U.S. patent number 3,925,170 [Application Number 05/435,844] was granted by the patent office on 1975-12-09 for method and composition for producing bright palladium electrodepositions.
This patent grant is currently assigned to American Chemical & Refining Company, Inc.. Invention is credited to Robert M. Skomoroski, Robert G. Zobbi.
United States Patent |
3,925,170 |
Skomoroski , et al. |
December 9, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
METHOD AND COMPOSITION FOR PRODUCING BRIGHT PALLADIUM
ELECTRODEPOSITIONS
Abstract
A composition for producing adherent deposits of palladium from
a cyanide-free bath uses small amounts of cobalt or nickel or the
combination thereof as the brightener. The bath employs as an
electrolyte alkali metal and ammonium sulfates, sulfamates,
phosphates, nitrates, nitrites and mixtures thereof. Preferably,
the brightener concentration is 0.004-0.02 gram mole per liter
nickel or 0.002-0.04 gram mole per liter cobalt, or the combination
thereof. Cetyltrimethylammonium bromide is an optional component
for the bath which is maintained at a pH of 7.5-11.0 and at a
temperature of 26.degree.-60.degree. Centigrade. For barrel
plating, the current density is 0.05-0.5 amperes per square
decimeter and for rack plating the current density is 0.2-2.0
amperes per square decimeter.
Inventors: |
Skomoroski; Robert M.
(Paterson, NJ), Zobbi; Robert G. (Southbury, CT) |
Assignee: |
American Chemical & Refining
Company, Inc. (Waterbury, CT)
|
Family
ID: |
23730043 |
Appl.
No.: |
05/435,844 |
Filed: |
January 23, 1974 |
Current U.S.
Class: |
205/143; 205/256;
205/257 |
Current CPC
Class: |
C25D
3/50 (20130101) |
Current International
Class: |
C25D
3/50 (20060101); C25D 3/02 (20060101); C25D
003/56 () |
Field of
Search: |
;204/43N,47,123 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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8769 |
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Mar 1970 |
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JA |
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25604 |
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Jul 1971 |
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JA |
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25605 |
|
Jul 1971 |
|
JA |
|
25606 |
|
Jul 1971 |
|
JA |
|
25607 |
|
Jul 1971 |
|
JA |
|
212,692 |
|
May 1968 |
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SU |
|
213,509 |
|
May 1968 |
|
SU |
|
Other References
KS. Indira et al., Metal Finishing, pp. 52-57, Vol. 6,
(1973)..
|
Primary Examiner: Kaplan; G. L.
Claims
Having thus described the invention, we claim:
1. In an aqueous bath for the electroplating of palladium, the
combination consisting essentially of:
A. 0.02-0.25 gram mole per liter of palladium ion;
B. 0.9-3.6 gram moles per liter of ammonium hydroxide;
C. 0.1-0.7 gram mole per liter of a soluble electrolyte selected
from the group consisting of alkali metal and ammonium sulfates,
sulfamates, phosphates, nitrates, nitrites and mixtures
thereof;
D. a soluble metallic brightener selected from the group consisting
of 0.002-0.04 gram mole per liter of cobalt ion, 0.004-0.02 gram
mole per liter of nickel ion and mixtures thereof providing
0.003-0.068 gram mole per liter of metal ions; and
E. up to 6.times.10.sup.-.sup.4 gram mole per liter of
cetyltrimethylammonium bromide;
said bath having a pH of 7.5-11.0.
2. The bath in accordance with claim 1 wherein said soluble
electrolyte is a sulfate salt.
3. The bath in accordance with claim 2 wherein said soluble salt is
potassium sulfate.
4. The bath in accordance with claim 1 wherein said palladium ion
is present in an amount of 0.05-0.1 gram mole per liter, said
ammonium hydroxide is present in an amount of 1.4-2.1 gram moles
per liter, said electrolyte is present in an amount of 0.2-0.4 gram
mole per liter, and wherein said bath has a pH of 8.5-9.5.
5. The bath in accordance with claim 4 wherein said electrolyte is
a sulfate salt and wherein said cetyltrimethylammonium bromide is
present in an amount of at least 3.times.10.sup.-.sup.5 gram per
liter.
