U.S. patent number 3,865,699 [Application Number 05/408,410] was granted by the patent office on 1975-02-11 for electrodeposition on non-conductive surfaces.
This patent grant is currently assigned to The International Nickel Company, Inc.. Invention is credited to Daniel Luch.
United States Patent |
3,865,699 |
Luch |
February 11, 1975 |
Electrodeposition on non-conductive surfaces
Abstract
A process for metalizing a non-conductive substrate wherein the
substrate is coated with an organic polymer-carbon black mixture,
having a volume resistivity of less than about 1,000
ohm-centimeters, the surface of the mixture is caused to contain
sulfur and the thus treated substrate is placed as a cathode in a
nickel, cobalt or iron plating bath to cause a rapid spread of
metal across the thus treated surface.
Inventors: |
Luch; Daniel (Warwick, NY) |
Assignee: |
The International Nickel Company,
Inc. (New York, NY)
|
Family
ID: |
23616178 |
Appl.
No.: |
05/408,410 |
Filed: |
October 23, 1973 |
Current U.S.
Class: |
205/158; 205/183;
205/167; 252/510 |
Current CPC
Class: |
C25D
5/56 (20130101); C25D 5/54 (20130101); H05K
3/188 (20130101) |
Current International
Class: |
C25D
5/56 (20060101); C25D 5/54 (20060101); H05K
3/18 (20060101); C23b 005/60 (); B44c 001/18 () |
Field of
Search: |
;204/20,30
;117/201,47A,47R ;252/510,511 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
196,063 |
|
Apr 1923 |
|
GB |
|
534,818 |
|
Mar 1941 |
|
GB |
|
437,430 |
|
Oct 1946 |
|
CA |
|
Other References
Chemical Abstracts, Vol. 40, 2673. .
Industrial Carbon, Mantell, Van Nostrand, 1946, p. 87. .
The Electrodeposition of Iron, A. D. Squitero Products
Finishing..
|
Primary Examiner: Tufariello; T. M.
Claims
I claim:
1. A process for metallizing comprising (1) introducing an
essentially solid surface in contact with a metallic conductor into
an electroplating bath from which a metal from the Group VIII of
the periodic table and alloys thereof can be plated; (2) said
essentially solid surface comprising an intimate mixture of an
organic polymer reactive with sulfur, a carbon black and a
substance from the group of sulfur and sulfur donors and having a
volume resistivity of less than about 1,000 ohm-centimeters and (3)
applying a potential to said surface through said metallic
conductor to cause metal from said group to deposit upon said
surface in an essentially uniform manner from the locus of said
metallic conductor.
2. A process as in claim 1 wherein the metal is from the group of
iron, nickel and cobalt.
3. A process as in claim 2 wherein the polymer is an elastomer.
4. A process as in claim 2 wherein the carbon black is a conductive
carbon black and the surface material has a volume resistivity of
about 1 to about 10 ohm-centimeters.
5. A process as in claim 2 wherein the potential is in excess of
about 0.2 volt cathodic.
6. A process as in claim 2 wherein the metal deposited is from the
group of nickel and cobalt.
7. A process as in claim 6 wherein the metal deposit is nickel.
8. A process as in claim 3 wherein the elastomer is an unsaturated
elastomer.
9. A process as in claim 8 wherein the elastomer is
polychloroprene.
10. A process as in claim 1 wherein the essentially solid surface
contains a conductive carbon black and comprises a coating on a
substrate.
11. A process as in claim 10 wherein a metal from the group of
iron, nickel and cobalt is deposited on said essentially solid
surface.
12. A process as in claim 10 wherein the substrate is a
non-conductor of electricity.
13. A process as in claim 12 wherein the substrate is a
plastic.
14. A process as in claim 11 wherein the composition used to form
the coating contains sulfur.
15. A process as in claim 11 wherein the composition used to form
the coating is treated subsequent to coating formation to enrich
the surface thereof with sulfur.
16. A process as in claim 11 wherein the material of the coating
has a volume resistivity in the range of about 1 to about 10
ohm-centimeters.
17. A process as in claim 10 wherein the metal deposited is from
the group of cobalt and nickel.
