aldehyde, benzaldehyde, 2,5-dimethoxybenzaldehyde, tolualdehyde,
cinnamaldehyde, and anisaldehyde.
21. The bath of claim 18 additionally including about 2.0 to 25.0
grams per liter of formaldehyde.
22. The bath of claim 14 wherein the amount of said stannous ion is
about 45.0 to 65.0 grams per liter and the amount of said lead ion
is about 30.0 to 20.0 grams per liter.
23. The bath of claim 1 wherein said metal ion is a mixture of
stannous and lead ion, wherein the amount of said stannous ion is
about 10.0 to 30.0 grams per liter and wherein the amount of said
lead ion is about 200.0 to 100.0 grams per liter.
24. The bath of claim 23 wherein the amount of stannous ion is
about 15.0 to 20.0 grams per liter and wherein the amount of said
lead ion is about 175.0 to 150.0 grams per liter, said bath
additionally containing about 0.5 to 5.0 grams per liter of a
polyethoxylated alkyl phenol secondary surfactant and having a pH
of about 0.1 to 1.5.
25. In a method of electroplating tin, lead or mixtures thereof,
the steps comprising:
a. preparing an aqueous acid plating bath comprising about 15.0 to
350.0 grams per liter of a metal ion selected from the group
consisting of stannous ion, lead ion, and mixtures thereof, at
least about 100.0 grams per liter of a radical selected from the
class consisting of fluoborate, fluosilicate, sulfamate, and
mixtures thereof, and about 10.0 - 25.0 grams per liter of an
alkoxylated fatty acid alkylolamide surfactant, said bath having a
pH less than about 3.0, said alkylolamide surfactant having the
formula ##SPC3##
wherein R.sub.1 is a fatty acid alkyl group containing eight to 22
carbon atoms, R.sub.2 is selected from the group ethylene,
propylene and mixtures thereof, m is an integer from 0 to 15, n is
an integer from 1 to 30, and the sum of m plus n is an integer from
2 to 30;
b. maintaining said bath at a temperature of about 50.degree. to
150.degree. Fahrenheit;
c. immersing in said bath a workpiece having a metallic surface and
at least one anode of a metal selected from the class consisting of
tin, lead, and alloys thereof; and
d. applying a voltage across said anode and said workpiece to
deposit said metal on said metallic surface, said voltage providing
a current density of about 2.0 to 2,000.0 amperes per square foot
at the surface of said workpiece.
26. The method of claim 25 wherein said bath contains at least
150.0 grams per liter of lead ion and is substantially free of tin
ions, wherein said metal of said class is lead, and wherein said
current density is less than about 100.0 amperes per square
foot.
27. The method of claim 26 wherein said bath additionally contains
about 0.5 to 5.0 grams per liter of a polyethoxylated alkyl phenol
secondary surfactant, wherein said radical of said class is
fluoborate, and wherein said pH is about 0.1 to 1.5.
28. The method of claim 25 wherein said bath contains about 100.0
to 150.0 grams per liter of stannous ion and is substantially free
of lead ion, wherein said metal of said class is tin, wherein said
current density is greater than about 400.0 amperes per square
foot, and wherein said workpiece and bath are moved relative to one
another at a rate of at least about 150 lineal feet per minute.
29. The method of claim 28 wherein said bath additionally contains
about 0.3 to 2.0 grams per liter of an aromatic aldehyde selected
from the group consisting of 2,4-dichlorobenzaldehyde and
2,6-dichlorobenzaldehyde and about 0.5 to 3.0 grams per liter of
1,2,4-trichlorobenzene, wherein said radical of said class is
fluoborate, and wherein said pH is about 0.1 to 1.5.
30. The method of claim 25 wherein said bath contains about 45.0 to
65.0 grams per liter of stannous ion and about 30.0 to 20.0 grams
per liter of lead ion, wherein said metal of said class is a
tin/lead alloy, wherein said pH is about 0.1 to 1.5, and wherein
said current density is less than 100.0 amperes per square
foot.
31. The method of claim 30 wherein said bath additionally contains
about 0.5 to 3.0 grams per liter of 1,2,4-trichlorobenzene and
wherein said current density is about 5.0 to 50.0 amperes per
square foot.
32. The method of claim 30 wherein said bath additionally contains
about 0.3 to 2.0 grams per liter of an aromatic aldehyde selected
from the group consisting of 2,4-dichlorobenzaldehyde and 2,
b-dichlorobenzaldehyde, and wherein said radical of said class is
fluoborate.
33. The method of claim 32 wherein said temperature is above about
80.degree. Fahrenheit.
34. The method of claim 32 wherein said bath additionally contains
about 0.5 to 3.0 grams per liter of 1,2,4-trichlorobenzene, about
2.0 to 25.0 grams per liter of formaldehyde, and about 2.0 to 15.0
grams per liter of an aromatic amine selected from the group
consisting of toluidines and aniline.