6. The bath in accordance with claim 1 wherein said
cetyltrimethylammonium bromide is present in an amount of at least
3.times.10.sup.-.sup.5 gram mole per liter.
7. The bath in accordance with claim 1 wherein said soluble
metallic brightener is a mixture of nickel and cobalt ions.
8. In the method of electroplating palladium deposits upon a
workpiece, the steps comprising:
A. immersing a workpiece having a conductive surface in an aqueous
bath consisting essentially of:
1. 0.02-0.25 gram mole per liter of palladium ion;
2. 0.9-3.6 gram moles per liter of ammonium hydroxide;
3. 0.1-0.7 gram mole per liter of a soluble electrolyte selected
from the group consisting of alkali metal and ammonium sulfates,
sulfamates, phosphates, nitrates, nitrites and mixtures
thereof;
4. a soluble metallic brightener selected from the group consisting
of 0.002-0.04 gram mole per liter of cobalt ion, 0.004-0.02 gram
mole per liter of nickel ion and mixtures thereof providing
0.003-0.068 gram mole per liter of metal ions; and
5. up to 6.times.10.sup.-.sup.4 gram mole per liter of
cetyltrimethylammonium bromide;
said bath having a pH of 7.5-11.0;
B. maintaining the temperature of said bath at
26.degree.-60.degree. Centigrade;
C. applying a potential across said workpiece and an anode inert to
said bath, said potential providing a current density of 0.05-2.0
amperes per square decimeter and the anode to cathode surface ratio
being 1.0-5.0:1.0; and
D. removing said workpiece from said bath upon deposition of the
desired thickness of palladium upon the surface thereof.
9. The method in accordance with claim 8 wherein said palladium ion
is present in an amount of 0.05-0.1 gram mole per liter, said
ammonium hydroxide is present in an amount of 1.4-2.1 gram moles
per liter, said electrolyte is present in an amount of 0.2-0.4 gram
mole per liter, and wherein said bath has a pH of 8.5-9.5.
10. The method in accordance with claim 9 wherein said electrolyte
is a sulfate salt and wherein said cetyltrimethylammonium bromide
is present in an amount of at least 3.times.10.sup.-.sup.5 gram
mole per liter.
11. The method in accordance with claim 8 wherein said solution,
workpiece and anodes are placed in contact within a barrel plating
installation and wherein the current density is maintained at about
0.05-0.5 amperes per square decimeter.
12. The method in accordance with claim 8 wherein said solution, a
workpiece and anodes are placed in contact within a rack plating
installation and wherein the current density is maintained at about
0.2-2.0 amperes per square decimeter.
13. The method in accordance with claim 8 wherein the temperature
of the bath is maintained at 46.degree.-52.degree. Centigrade and
wherein vigorous agitation is employed.
14. The method in accordance with claim 8 wherein the surface of
said anode is a noble metal.
15. The method in accordance with claim 8 wherein said soluble salt
is potassium sulfate.
Description
BACKGROUND OF THE INVENTION
Various compositions have been proposed for the deposition of
palladium and various electrolytes have been utilized to provide
sufficient conductivity in such compositions. As is true with many
of the noble metals, cyanide electrolytes have enjoyed considerable
commerical application, and it is the desire to control pollution
problems which has created an increasing trend toward the
substitution of other electrolytes.
As is true with many of the noble metals, small amounts of
brighteners are highly desirable to effect optimum specular
brightness in the electrodeposit. Although some brighteners will
produce specular brightness, there is sometimes a tendency for the
brightener itself to reduce the ductility of the deposit or to
reduce the adhesion to the substrate.
It is an object of the present invention to provide a novel
composition for the electrodeposition of palladium in bright,
highly adherent coatings upon various types of conductive
substrates.
It is also an object to provide such composition which is operable
over a wide range of current density and at ambient to low elevated
temperatures.
Another object is to provide a method for the electroplating of
palladium which is relatively trouble-free and relatively
insensitive to minor variations in operating conditions and which
will produce bright, highly adherent electrodeposits of
palladium.