18. A process as in claim 17 wherein the metal deposited is
nickel.
19. A process as in claim 17 wherein the metal deposited on said
surface spreads rapidly across said surface behind a sharply
defined plating front.
20. A process as in claim 10 wherein the solid surface contains an
elastomer.
21. A process as in claim 20 wherein the elastomer is an
unsaturated elastomer.
22. A process as in claim 21 wherein the unsaturated elastomer is
polychloroprene.
23. A process as in claim 12 wherein the substrate is a fiberous
aggregation.
24. A process as in claim 1 wherein said essentially solid surface
is the surface of a mass having an essentially uniform composition
therethrough.
25. A process as in claim 24 wherein the uniform composition
includes an elastomer.
26. A process as in claim 24 wherein nickel is deposited on said
essentially solid surface.
27. A process as in claim 24 wherein the uniform composition
includes polyethylene or polypropylene.
28. A process as in claim 25 wherein the elastomer is an
ethylene-propylene terpolymer.
29. A process as in claim 27 wherein the final electrodeposit is
aged on said uniform composition to increase the adhesion of said
deposit to said composition.
Description
The present invention is concerned with electrodeposition and more
particularly with electroplating of a non-electrically conductive
substrate.
BACKGROUND OF THE INVENTION
Since the start of electroplating, a large number of proposals have
been made with respect to electroplating on
non-electrically-conductive substrates ranging in size and shape
across the gamut of leaves, flowers, baby shoes, plastic knobs,
bottle tops, molded plastic parts for automotive usage and
uncounted other practical and decorative structures. Basically, two
processes have been used. The first process involves the coating of
the non-conductive object with an electrically conductive lacquer
followed by electroplating. The second process involves sensitizing
the non-conductive object, chemically depositing a metal on the
sensitized surface and thereafter electroplating the thus
metallized surface.
The two generally available processes as practiced in the prior art
have certain disadvantages. Because of high loadings of conductive
pigments such as graphite or metal, prior art conductive lacquers
are generally very weak and thus constitute a weak link in the
ultimate electroplated structure. A variation of the lacquer
process which involves coating the tacky lacquer surface with
graphite again produces very weak bonds between electrodeposited
metal and the lacquer much like the ephemeral bond produced between
graphitized wax and electrodeposited metal in the electrotyping
process. If lower pigment loadings are used in a conductive lacquer
to give greater strength in the lacquer, the rate of initial metal
coverage of the article during electroplating is radically
decreased necessitating the use of multiple electrical contact
points on the object to be plated or allowance of a long time for
metal coverage and consequent uneven plating thicknesses.
The second process as generally practiced by the prior art, can
achieve good results but only at a cost of employing a large number
of individual processing operations carried out with very great
care by skilled personnel. Furthermore, because the underlying
chamically deposited metal can be different from metal subsequently
electrochemically deposited, there is a good chance of forming an
electrochemical couple between the two even when, nominally the
metals are the same. Thus the possibility of accelerated, localized
corrosion exists wherever and whenever the outer electrodeposited
layer is not continuous.
Recently, U.S. Pat. No. 3,523,875 to Minklei and U.S. Pat. No.
3,682,786 to Brown et al. have issued. These recently issued
patents are worthy of discussion because, superficially they might
appear to resemble the process of the present invention. Minklei
proposed to treat a plastic surface with an aqueous solution of
alkali metal sulfide followed by contacting the treated surface
with a metal salt prior to electroplating. Brown et al. proposed
contacting a plastic surface with a solution or dispersion of
sulfur in an organic medium and contacting the treated surface with
an aqueous solution of cuprous salt prior to plating. In both
instances, the proposals involve the formation of a metal sulfide
on the plastic surface and not the type of metal-polymer bond,
which, as will become apparent from the subsequent description, is
formed by virtue of the process of the present invention.
OBJECTS
It is an object of the present invention to provide a process for
electrodepositing metal on non-electrically-conductive
substrates.
It is another object of the present invention to provide a process
for electrodeposition on substrates which are not amenable to
ordinary electrodeposition techniques.