35. The method of claim 30 wherein said bath additionally contains
at least 0.1 to 10.0 grams per liter of a carbonyl-containing
compound selected from the group consisting of benzylidene acetone,
3-hydroxybutanal, thiophene aldehyde, benzaldehyde,
2,5-dimethoxy-benzaldehyde, tolualdehyde, cinnamaldehyde, and
anisaldehyde, and about 2.0 to 15.0 grams per liter of an aromatic
amine selected from the group consisting of toluidines and
aniline
36. The method of claim 25 wherein said bath contains about 15.0 to
20.0 grams per liter of stannous ion and about 175.0 to 150.0 grams
per liter of lead ion, wherein said metal of said class is a
tin/lead alloy, wherein said bath additionally contains about 0.3
to 2.0 grams per liter of an aromatic aldehyde selected from the
group consisting of 2,4-dichlorobenzaldehyde and
2,6-dichlorobenzaldehyde, about 0.5 to 3.0 grams per liter of
1,2,4-trichlorobenzene, and about 2.0 to 25.0 grams per liter of
formaldehyde, wherein said pH is about 0.1 to 1.5, wherein said
current density is greater than about 400.0 amperes per square
foot, and wherein said workpiece and bath are moved relative to one
another at a rate of at least about 150.0 lineal feet per minute.
Description
BACKGROUND OF THE INVENTION
As is well known, electrodeposits of tin and/or lead are employed
in a wide variety of decorative and functional applications.
Notwithstanding the availability of different types of formulations
for the production of such deposits, there has remained a need for
a bath having an optimum combination of characteristics. In many
instances the electrodeposits produced from the presently available
baths are deficient in one or more desired physical characteristics
such as smoothness, uniformity, fine grain structure, and freedom
from porosity; frequently the baths produce satisfactory results
only under limited conditions of operation which are often not
entirely practical or economically desirable.
Recently there has been developed a highly satisfactory bath for
the electrodeposition of tin/lead alloys which is described and
claimed in copending United States Application for Letters Patent
of Grace F. Hsu, Ser. No. 83,229, filed on Oct. 22, 1970, and
assigned to the assignee of the present invention. In the course of
the developmental activity with respect to the aforementioned
invention it was found that tin and lead alone, or in combination,
could be plated advantageously and efficiently from a novel bath.
It was also found that the conditions of operation and composition
could be varied depending upon the metal being electrodeposited and
the characteristics desired in the metal deposit.
Accordingly, it is an object of the present invention to provide a
novel electroplating bath which is capable of producing highly
desirable deposits of tin, lead and alloys thereof.
It is also an object of the invention to provide such a bath which
is capable of producing a deposit that is smooth, substantially
free of porosity, uniform, relatively fine in grain structure
and/or bright when so desired, and which may also be of an optimum
composition for soldering in the case of the alloy
compositions.
Another object is to provide such a bath which operates with good
efficiency and over a broad range of current density.
Still another object of the invention is to provide a novel
electroplating method for the production of a high quality tin,
lead or tin/lead alloy deposit, which method is rapid, efficient,
and effective, and which may be conducted under convenient and
practical conditions over a broad range of current density.
A further object is to provide a high speed electroplating method
for tin, lead and alloys thereof based upon the novel bath and
particularly advantageous for wire plating operations.
SUMMARY OF THE DISCLOSURE
It has now been found that the foregoing and related objects can be
readily attained in an aqueous acid plating bath comprising about
15.0 to 350.0 grams per liter of an ion selected from the group
consisting of stannous ion, lead ion, and mixtures thereof, and
about 100.0 to 500.0 grams per liter of a radical selected from the
group consisting of a fluoborate, fluosilicate, sulfamate, and
mixtures thereof. The bath contains about 5.0 to 50.0 grams per
liter of an alkoxylated fatty acid alkylolamide surfactant, and it
has a pH less than about 3.0.
Preferably, the alkylolamide surfactant is present in an amount of
about 10.0 to 25.0 grams per liter, the bath has a pH of about 0.1
to 1.5, and the electrolyte radical is fluoborate. The bath may
also contain, in addition to the foregoing components, about 0.1 to
10.0, and preferably about 0.3 to 2.0 grams per liter, of a ring
halogenated aromatic aldehyde which may be selected from the group
consisting of 2,4-dichlorobenzaldehyde and
2,6-dichlorobenzaldehyde; about 2.0 to 15.0 grams per liter of an
aromatic amine which may be selected from the group consisting of
toluidines and aniline; about 0.5 to 3.0 grams per liter of a
trichlorinated benzene derivative which is most desirably
1,2,4-trichlorobenzene; and/or about 2.0 to 25.0 grams per liter of
a lower aliphatic aldehyde containing one to four carbon atoms,
which is most desirably formaldehyde. The bath may also include, in
combination with an aromatic amine, about 0.1 to 10.0 grams per
liter of a carbonyl-containing compound selected from the group
consisting of benzylidene acetone, 3-hydroxybutanal,
thiophenealdehyde, benzaldehyde, 2,5-dimethoxybenzaldehyde,
tolualdehyde, cinnamaldehyde, and anisaldehyde.