SUMMARY OF THE INVENTION
It has now been found that the foregoing and related objects may be
obtained in an aqueous bath for the electroplating of palladium
which consists essentially of 0.02-0.25 gram mole per liter of
palladium ion; 0.9-3.6 gram moles per liter of a soluble
electrolyte selected from the group consisting of alkali metal and
ammonium sulfates, sulfamates, phosphates, nitrates, nitrites and
mixtures thereof; and a soluble metallic brightener selected from
the group consisting of 0.002-0.04 gram mole per liter of cobalt
ion, 0.004-0.02 gram mole per liter of nickel ion and mixtures
thereof providing 0.003-0.068 gram mole per liter of the metal ions
combined. The bath may contain up to 6.times.10.sup.-.sup.4 gram
mole per liter of cetyltrimethylammonium bromide, and the pH
thereof is adjusted to be within the range of 7.5-11.0.
The preferred soluble electrolyte is a sulfate salt and potassium
sulfate has been found highly advantageous. The preferred
compositions employ cetylitrimethylammonium bromide in an amount of
at least 3.times.10.sup.-.sup.5 gram mole per liter. The palladium
ion is desirably present in the amount of 0.05-0.1 gram mole per
liter; the ammonium hydroxide is preferably present in an amount of
1.4-2.1 gram moles per liter; and the electrolyte is desirably
present in an amount of 0.2-0.4 gram mole per liter; this preferred
bath composition is desirably utilized at a pH of 8.5-9.5.
In the method of electroplating, a workpiece having a conductive
surface is immersed in the aqueous bath described hereinbefore
while the temperature is maintained at 26.degree.-60.degree.
Centigrade. A potential is applied across the workpiece and an
anode inert to the bath so as to provide a current density of
0.05-2.0 amperes per square decimeter, and the anode to cathode
surface ratio is maintained at about 1.0-5.0:1.0. After application
of the potential for a period of time sufficient to develop the
desired thickness of palladium deposit, the workpiece is removed
from the bath. In barrel plating, the current density is maintained
at about 0.05-0.5 amperes per square decimeter and in rack plating
the current density is maintained at about 0.2-2.0 amperes per
square decimeter. The preferred baths are operated at a temperature
of 46.degree.-52.degree. Centigrade under conditions of vigorous
agitation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As has been indicated hereinbefore, the compositions of the present
invention essentially comprise an aqueous solution of palladium
ion, an electrolyte, a brightener selected from the group
consisting of cobalt ion, nickel ion or the combination thereof,
and ammonium hydroxide sufficient to provide a pH of about
7.5-11.0. A desirable optional additive is cetyltrimethylammonium
bromide.
Turning first in detail to the palladium ion, it may be introduced
as any soluble compound having a non-interfering anion. Thus, the
palladium may be introduced as palladium sulfate, palladium
chloride, palladium nitrate, or as a palladium complex such as
diaminepalladium hydroxide, dichlorodiaminepalladium or
tetraminepalladium chloride. The amount of palladium in the bath
may broadly range from 0.02-0.25 gram mole per liter and is
preferably within the range of 0.05-0.10 gram mole per liter.
As indicated hereinbefore, the electrolyte may be provided by any
one or mixture of alkali metal and ammonium sulfates, sulfamates,
phosphates, nitrates and nitrites. Of the various electrolytes, the
alkali metal and ammonium sulfates have proven to be most
advantageously employed; potassium sulfate is preferred. The
concentration of the electrolyte salt may vary from as little as
0.1 gram mole per liter to as much as 0.7 gram mole per liter.
Preferably, the concentration of the electrolyte salt is within the
range of 0.2-0.4 gram mole per liter.
Ammonium hydroxide is advantageously used to regulate the pH of the
bath and is present in an amount of 0.9-3.6 gram moles per liter
calculated as ammonium hydroxide exclusive of water. For the
preferred compositions, the ammonium hydroxide is present in an
amount of 1.4-2.1 gram mole per liter. Most desirably, the ammonium
hydroxide is added as a highly concentrated aqueous solution (29
percent by weight) in order to minimize dilution, although less
concentrated compositions may also be employed if the water
introduced thereby is entered into the calculations as to
concentration of the remaining ions.