Other objects and advantages will become apparent in light of the
following description taken in conjunction with the drawing in
which
FIG. 1 depicts electrodeposit growth obtained in accordance with
the present invention and;
FIG. 2 depicts undesirable electrodeposit growth obtained when an
essential requirement of the process of the present invention is
omitted.
DESCRIPTION OF THE INVENTION
Generally speaking the present invention contemplates a process
wherein at least part of a substrate for electrodeposition
comprises or is coated with an adherent layer of a mixture of an
organic polymer and an electrically conductive carbon black of such
proportion so as to have an electrical resistivity of less than
about 1,000 ohm-centimeter; at least the exposed surface of the
layer is caused to contain an effective amount of sulfur, and the
thus coated object is then introduced into a nickel, cobalt, or
iron plating bath as the cathode to cause rapid deposition of metal
across the coated surface. Thereafter the metal coated object can
be subjected to further electrodeposition in ways well known to
those skilled in the art.
The polymer used along with conductive carbon black in the coating
layer (and which may also constitute the substrate) is,
advantageously a member of the group of organic polymers which
readily react with molecular sulfur or a sulfur donor of the type
described herein. Advantageous polymers for use in the process of
the present invention include hydrocarbonaceous and substituted
hydrocarbonaceous elastomers such as natural rubber, a
polychloroprene, butyl rubber, chlorinated butyl rubber,
polybutadiene rubber, acrylonitrile-butadiene rubber,
styrene-butadiene rubber, etc. These elastomers are unsaturated and
readily combine with molecular sulfur through either unsaturated
linkages in the carbon skeletal structure of the polymer or through
activated sites on the polymer structure associated with
unsaturated linkages or pendant substituent atoms. Another
advantageous type of polymer for use in the process of the present
invention is an ethylene-propylene terpolymer comprising a
saturated poly-ethylene-propylene main chain having unsaturated
groups derived from non-conjugated dienes, e.g., hexadiene,
dicyclopentadiene etc., pendant from the main chain. Such a
terpolymer is readily vulcanized with sulfur. Other polymers useful
in the process of the present invention include essentially
saturated polymers such as polystyrene, polyvinyl chloride,
polyurethane etc., which apparently possess active sites for
reaction with sulfur. While polyethylene (and similar polymers of
limited solubility) are not readily suited for use in coating
formulations, it has been found that milled and molded polyethylene
compositions containing carbon black and a sulfur donor can
advantageously be employed in the process of the present invention.
Undoubtedly some organic polymers, for example, perhaps,
polytetrafluoroethylene are too inert to react with sulfur and
these polymers are excluded from the ambit of the present
invention. However, the great bulk of normally used organic
polymeric materials appears to be useable in the process of the
present invention.
Of those polymers which react with sulfur, those having elastomeric
characteristics e.g., rubbers, elastomeric polyurethane etc., are
considered to be advantageous when used as a coating covering a
rigid base and overlied by the deposited metal, because an
elastomer has the ability to dampen stress concentrations which can
result in failure of the deposited coating upon exposure to applied
stress or thermal cycling. In addition, with most elastomers, the
carbon black included for the purpose of providing a proper degree
of electrical conductivity acts as a reinforcement agent to improve
the physical characteristics of the elastomer. Further factors
which make elastomers most advantageous include rapidity of metal
coverage and relatively low cost of materials. Among the
elastomers, the unsaturated elastomers are deemed to be the most
advantageous.
Those skilled in the art will appreciate that in the foregoing
description of polymers operable in the process of the present
invention the examples given are merely illustrative and that many
other polymeric and copolymeric materials and mixtures can be used
in place of the specifically mentioned substances. For example,
very often in rubber formulations amounts of compatible
non-elastomeric resins are included for various purposes. Polymers
other than rubber can, and often are compounded with plasticizers
in order to obtain a product having flexibility. Such compounded
materials as well as copolymers and mixed polymers are operable for
purposes of the present invention.