For the production of optimum lead deposits the bath, generally
comprised as hereinbefore set forth, will contain at least about
75.0 grams per liter of lead ion and will be substantially free of
tin ions. Preferably, such a lead bath will contain at least about
150.0 grams per liter of lead ion, and will additionally contain
about 0.5 to 5.0 grams per liter of a polyethoxylated alkyl phenol
secondary surfactant.
When employed for the production of a tin deposit, the bath will be
substantially free of lead ion and will contain at least about 75.0
grams per liter of stannous in. Preferably, such a bath will
contain about 100.0 to 150.0 grams per liter of the stannous ion,
and it may advantageously include about 0.5 to 3.0 grams per liter
of a trichlorinated benzene derivative.
To produce tin/lead alloy deposits in which the amount of tin
advantageously predominates, the concentration of stannous ion in
the bath will be about 10.0 to 180.0 grams per liter, and that of
the lead ion will be about 90.0 to 6.0 grams per liter. Preferably,
the electrolyte in such a bath is provided by at least about 150.0
grams per liter of the fluoborate radical, with the bath containing
at least about 50.0 grams per liter of free fluoboric acid and free
boric acid from at least about 10.0 grams per liter to saturation.
The bath may desirably contain an aromatic aldehyde or a
trichlorinated benzene derivative as set forth above, and most
desirably these components are present in combination. It may, in
addition, contain an aromatic amine and/or formaldehyde; when the
aromatic amine is present, a carbonyl-containing compound of the
group hereinbefore identified may also be included. It is
especially desirable that the amount of the stannous ion in such an
alloy bath be about 45.0 to 65.0 grams per liter and that the
amount of lead ion therein be about 30.0 to 20.0 grams per
liter.
The bath may also be optimally composed to produce tin/lead alloy
deposits wherein the amount of lead advantageously predominates, in
which instance it should contain about 10.0 to 30.0 (most desirably
about 15.0 to 20.0) grams per liter of stannous ion and about 200.0
to 100.0 (most desirably about 175.0 to 150.0) grams per liter of
the lead ion. For especially desirable results, the bath will
contain about 0.5 to 5.0 grams per liter of a polyethoxylated
alkylphenol secondary surfactant.
Highly desirable metal deposits are readily attained under
economically advantageous conditions in an electroplating method
wherein the aqueous acid plating bath, comprised as has
hereinbefore been described, is prepared and maintained at a
temperature of about 50.degree. to 150.degree. Fahrenheit. A
workpiece having a metallic surface, and at least one anode of a
metal selected from the class consisting of tin, lead, and alloys
thereof, are immersed in the bath, and a voltage is applied
thereacross to provide a current density of about 2.0 to 2,000.0
amperes per square foot at the workpiece, thereby depositing the
metal upon the metallic surface; preferably, the bath and/or the
workpiece is agitated.
In instances in which the bath contains at least 150.0 grams per
liter of lead ion and is substantially free from tin ions, or in
which it contains about 45.0 to 65.0 grams per liter of stannous
ion and about 30.0 to 20.0 grams per liter of lead ion, the current
density at the workpiece may preferably be less than about 100.0
amperes per square foot. When the bath contains about 100.0 to
150.0 grams per liter of stannous ion and is substantially free
from lead ion, or when it contains about 15.0 to 20.0 grams per
liter of stannous ion and about 175.0 to 150.0 grams per liter of
lead ion, the current density may preferably be greater than about
400.0 amperes per square foot, and most desirably it is at least
about 600.0 amperes per square foot; the workpiece and the bath may
be moved relative to one another at a rate of at least about 150.0
lineal feet per minute to provide a high speed plating method. The
various additives and combinations thereof hereinbefore set forth
may be included in the baths used in the practice of the novel
method of the invention, and in most cases the pH of the bath
employed will preferably be about 0.1 to 1.5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As will be appreciated, the amounts of the tin and/or lead ions
present in the bath will depend upon a number of factors, primary
considerations being the desired composition of the
electrodeposited metal and, to lesser degrees, the technique
employed, the conditions of the operation, etc. In any event, to
obtain satisfactory results the concentration of the cation to be
electrodeposited (be it tin, lead, or a mixture thereof) must be
from about 15.0 to 350.0 grams per liter because amounts outside of
the range will result in poor efficiency, sludging, precipitation,
etc., and will tend to produce deposits of unacceptable quality.
When either the tin ion or the lead ion is employed in the
substantial absence of the other, it is preferred that the
concentration of the cation be at least about 75.0 grams per liter;
most desirably, when lead is employed alone it will be present in
an amount of at least 150.0 grams per liter and, when tin is the
only cation present, its concentration should be in the range of
about 100.0 to 150.0 grams per liter.