In the event that it is desired to adjust the pH downwardly (i.e.,
to make it more acid), and acid having non-interfering anion should
be employed. Most conveniently, this is sulfuric acid, although
nitric acid, hydrochloric acid and sulfamic acid may be
employed.
As has been indicated heretofore, the brightener is a metal ion
selected from the group consisting of cobalt, nickel and the
combination thereof. As such, the metal ions may be introduced in
the form of any soluble compound which will not introduce an
interfering anion. For the preferred sulfate baths, these metal
ions are introduced as sulfate salts. However, they may also be
introduced as chloride or nitrate salts and as complexes such as
diaminecobalt chloride, hexaminecobalt chloride, hexaminecobalt
nitrate, aquapentaminecobalt chloride, diaquatetraminenickel
nitrate, hexaminenickel nitrate and hexaminenickel chloride.
When cobalt is used alone as the brightener, it is present in an
amount of 0.002-0.04 gram mole per liter and preferably 0.003-0.02
gram mole per liter. When nickel is used alone as the brightener,
it is present in an amount of 0.004-0.02 gram mole per liter and
preferably 0.010-0.015 gram mole per liter. When the two metal ions
are used in combination with each other, the total amount thereof
should provide about 0.5-4.0 grams per liter of metal ion or about
0.003-0.068 gram mole per liter of ions combined. Preferably, the
metal ions combined equal 0.8-2.0 grams per liter or about
0.005-0.034 gram mole per liter.
The ratio of palladium ion to cobalt or nickel ion must be fairly
closely controlled in order to obtain stress-free deposits. The
weight ratio of palladium to cobalt should adjusted to within the
range of 10-50 and preferably 10-33. The palladium to nickel metal
weight ratio should be adjusted to within the range 7.5-19.2 and
preferably 7.5-12.8.
Cetyltrimethylammonium bromide is an optional but desirable
additive to effectively eliminate gas pitting in the palladium
deposit. The amount of this additive should be closely controlled
since excessive amounts will produce excessive foaming and
interfere with the plating operation. As a result, the maximum
amount which should be employed is about 6.times.10.sup.-.sup.4
gram mole per liter or 0.2 gram per liter. Preferably, the maximum
concentration is less than 0.06 gram per liter. An amount of as
little as 2.7.times.10.sup.-.sup.5 gram mole per liter and
preferably 8.times.10.sup.-.sup.5 gram mole per liter (0.01 and
0.03 gram per liter respectively) will produce highly advantageous
results.
The pH of the bath is maintained within the range of 7.5-11.0 and
preferably within the range of 8.5-9.5. As indicated hereinbefore,
the pH may be adjusted by the addition of ammonium hydroxide or by
use of a suitable acid providing a non-interfering anion such as
sulfuric acid.
The temperature of the bath should be within the range of
26.degree.-60.degree. Centigrade, and preferably
46.degree.-52.degree. Centigrade. Although the bath may be utilized
without agitation, it is desirable to employ agitation and vigorous
agitation has been found extremely beneficial. Filtration is highly
desirable if pore-free adherent deposits are to be obtained because
the presence of any solid contaminants will have a profound effect
upon the quality of the deposit. Standard filter cartridges of
polypropylene or other filter media may desirably be employed for
continuous filtration of the bath.
The anode to cathode surface area ratio should be within the range
of 1.0-5.0:1.0 and preferably 2.0:1.0. For rack plating, the
current density should be within the range of 0.2-2.0 amperes per
square decimenter and preferably about 0.5-1.0 amperes per square
decimeter. For barrel plating, the current density should be within
the range of 0.05-0.5 amperes per square decimeter and preferably
about 0.1-0.3 amperes per square decimeter.
It has been found that the palladium deposits produced by the
present invention are relatively stress-free and can be employed
without further treatment for the great bulk of intended
applications. In some instances, where the workpiece is to be
subjected to severe mechanical deformation or to heavy wearing and
abrasion, it is desirable to heat treat the workpieces at a
temperature of about 300.degree.-450.degree. Centigrade for 1/2 to
3 hours in order to relieve all residual internal stresses. The
heat treatment may be conducted either under vacuum or in an inert
gas atmosphere.