When as is always advantageous the exposed surface of the
polymer-conductive carbon black composition is caused to contain
sulfur it is possible that the sulfur initially attacks the polymer
chain at activated positions, to provide activated sites for
bonding of nickel to the polymer. Regardless of the theoretical
explanation however, applicant's experiments have shown that when
nickel deposits are made in accordance with the teachings of the
present invention very strong, highly useful metal to organic bonds
are formed very strong, highly useful metal to organic bonds are
formed very rapidly on polymer-carbon black surfaces. It is
important to avoid overcuring of a polymer with sulfur (or other
curative) prior to plating. It appears that a polymer-sulfur-metal
bond can occur with most polymers as long as activated sites on the
polymer chain exist. Heavy curing, especially in sulfur
monochloride will remove these sites from an unsaturated elastomer
causing poor plating both as to speed of coverage and as to
adherence of the metal.
The exposed surface of the polymer-carbon black plating substrate
can contain sulfur by inclusion of sulfur in the whole mass of the
plating substrate or by enriching the exposed surface with
sulfur.
Normally, a plating substrate containing an unsaturated polymeric
elastomer will contain about 0.5% to about 5% of sulfur based upon
weight of elastomer in order to permit curing of the elastomer.
When agents other than sulfur or sulfur compounds are used for
curing the exposed surface of the elastomer can be enriched in
sulfur by contacting the surface with a solution containing
elemental sulfur or by exposing the surfaces to a sulfur-containing
vapor e.g., the vapor of sulfur monochloride (S.sub.2 Cl.sub.2).
The plating substrate will normally contain ingredients other than
sulfur, elastomer and conductive carbon black such are normally
included in rubber compositions. Such other ingredients include
vulcanization accelerators and modifiers, antioxidants and similar
types of materials which have been found to be useful in rubber
technology. For best results, particularly with respect to adhesion
of electrodeposited metal all ingredients should be limited in
amount to amounts which will be permanently soluble in the cured
elastomer at normal temperatures i.e., about 25.degree.C.
Plating substrates used in the present invention usually contain
carbon black and polymer in weight ratios of about 0.2 to about 1.5
(conductive carbon black to polymer) although somewhat higher or
lower weight ratios can be used. It is usually more advantageous to
employ weight ratios of conductive carbon black to polymer in the
range of about 0.5 to 1.0. It has been noted with coatings on
non-electrically conductive substrates that speed of coverage of
polymer-carbon black surfaces becomes very low at very high
loadings of carbon black indicating that a minimum surface
concentration of polymer is necessary not only for attaining
mechanical strength but also for purposes of facilitating the metal
spreading mechanism of the invention. Because carbon blacks vary
greatly depending upon sources and methods of manufacture, it is
not practical to specify with more precision the relative amounts
of polymer and carbon black required in accordance with the present
invention. In addition to variations involved in different types of
carbon black, difference in dispersion conditions when compounding
with polymer can also introduce variations in the polymer-carbon
black mixtures. For example, if an acetylene black sold by
Shawinigan Products Corp. of Englewood Cliffs, N.J., is milled with
an elastomer in a Banbury-type mill, it is likely that at least
part of the chain-like structures of the acetylene black will be
broken. On the other hand using less agressive mixing techniques,
the chain structure will be retained. Consequently, the composition
milled in the Banbury mixer will exhibit a higher volume
resistivity than will a composition milled in solution form in a
blender event though the loading of the carbon black is the same.
Thus for purposes of the invention, the criterion of operability of
a particular polymer-carbon black mixture is the electrical volume
resistivity. As stated hereinbefore, the volume resistivity must be
less than about 1,000 ohm-centimeters and more advantageously is
less than about 10 ohm-centimeters. Ordinarily it is neither
possible nor desirable to obtain polymer-carbon black mixtures
having volume resistivities less than about 1 ohm-centimeter. At
such low resistivities, the strength of the polymer-carbon black
mixture is low. Optimum results have been obtained using conductive
carbon blacks made from acetylene such as sold by Shawingan
Products Corporation under the trade designation Acetylene Carbon
Black. Another commercially available conductive carbon black which
possesses relatively high resistance to mechanical breakdown during
milling with a polymer is sold by Cabot Corporation under the trade
designation of Vulcan XC72. If desired, mixtures of conductive and
non-conductive carbon blacks can be used provided that the final
polymer-carbon black product has a volume resistivity in the range
set forth hereinbefore. In some instances the proper volume
resistivity can be achieved in polymer-carbon black compositions
which are made entirely with non-conductive carbon blacks for
example, furnace blacks. Such compositions ordinarily do not have
adequate electrical characteritics when used as coatings and dried
on a substrate. However, these compositions may have adequate
characteristics for use as molded, extruded or like-formed shapes
which can be treated electrochemically in accordance with the
present invention without a separate preliminary coating step.