When the bath is utilized for the production of a tin/lead alloy
deposit wherein tin predominates, the concentrations of tin and
lead will generally be about 10.0 to 180.0 and about 90.0 to 6.0
grams per liter, respectively; most desirably, such a bath will
contain about 45.0 to 65.0 grams per liter of the stannous ion and
about 30.0 to 20.0 grams per liter of the lead ion. On the other
hand, when the alloy deposit is to contain a predominant amount of
lead, the bath may advantageously contain about 10.0 to 30.0 grams
per liter of stannous ion and about 200.0 to 100.0 grams per liter
of lead ion; preferably, the concentrations of the respective
metals in such a bath will be about 15.0 to 20.0 and about 175.0 to
150.0 grams per liter. One desirable feature of the present
invention is that it enables the formation of an electrodeposit
having a composition at or near the eutectic point for tin/lead
alloys. The most desirable ranges for the concentrations of the
ions in such a bath are about 53.0 to 57.0 grams per liter of
stannous ion and about 27.0 to 23.0 grams per liter of lead
ion.
The electrolyte radical is fluoborate, fluosilicate, sulfamate, or
mixtures thereof, although other non-interfering radicals may be
present as the result of using salts to furnish all or a portion of
the tin and lead ions with the desired radical. Thus, the
electrolyte radicals may be provided as the acids or as salts of
non-interfering cations. It should be appreciated that the terms
"fluoborate," "fluosilicate," and "sulfamate" are used generically
herein and encompass the more complex salts thereof, such as the
phenolsulfamate compounds. Fluoborate electrolytes are preferred
and, to be satisfactory, the bath should contain about 100.0 to
500.0 grams per liter of the fluoborate radical; preferably, the
amount of the radical will be not less than about 150.0 grams per
liter. Typically, such a bath will contain at least about 50.0
grams per liter of free fluoboric acid and at least about 10.0
grams per liter of free boric acid, although these quantities may
vary considerably to obtain optimum results in specific baths. In
many cases the bath will desirably be maintained at saturation with
boric acid, and this condition can be assured simply by suspending
a porous bag of boric acid in the solution.
The third essential component of the baths is a polyoxyalkylated
fatty acid alkylolamide surfactant, which must be present in an
amount of about 5.0 to 50.0 grams per liter, and preferably in an
amount of about 10.0 to 25.0 grams per liter; at concentrations
lower than about 10.0 grams per liter there is some tendency for
the deposit to darken and to become porous, whereas more than about
25.0 grams per liter of the surfactant tends to cause coarseness.
Alkylolamide surfactants that are suitable for use herein may have
the following structural formula: ##SPC1##
where R.sub.1 is a fatty acid alkyl group, containing eight to 22
carbon atoms, R.sub.2 is selected from the group consisting of
ethylene, propylene, and mixtures thereof, m is an integer from
zero to 15, n is an integer from one to 30, and the sum of m plus n
is an integer from two to 30; generally, when m is other than zero
it will be equal to n. Commercial products which may be employed to
furnish the alkylolamide surfactant include the fatty acid
derivatives sold by Stepan Chemical Company of Northfield, Ill.
under the trademark AMIDOX. Specifically, the products designated
by Stepan as AMIDOX C-2, C-5, L-2, and L-5 have been found to be
particularly beneficial, and that designated AMIDOX C-5 is
preferred. It is believed that the AMIDOX products of the C series
are ethoxylated coconut fatty acid monoethanolamides, and that the
members of the L series are ethylene oxide condensates of lauric
monoethanolamide. The associated numbers are believed to indicate
the number of moles of ethylene oxide that have been used per mole
of amide in producing the product. A second manufacturer of
products that may be appropriate to provide this component of the
baths is Armour Industrial Chemical Company of Chicago, Ill., which
sells them under the trademark ETHOMID. Specific products are
designated ETHOMID HT/15, HT/60 and O/15, wherein the designation
HT and O indicate that the product is either a hydrogenated-tallow
amide or an oleamide derivative, respectively; subtraction of 10
from the associated numeral indicates that the number of moles of
ethylene oxide that are believed to be present in a molecule of the
compound. It should be appreciated that, in some instances, best
results may be achieved when a combination of two or more of the
foregoing alkylolamide surfactants is utilized.
In some of the baths falling within the scope of the present
invention, a secondary surfactant may be utilized in combination
with the fatty acid alkylolamide derivative to produce optimum
properties in the deposit. Exemplary of such secondary surfactants
are polyalkoxylated alkylphenols, and especially the condensates of
alkylphenols having six to 12 carbon atoms in the alkyl chain with
an alkylene oxide selected from the class consisting of ethylene
oxide, propylene oxide and mixtures thereof. Generally, these
products will contain about five to 30 alkylene oxide groups in
each molecule. Specific commercial products that may be
advantageously employed are those sold by Atlas Chemical
Industries, Inc. of Wilmington, Del. under the designations RENEX
650 and RENEX 697; the product sold by General Aniline and Film
Corporation of New York, N.Y. under the designation IGEPAL CO-710;
and the products designated NEUTRONYX 640, 656 and 675, which are
sold by Onyx Chemical Company of Jersey City, N.J. The amount of
the secondary surfactant employed will generally be in the range of
about 0.5 to 5.0 grams per liter, and normally about 1.5 grams per
liter thereof will be most satisfactory. Mixtures of different
types of secondary surfactants may also be used, and specific
alternative surfactants will be apparent to those skilled in the
art in view of the foregoing disclosure.