Various anodes which are inert to the plating bath may be employed
and generally such anodes will have a surface of noble metal,
although carbon anodes do have limited utility. The preferred
anodes are platinum-clad tantalum although gold-clad tantalum,
platinum and palladium electrodes have all been employed
effectively.
Exemplary of the present invention are the following specific
examples:
EXAMPLE ONE
A bath is prepared by adding to deionized water palladium sulfate
sufficient to provide 5.0 grams per liter as palladium metal, 80
c.c. per liter of ammonium hydroxide (29 percent by weight
NH.sub.3), 1.05 grams per liter cobalt sulfate, 50 grams per liter
potassium sulfate and 0.04 grams per liter cetyltrimethylammonium
bromide. The resulting bath has a pH of 8.5 and is introduced into
a plating cell where the temperature is maintained at 44.5.degree.
Centigrade.
A potential of 1.7 volts is applied across a platinum surfaced
anode and a Hull cell panel 3 centimeters by 5 centimeters in
dimension, the anode to cathode surface area ratio being 3;1. The
current density is determined to be 0.5 amperes per square
decimeter and the current is continued for 20 minutes during which
there is fast agitation of the plating bath.
The panel is then removed and the palladium deposit thus formed is
found to have a thickness of 2.5 microns and to be specular bright.
Flexing of the panel repeatedly indicates that the deposit is
highly adherent.
EXAMPLE TWO
To deionized water are added the various components in amounts
suffcient to provide 9.0 grams per liter of palladium determined as
the metal, 100 c.c. per liter of ammonium hydroxide (29 percent by
weight NH.sub.3), 2.63 grams per liter nickel sulfate, 100 grams
per liter potassium sulfate and 0.03 gram per liter
cetyltrimethylammonium bromide. The pH of the formulation is 7.9
and the temperature is maintained at 37.8.degree. Centigrade.
A Hull cell panel is used as the cathode and a platinum surfaced
anode is employed. A potential of 2.2 volts is applied thereacross
during fast agitation of the solution in the cell. The anode to
cathode surface area ratio is 3:1 and the current density is 0.5
amperes per square decimeter.
After plating for 20 minutes, the panel is removed and is found to
have a specular bright palladium deposit of 1.9 microns thickness.
Flexing the panel indicates the deposit to be highly adherent.
EXAMPLE THREE
To evaluate the effect of other electrolytes, a mixed electrolyte
is prepared using 25 grams per liter potassium sulfate, 2 grams per
liter ammonium nitrate and 1 gram per liter ammonium chloride. The
bath contains palladium sulfate sufficient to provide 5 grams per
liter of palladium as metal and 60 c.c. per liter ammonium
hydroxide (29 percent by weight NH.sub.3) and 0.06 gram per liter
cetyltrimethylammonium bromide. Used as the brightener is 0.46 gram
per liter cobalt sulfate. The pH of this formulation is 9.9 and the
bath is introduced into a test barrel plating installation wherein
it is maintained at 49.degree. Centigrade.
The workpieces to be plated are nickel pins about one centimeter in
length and about 0.5 millimeters in diameter. The anode to cathode
surface area ratio is calculated at 1:1 and a potential of 5 volts
is applied to provide a current density of 0.2 amperes per square
decimeter. The plating operation is continued for a period of 90
minutes after which the parts are removed and found to have a
specular bright deposit of 2.5 microns thickness. The deposit is
highly adherent as evidenced by the lack of exfoliation after
bending of the pins through 90.degree..
Thus it can be seen from the foregoing detailed specification and
examples that the baths of the present invention provide bright,
highly adherent electrodeposits on various types of conductive
substrates. They are operable over a wide range of current density
and at ambient to low elevated temperatures. The plating operation
is relatively trouble-free and relatively insensitive to minor
variations in operating conditions and will yield deposits which
are substantially free from internal stresses.
* * * * *