The rate of coverage of nickel cobalt or iron on a cathode having a
surface of polymer-carbon black mixture in accordance with the
present invention extending from a point of contact with an
electronic conductor (e.g., a metal) is dependent at least upon the
resistivity of the mixture, the sulfur content at the mixture
surface, the applied voltage across the anode-electrolyte-cathode
circuit; and the nature of the polymer. Generally speaking in
accordance with the present invention the minimum rate at which
nickel spreads across the cathode surface at a voltage of 3.0 volts
is about 0.5 centimeter per minute (cm/min.). A series of
polymer-acetylene black compositions were made containing 100 parts
by weight of polymer and 50 parts by weight of the carbon black.
The compositions devoid of sulfur were coated on an ABS panel
having a metal contact point at one end. In a first series of tests
the panels were immersed in a Watts' type nickel plating bath as
cathodes at a voltage of 3.0. The rate of nickel coverage was
measured. In a second series of tests, the panels were dipped in a
solution of 1% (by weight) of sulfur in cyclohexane, removed and
the cyclohexane allowed to evaporate prior to electrolytic
treatment in exactly the same manner as was the first series. The
results of these tests are set forth in Table I.
TABLE I ______________________________________ Polymer Ni coverage
rate (cm/min) Series I Series II
______________________________________ Polystyrene 0.25 1.19
Polyvinyl chloride 0.15 0.99 Chlorinated Rubber (Parlon) 0.31 0.89
Nitrile Rubber (Paracril BJLT) 0.31 2.24 Natural Rubber (Smoked
Sheet) 0.31 0.89 Neoprene Rubber (Neoprene AD) 0.58 1.78
______________________________________
Table I shows that a very small amount of sulfur incorporated in
the exposed surface of the polymer increases nickel coverage rates
by a factor of at least about 2.5. When sulfur is included in the
polymer-carbon black compositions and not merely in the very
surface layer as in the materials of Series II Table I, rates of
nickel coverage can be much higher. For example, with a composition
containing 100 parts by weight nitrile rubber, 50 parts by weight
acetylene black and 4 parts by weight sulfur, nickel coverage rates
at 3.0 volts of over 6 cm/min. can be obtained. The rate of nickel
coverage increases linearly with increases in voltage. Using a
composition containing a weight ratio of 2 to 1 of nitrile rubber
to acetylene black and 2.5% by weight of sulfur based upon the
weight of rubber, a nickel coverage rate of about 9.5 cm/min. was
obtained at a voltage of 3.0 and a rate of about 14.7 cm/min. at a
voltage of 4.5. It is important that the sulfur present in the
polymer-carbon black compositions be in the form of non-ionic
sulfur, i.e., that it not be tied up as a metal sulfide or in a
stable ion such as the sulfate ion. Ordinarily, elemental sulfur is
used but, if desired, sulfur in the form of a sulfur donor such as
sulfur chloride, 2-mercapto-benzothiazole,
N-cyclohexyl-2-benzothiozole sulfonomide, dibutyl xanthogen
disulfide and tetramethyl thiuram disulfide or combinations of
these and sulfur can also be employed. Those skilled in the art
will recognize that these sulfur donors are the materials which
have been used or have been proposed for use as vulcanizing agents
or accelerators.
The advantage obtained when sulfur is included in the
polymer-carbon black surface is dramatically depicted in the
drawing. Referring now thereto both FIGS. 1 and 2 depict indentical
acrylonitrile-butadiene-styrene plaques 11 coated with
polymer-carbon black coating 12 containing 20 parts by weight of
neoprene and 10 parts by weight of acetylene black and having a
wire contact 13.