In most instances, the baths will contain one or more carbonyl
containing compounds to increase the level of brightness of the
deposit. It is possible to employ any of a variety of different
types of compounds for this purpose, such as the ring halogenated
benzaldehydes, benzylidene actone, 3-hydroxybutanal, thiophene
aldehyde, benzaldehyde, 2,5-dimethoxybenzaldehyde, tolualdehyde,
cinnamaldehyde, anisaldehyde, etc. The ring halogenated
benzaldehydes are preferred and particularly desirable results have
been obtained using either 2,4-dichlorobenzaldehyde, or
2,6-dichlorobenzaldehyde. It has been found that the presence of
about 2.0 to 15.0, and preferably about 3.0 to 8.0 grams per liter
of a primary or secondary aromatic amine (such as ortho-toluidine,
meta-toluidine, N-ethyl-ortho-toluidine, aniline, etc.) is highly
desirable to obtain optimum results in the baths of the present
invention using other than the ring halogenated benzaldehydes,
whereas the ring halogenated benzaldehydes can produce comparable
deposits in the absence of such amines. Although the specific
amount will depend upon the particular carbonyl compound involved,
the minimum effective concentration of these compounds will
generally be at least about 0.1 gram per liter; usually, at least
about 0.3 gram per liter thereof will yield desirable results. More
than about 10.0 grams per liter will, in most cases, be without
additional benefit; the preferred upper limit is about 2.0 grams
per liter from the standpoint of economy and minimizing unnecessary
concentrations of components.
When the bath contains a carbonyl compound or other brightening
agent, it will usually be desirable to also include at least about
2.0 to 25.0 grams per liter of a lower aliphatic aldehyde (i.e.,
one containing one to four carbon atoms). The presence of this
additive appears to widen the range of current density over which a
bright deposit is obtained and to otherwise improve operation (such
as making the bath less sensitive to variations); formaldehyde is
preferred. An additional additive that is very beneficially
included in the bath is a trichlorinated benzene derivative, and
most often 1,2,4-trichlorobenzene will be employed. Its use in an
amount of about 0.5 to 3.0 grams per liter tends to increase
brightness at the lower end of the current density range and to
smooth the deposit and reduce or eliminate the so-called "orange
peel" effect which may otherwise occur.
Among the other additives which may be included to modify the
operation of the present bath are auxiliary surfactants, secondary
brighteners, and other materials, such as the polyvinyl alcohols,
peptone, resorcinol, glue, gelatine, beta-naphtol, etc. When used,
these additives should usually be included in amounts of about 0.5
to 7.5 grams per liter, and it has been found that about 0.5 to 5.0
grams per liter of cresylic acid may also be somewhat desirable.
Although little or no tendency for metal sludge or precipitate
formation has been noted in baths properly prepared and operated in
accordance with the invention, in some instances it may be
desirable to incorporate a chelating agent wuch as a citric acid,
malic acid, or the aminopolyacetic acids (e.g., ethylenediamine
tetraacetic acid, ethylenetriamine pentaacetic acid,
nitrilotriacetic acid). Such chelating agents, when employed, are
generally included in an amount of about 5.0 to 20.0 grams per
liter.
Since some of the suitable brighteners and other components which
may desirably be included in the bath exhibit relatively low
solubility therein, it may be necessary or desirable to employ a
solvent solution thereof to facilitate formulation of the bath.
Among the various solvents that may be employed, depending upon the
particular component involved, are the low molecular weight
alcohols (methanol, ethanol, and propanol) and the low molecular
weight glycol ethers (ethylene glycol monoethyl ether, etc.).
Generally, the component will be added as a 0.1 to 5.0 and
preferably as a 0.5 to 2.0 percent by weight solution so as to
obtain a stable solvent solution which may be readily dispersed in
the acid bath. In some instances, it may be most convenient to
provide the majority or all of the bath components as a premixed
solvent or concentrate solution, in which event the concentration
of inert solvent (other than water) in the ultimate bath may be
quite high.
Formulations falling within the scope of the present invention may
be employed in rack, barrel, and wire plating operations, and
accordingly the conditions under which they will be used may vary
considerably. Thus, depending upon the type of plating operation
and other factors such as temperature, agitation, etc., the current
density may vary from about 2.0 to 2,000.0 amperes per square foot
(ASF). In rack and barrel plating operations, the average current
density will not generally exceed about 100.0 ASF, and will
preferably be about 5.0 to 50.0 ASF; for wire plating operations
the current density will not usually be less than about 400.0 ASF,
and for bright deposits it will generally exceed about 600.0 ASF.
With baths intended for the production of alloy deposits having a
substantially eutectic composition, a narrow current density range
of about 25.0 to 35.0 ASF has been found to be most desirable.
Although it is desirable in most instances to agitate the workpiece
and/or the bath to obtain high quality uniform deposits and to
avoid the development of sludge or film, particularly under
conditions of high current density and/or temperature, agitation is
not essential. Of course, in wire plating operations the workpiece
and bath move rapidly relative to one another and the novel
composition of the instant invention may be formulated to operate
at wire speeds in excess of about 150, and preferably above 200,
lineal feet per minute.