The coating 12 of FIG. 1 initially contained a small amount of
thiuram and was treated with a 1% by weight solution of sulfur in
cyclohexane prior to plating so as to incorporate a small effective
amount of sulfur in the coating. Coating 12 of FIG. 2 was made with
a neoprene free of thiruam, was not exposed to a sulfur solution
and therefore contained no sulfur. Both plaques were made cathodic
under identical voltage conditions (3 volts closed circuit cell
potential) in the same nickel plating bath. After 1 1/2 minutes the
area 15 above line 14 in FIG. 1 was uniformly coated with a highly
adherent nickel deposit. At this time the plaque was removed from
the plating bath. If it were not removed from the bath, the plating
front, as depicted by line 14, would continue downwardly across
plaque 11 of FIG. 1 until, at the end of about 5 minutes the whole
plaque would be coated with a firm, adherent, even deposit of
nickel. In contrast, the plaque of FIG. 2, after 20 minutes in the
plating bath, had a loosely adherent fern-like deposit on the area
external of closed, irregular curves 16 and 17 leaving sulfur-free
coating 12 exposed internally of closed irregular curves 16 and 17.
A comparison of FIGS. 1 and 2 of the drawing clearly shows that
plating practice in accordance with the present invention is highly
advantageous.
The cathodic electrolytic treatment used according to the present
invention to induce nickel coverage across the expanse of
polymer-carbon black mixture surface is carried out in an
electrolyte bath from which nickel can be deposited and which,
ordinarily is aqueous and contains about 70 to about 120 grams per
liter (gpl) of nickel ion, complementing anion from the group of
sulfate, chloride, sulfamate, fluoborate and mixtures thereof and
exhibits a pH of about 2.8 to about 4.5 stabilized by inclusion of
a buffer such as boric acid in the bath. An ordinary Watts bath is
quite satisfactory for use both as the initial bath for nickel
coverage and for subsequentt plating. If desired, after nickel
coverage has been established, one can plate in a nickel bath
containing any kind of additive, e.g., levelling agents or
brightening agents, etc., known to the art. Further, after nickel
coverage is established one can plate not only with nickel but also
with any other electrodepositable metal compatible with nickel,
e.g., chromium, copper. zinc, tin, silver, gold, platinum,
palladium, cadmium etc.
The cathodic treatments in accordance with the invention to induce
the growth of iron or cobalt across the polymer carbon-black
surface can be carried out in any electroplating bath from which
these metals can be deposited. For example, the process of the
invention has been carried out using an aqueous ferrous chloride
bath to deposit iron and an aqueous cobalt chloride-cobalt sulfate
bath to deposit cobalt. Details of operation for these and other
iron, cobalt and nickel baths can be obtained from any text on
electroplating, for example, Electoplating Engineering Handbook,
edited by A. Kenneth Graham, Reinhold Publishing Corporation,
Copyright 1955. Those skilled in the art will appreciate that for
particular purposes it may be advantageous to deposit alloys of
nickel, cobalt and iron such as iron-nickel alloys, nickel-cobalt
alloys etc.
In addition to iron, nickel and cobalt, other metals of Group VIII
of the Periodic Table of Elements can be deposited in the manner as
depicted in FIG. 1 of the drawing, that is initially behind a
deposition front moving across the polymer-carbon black surface. In
particular palladium has been found to spread across a
polymer-carbon black surface at a rate roughly equivalent to the
rate at which iron spreads, which rate is somewhat slower than the
spreading rate of nickel and cobalt all other conditions being
equal.
While the present invention is especially concerned with
electrodeposition of metal on a wide variety of plastic and other
non-conductors (and on other materials which are not generally
amenable to ordinary electroplating techniques) using a coating
technique involving an essentially solid polymer
carbon-black-sulfur-containig coating adhered directly or through
an intermediate layer onto a base, the invention is also applicable
to bases having the requisite carbon black-polymer-sulfur
composition. As an example, a sample of EPDM synthetic rubber
having a volume resistivity of about 235 ohm-centimeters and
containing reinforcing type, furnace carbon black and sulfur is
directly plateable in a Watts-type nickel bath to provide a highly
adherent, rapidly formed overall deposit of nickel. The spreading
of the deposit from a point of metallic conduction differs somewhat
in the case of a solid base of polymer-carbon black-sulfur from the
spreading depicted in FIG. 1 of the drawing which is typical of
metal spreading using coatings. With a solid polymer-carbon
black-sulfur base the electrodeposited metals tends to rapidly film
over the entire surface of the object blurring to a certain extent
the metal deposition front depicted in FIG. 1 of the drawing.