The plating efficiency of the bath is generally high, and in the
optimum case will range up to about 95 percent, and above, based
upon the theoretical rate of deposition. The applied voltage should
be about 0.2 to 10.0 volts, and preferably plating will be carried
out at about 0.5 to 5.0 volts; once again, the most desirable
voltage level will depend upon the plating technique and conditions
employed.
The baths should be operated at a temperature of about 50.degree.
to 150.degree., and preferably from about 60.degree. to 90.degree.,
Fahrenheit; temperatures above about 80.degree. Fahrenheit are
often most desirable. Operation below about 50.degree. Fahrenheit
tends to be inefficient and to produce undesirable deposits,
whereas temperatures higher than about 90.degree. Fahrenheit may
tend to cause oxidation of the tin ion (in the tin and tin/lead
baths) to the stannic state and to produce somewhat dull and rough
deposits; low temperatures are also preferred because of a tendency
for the bath to be consumed at an excessive rate at temperatures
that are unduly high. The pH should be less than 3.0, and
preferably it will be 1.5 or below; generally, a pH of about 0.1
will represent the practical lower end of the range.
Any metallic substrate or metal-surfaced article which can be
plated with tin or lead using prior art baths may generally be
coated in accordance with the present invention. For example, good
deposits may be produced upon articles of copper, nickel, iron,
steel, etc. The best results are obtainable with these baths if
relatively pure anodes of the respective metals are employed, and
to produce tin/lead deposits either alloy anodes or separate tin
and lead anodes may be used. It should be noted that the
composition of the anode has a significant effect upon the
composition of the alloy deposit, and that it is generally
desirable to employ an anode having a proportion of metals
approximating that desired in the plated deposit. The composition
of the deposit may also be controlled by use of separate anodes of
tin and lead, to which the current may be proportioned
appropriately.
Filtration of the bath is not essential, but will normally be
beneficial when contamination is encountered due to air-borne
impurities and/or carryover from other finishing operations;
preferably, it will be effected on a continuous basis. Various
filtering media may be utilized including fabrics (such as of
polypropylene) and other conventional filtering materials. The
depletion of the various components of the bath is best corrected
by analysis for the several components on a periodic basis which
can be established for a given facility. To determine the amounts
of stannous salt required, an iodine titration technique may be
used; the lead content may be checked by precipitation with dilute
surfuric acid. The amount of the surfactants and other components
may be best evaluated by testing a sample of the bath in a suitable
test cell, and a suitable schedule may be established for a given
facility and workpiece.
As has previously been discussed, the baths of the present
invention may be employed for the production of deposits containing
either lead or tin, or to produce an alloy containing these
elements in substantially any proportion, depending upon the
characteristics desired in the ultimate product and the use for
which it is intended. As has also been mentioned, tin/lead deposits
having a composition at or near the eutectic value for the alloy
(about 63/37) are optimum for soldering purposes and the present
baths may be employed advantageously for the production thereof.
Electro-deposits containing tin and lead in a 7:93 ratio, typically
used for bearing contact surfaces, may also be produced with these
formulations by proper selection of the bath components and the
conditions of operation.
Depending upon the several variables hereinbefore discussed, the
deposits produced in accordance herewith may vary from quite dull
to specular brightness. They are generally very smooth and uniform
in appearance, substantially free from porosity, and they tend to
have relatively fine grain structures withou undesirable crystal
growth (i.e., treeing). In addition, the deposits are fully
adherent to the surface of the workpiece, and the bath composition
may be such that even heavy deposits, i.e., those of about 1 to 4
mils in thickness, are free from peeling and cracking.
Illustrative of the efficacy of the present invention are the
following specific examples, wherein all parts and percentages are
on a weight basis unless specified to the contrary. Although the
solutions employed are stable over long periods of use, a fresh
solution is utilized in each of the Examples and no "working in"
period is required.
EXAMPLE ONE
PART A
Into a 267 milliliter Hull cell is introduced an aqueous lead
plating bath containing water and amounts of lead fluoborate,
fluoboric acid, and boric acid sufficient to provide therein about
168.0 grams per liter of lead metal, about 15.0 grams per liter of
free fluoboric acid, about 22.5 grams per liter of free boric acid
and a pH less than about 1.5. Also included in the bath is about
15.0 grams per liter of a coconut fatty acid alkylolamide
surfactant containing about 5 moles of ethylene oxide per mole
thereof (sold by Stepan Chemical Company of Northfield, Illinois as
AMIDOX C-5), and about 1.5 grams per liter of an ethoxylated
nonylphenol surfactant containing about 30 moles of ethyleneoxide
per molecule thereof (sold by Atlas Chemical Industries of
Wilmington, Delaware under the trademark RENEX 650). Into the cell
is placed a clean steel panel and a lead anode, and plating is
effected with a current of two amperes for 5 minutes at room
temperature, without agitation. Over a wide current density range
of about 2.0 to 100.0 amperes per square foot, a uniform lead
deposit is produced which is light grey in color, exhibits a slight
sheen, is fine in grain structure and is substantially free from
undesirable crystal growth; it is found to be substantially
non-porous and very adherent to the panel, the edge characteristics
are good, and there is no evidence of cracking or peeling even at
thicknesses of about 4 mils.
PART B
The bath described in Part A thereof is employed at temperatures of
80.degree., 90.degree., 100.degree., 110.degree., and 130.degree.
Fahrenheit, and at voltages of 3.5, 3.5, 3.0, 3.0, and 2.75
respectively. It is seen that the increase in temperature refines
the grain structure of the deposit at current densities above about
50.0 ASF, and that the high temperatures do not significantly
deteriorate the quality of the deposit obtained.
PART C
Part A of this example is repeated using the same bath, but
omitting the secondary surfactant (i.e., the nonylphenol
derivative) therefrom. Although some porosity is encountered at the
extreme low end of the plating range, the deposit is of good
quality and free from porosity at current densities of about 10.0
to 80.0 ASF. Substitution of the nonylphenol ethoxylated product
sold by Atlas Chemical Industries under the trademark RENEX 697,
and that sold by General Aniline and Film Corporation under the
trademark IGEPAL CO-710 for the RENEX 650, is found to produce
results that are substantially equivalent to those obtained in Part
A.
EXAMPLE TWO
PART A
An aqueous bath is prepared by admixing with water sufficient
quantities of stannous fluoborate and fluoboric acid to provide
about 120.0 grams per liter of stannous ion and about 140.0 grams
per liter of free fluoboric acid; boric acid is added and a porous
bag thereof is suspended in the bath to ensure its saturation
therewith. The bath also contains about 15.0 grams per liter of the
AMIDOX C-5 product, about 0.75 gram per liter of
2,4-dichlorobenzaldehyde and about 1.0 gram per liter of
1,2,4-trichlorobenzene. Plating is carried out at a pH of about 1.2
and at room temperature, utilizing a block of tin as the anode and
a length of copper wire wound spirally upon a one inch diameter
mandrel as the cathode. During the plating operation, the mandrel
is rotated in the bath at several speeds to simulate wire plating
at rates of from about 200 to 1,800 lineal feet per minute, and the
current density at the cathode is varied from about 400.0 to
2,000.0 amperes per square foot. Under all conditions, good quality
electrodeposits of tin are produced upon the wire workpiece.
Although the plate is somewhat dull at current densities below
about 600.0 amperes per square foot, in terms of wire plating
criteria the deposit is bright thereabove.
PART B
The procedure of Part A of this Example is repeated utilizing a
bath having the composition specified, except that the
dichlorobenzaldehyde and trichlorobenzene components are omitted
therefrom. The deposits produced are of good quality, but are
somewhat duller than those produced in accordance with Part A.
EXAMPLE THREE
PART A
An aqueous plating bath is prepared by admixing with water
sufficient quantities of stannous and lead fluoborate concentrate,
fluoboric acid, and boric acid, to provide about 55.0 grams per
liter of stannous ion, about 25.0 grams per liter of lead ion,
about 100.0 grams per liter of fluoboric acid absolute, and 25.0
grams per liter of boric acid. The bath also contains a brightener
system consisting of about 15.0 milliliters per liter of the AMIDOX
C-5, 6.0 milliliters per liter of ortho-toluidine, about 30.0
milliliters per liter of 37.0 percent formaldehyde, 0.5 to 3.0
grams per liter of 1,2,4-trichlorobenzene, and about 6.0
milliliters per liter of a 10.0 percent methanol solution of
2,4-dichlorobenzaldehyde. About 7.5 milliliters per liter of a 10.0
percent methanol solution of cresylic acid is also included in the
bath, and the pH is less than 1.0. Plating is effected in a Hull
cell at room temperature, using as the anode an alloy of 60/40
tin/lead. The bright plating current density range is found to
extend from about 10 to more than 120 ASF, and even below 10 ASF
the deposits are of good quality, albeit with a slightly milky
appearance.
PART B
In a series of barrel plating runs, the same formulation as was
described in Part A hereof is employed, the temperature and current
density being varied to demonstrate the characteristics of the
bath. As a result, it is found that the optimum temperature of
operation for this bath is about 70.degree. to 85.degree.
Fahrenheit; higher temperatures are found to be less desirable
since oxidation of tin to the stannic state is more pronounced and
since operation is required within a higher current density range
for bright deposits. At current densities of less than about 75.0
ASF, plating efficiency is found to be considerably higher than
about 90 percent; at a current density of about 30.0 ASF a nearly
eutectic alloy, containing about 64 percent of tin, is produced.
Mild agitation during plating is found to result in deposits of
excellent appearance, the covering power is outstanding, and the
throwing power of the bath appears to be very good, particularly
for an acidic system.
PART C
A bath comparable to that of Part A hereof is prepared to contain
about 70.0 grams per liter of tin, about 10.0 grams per liter of
lead, and about 20.0 milliliters per liter of formaldehyde. Under
the same conditions of operation set forth herein the range of
current density in which the deposit is bright is found to be about
15.0 to 50.0 ASF; the deposit is analyzed to have about a 90/10
tin/lead composition.