In order to give those skilled in the art a better understanding
and appreciation of the invention the following examples are
given:
EXAMPLE I
A coating formulation was made up as follows:
Material Parts-by-weight ______________________________________
Natural Rubber (Smoked Sheet) 100 Nitrile Rubber (Paracril
BJLT).sup.1 100 Acetylene Carbon Black.sup.2 100 Sulfur 4
Trichloroethylene 10,000 ______________________________________ (1)
Product of Uniroyal Chemical, Naugatuck, Conn. (2) Product of
Shawinigan Products Corp., Englewood Cliffs, N.J.
The aforedescribed coating formulation was sprayed on an
acrylonitrile-butadiene-styrene (ABS) surface to provide a dried
coating about 0.0025 cm. thick. The coated and dried ABS surface
was then exposed for 40 seconds to the vapor above sulfur
monochloride held at room temperature (about 25.degree.C). The
surface having a single metal contact was then placed in a
Watts-type nickel plating bath as a cathode with a driving voltage
of about 3 volts in opposition to a nickel anode. The nickel
deposit grew rapidly across the coated ABS surface and deposition
was continued until the deposited nickel had a substantially
uniform thickness of about 0.0025 cm. The electrodeposit showed a
90.degree. peel strength of about 1.88 kilogram per centimeter
(kg/cm) width (10.5 lb/in width) when pulled at 2.54 cm/minute.
EXAMPLE II
The following coating formulations were prepared:
Coating A Material Parts-by-Weight
______________________________________ Nitrile Rubber (Paracril
BJLT) 9.87 Stearic Acid 0.099 Zinc Oxide 0.493 Dibutyl Xanthogen
Disulfide (C-P-B).sup.1 0.394 Zinc diethyl dithiocarbamate
(Ethazate).sup.1 0.025 Dibenzylamine (D-B-A).sup.1 0.394 Sulfur
0.394 Methyl Ethyl Ketone (MEK) 11.3 Xylene 77.5 Coating B Material
Parts-by-Weight ______________________________________ Acetylene
Carbon Black 4.39 Nitrile Rubber (Paracril BJLT) 8.78 Stearic Acid
0.088 Zinc Oxide 0.044 Butyl Rubber 0.044 Dibutyl Xanthogen
Disulfide (C-P-B).sup.1 0.351 Zinc diethyl dithiocarbamate
(Ethazate).sup.1 0.022 Dibenzylamine (D-B-A).sup.1 0.351 Sulfur
0.351 Trichloroethylene 32.9 Xylene 52.6
______________________________________ .sup.1 Products of Uniroyal
Chemical, Naugatuck, Conn.
Coating A was applied by brushing onto a poly-(vinyl chloride)
(PVC) plaque, and then coating B was applied in similar fashion
over the dried coating A. After curing in an air oven for 3 hours
at 90.degree.C. the plaque was dipped into a 1 w/o solution of
sulfur in cyclo-hexane, then plated to a thickness of about 0.001
inch with Watts nickel. Initially the nickel deposit grew rapidly
across the surface of the plaque from a single metal contact. A
90.degree. peel strength of 2.5 kg/cm (12 lb/in) was achieved for
the electrodeposit.
EXAMPLE III
The following coating formulations were prepared:
Coating C Material Parts-by-Weight
______________________________________ Neoprene AF.sup.1 50 Neozone
D.sup.1 1 Magnesia 2 Zinc Oxide 2.5 Alkyl Phenolic Resin
(SP-136).sup.2 20 Ethyl Acetate 80 Hexane 82 Toluene 81 Water 0.5
Coating D Material Parts-by-Weight
______________________________________ Acetylene Carbon Black 15
Natural Rubber (Smoked Sheet) 7.5 Styrene Butediene Rubber
(Naugapel 7.5 (1503).sup.3 Sulfur 0.9 Heptane 240 Turpentine 70
Trichloroethylene 75 ______________________________________ .sup.1
Products of E. I. Dupont de Nemours and Co. .sup.2 Product of
Schenectady Chemical Inc., Schenectady, N.Y. .sup.3 Product of
Uniroyal Chemical, Naugatuck, Conn.