PART D
A bath having the same composition as that set forth in Part A of
this Example is prepared, omitting the formaldehyde and
1,2,4-trichlorobenzene components therefrom; in addition, an equal
weight of 2,6-dichlorobenzaldehyde is substituted for the
2,4-dichlorobenzaldehyde, and an equal weight of an ethylene oxide
condensate of lauric monoethanolamide (AMIDOX L-2) is substituted
for the alkylolamide surfactant employed therein. At room
temperature, the deposit is found to be semi-bright from about 1.5
to 12.0 ASF; in the range of about 12.0 to 75.0 ASF the deposit is
white but somewhat streaked; and from about 75.0 to about 150.0 ASF
the deposit is somewhat brighter, and slightly less streaking is
evident. Utilizing the same bath at about 90.degree. Fahrenheit
generally improves the quality, and produces a dull-bright deposit
at current densities of about 2.0 to 18.0 ASF and a bright hazy
deposit from about 18.0 to 100.0 ASF.
PART E
Part D hereof is substantially repeated, with the sole exception
that about 5.0 grams per liter of ortho-toluidine and various
amounts of a carbonyl-containing compound other than the
2,6-dichlorobenzaldehyde is employed therein. In combination with
the ortho-toluidine, equivalent results to those obtained in Part D
of this example are realized with (1) about 0.5 gram per liter of
benzylidene acetone, (2) about 5.0 grams per liter of
3-hydroxybutanal, (3) about 0.1 gram per liter of thiophene
aldehyde, (4) about 0.1 gram per liter of
2,5-dimethoxybenzaldehyde, and (5) about 1.0 gram per liter of
anisaldehyde.
PART F
A bath is prepared as in Part A hereof to contain about 50.0 grams
per liter of stannous ion, about 25.0 grams per liter of lead ion,
about 17.0 grams per liter of the AMIDOX C-5 surfactant, and about
1.3 grams per liter of 1,2,4-trichlorobenzene. Operation at current
densities of about 5.0 to 50.0 ASF and at room temperature produces
a nominal 60/40 tin/lead alloy deposit which is smooth and exhibits
a semi-bright sheen.
PART G
Part A is again repeated utilizing sufficient stannous fluoborate
and lead fluoborate to provide about 17.5 and 157.5 grams per liter
of stannous ion and lead ion respectively. The bath contains about
15.0 grams per liter of the AMIDOX C-5 surfactant, and about 1.5
gram per liter of the RENEX 650 secondary surfactant referred to in
Part A of Example One. Operation at current densities of about 2.0
to 100.0 ASF and at room temperature is found to produce a 10/90
tin/lead alloy deposit that exhibits a slight sheen and has a
refined grain structure that is substantially free of treeing.
EXAMPLE FOUR
Sufficient amounts of stannous fluoborate and lead fluoborate are
admixed in water to provide about 150.0 grams per liter of stannous
ion and about 75.0 grams per liter of lead ion. In addition, the
bath also contains about 15.0 grams per liter of AMIDOX C-5
surfactant, about 0.3 gram per liter of 2,4-dichlorobenzaldehyde,
about 1.0 gram per liter of 1,2,4-trichlorobenzene, and about 10.0
milliliters per liter of a 37 percent solution of formaldehyde.
Utilizing an anode of 60/40 tin/lead alloy and a length of copper
wire in the apparatus described in Example Two a relatively bright
60/40 deposit is produced at current densities of about 400.0 to
2,000.0 ASF with the wire moving through the bath at a rate of
about 200 to 1,800 lineal feet per minute.
EXAMPLE FIVE
Stannous fluoborate and lead fluoborate are admixed with water in
quantities sufficient to provide about 15.0 and 10.0 grams per
liter thereof, respectively. The bath also contains about 15.5
grams per liter of the AMIDOX C-5 surface active agent, about 0.78
gram per liter of 2,4-dichlorobenzaldehyde, about 1.0 gram per
liter of 1,2,4-trichlorobenzene, and sufficient fluoboric acid to
provide about 400.0 grams per liter of the free acid; the pH of the
bath is 0.2 or below. Using an anode of 60/40 tin/lead alloy in a
Hull cell, and operating at room temperature, bright deposits
nominally containing tin and lead in a 60/40 ratio are produced at
current densities of about 5.0 to 50.0 ASF. Adding about 0.5 to 3.0
percent by volume of a 37 percent solution of formaldehyde is found
to brighten the bath and to render it somewhat less sensitive to
variations.
Thus, it can be seen that the present invention provides a novel
electroplating bath which is capable of producing highly desirable
deposits of tin, lead and tin/lead alloys. The bath operates with
good current efficiency and over a broad range of current density
to produce a deposit that is smooth, relatively non-porous,
uniform, of fine grain structure, and/or bright when so desired;
the deposit may be of an optimum composition for soldering in the
case of the alloy compositions. The invention also provides a novel
method for the production of a high quality metal deposit, which
method is rapid, efficient and effective, and which may be
conducted under convenient and practical conditions over a broad
range of current density. It may, in addition, be effected at high
relative speeds between workpiece and bath for wire plating
operations.
* * * * *