An ABS panel was dipped in coating C, air dried, then dipped into
coating D, and again air dried. It was then directly electroplated
in a Watts bath and the resulting nickel electrodeposit had a
90.degree. peel strength of 1.79 kg/cm of width (10 lb/in.).
EXAMPLE IV
Coatings A and B from Example II were modified so that the
concentration of curatives (C-P-B, Ethazate, D-B-A and sulfur) was
doubled. In addition, MEK was added to coating A such that its
final weight equaled that of the xylene (i.e., from 11.3 to 77.5).
An ABS panel was successively dipped in modified coating A, then
into modified coating B. The panel was cured at 85.degree.C for
11/2 hours, during which time a noticeable sulfur bloom appeared on
the surface. The panel was then directly electroplated with Watts
nickel with a rapid initial rate of coverage. The resulting metal
deposit exhibited a 90.degree. peel adhesion of about 3.58 kg/cm of
width (20 lb/in).
EXAMPLE V
An ABS panel (Cycolac standard test plaque) was coated by
successively dipping in first coating A, then coating B of Example
II. After curing 15 hours in air at 85.degree.C, the panel was
dipped into a 1 w/o solution of sulfur in cyclohexane. It was then
plated with a Watts FLASH, 0.0009 inch of semibright (Perflow)
nickel, 0.0003 inch of bright (Udylite) nickel and 15 .mu. in
conventional chromium. The plated panel was given a thermal cycle
of 90.degree.C for 2 hours, room temperature for 1 hour,
-40.degree.C for 2 hours, and then given a 16-hour exposure to CASS
testing. No detectable failure resulted on the panel from this
treatment.
Those skilled in the art will appreciate that although in most of
the foregoing examples ABS plastic plaques were used, the process
of the present invention is equally as well adapted to the
electroplating of utilitarian and decorative objects made of other
plastics such as polystyrene, phenol formaldehyde resins,
urea-formaldehyde resins, polyacrylates and methacrytates,
polyurethane, silicones, vinyls, vinylidenes, epoxys, polyolefins
and similar thermoplastic and thermosetting resinous materials. In
addition, the process of the present invention can also be used to
plate metals which are coated with non-metallic, non-electrically
conductive coatings, e.g., varnished aluminum and the like. Those
skilled in the art, in considering the scope of utility of the
process of the present invention, will recognize that with some
base materials it will be necessary to include an adhesive layer
between the polymer carbon black plating substrate and the
particular base material. While the form and character of the base
material is not of significance to the operability of the process
of the present invention, particular base materials can provide
qualities of utility not ordinarily contemplated. For example, a
loosely matted paper was coated with a polymer-carbon black-sulfur
mixture to provide after metal deposition a novel useful electrode
skeleton for a battery plaque, fuel cell electrode or the like. In
this regard special attention is directed to the deposition of
precious metals from Group VIII. While economic factors make it
unlikely that platinum, palladium, rhodium, iridium, ruthenium and
osmium would find much use in the decorative plating of plastics,
these metals can be usefully deposited in the form of electrodes,
catalysts, etc., where their particular chemical and
electrochemical characteristics can be utilized.
EXAMPLE VI
A sample plastic treated and coated as in Example III was immersed
as a cathode in an aqueous plating bath containing 300 gpl of
ferrous chloride, 150 gpl of calcium chloride adjusted to a pH of
1.2 to 1.8 and held at a temperature of about 87.degree.C. Upon
passage of current through the bath at a voltage of 6 volts, the
surface of the sample became covered with a smooth adherent coating
of iron.
EXAMPLE VII
The sample of Example VI was immersed as a cathode in an aqueous
cobalt plating bath containing about 335 gpl of cobalt sulfate,
about 74 gpl of cobalt chloride, about 46.5 gpl of boric acid and
about 1.2 gpl of sodium fluoborate. Upon passage of current through
the bath, the sample rapidly filmed over with cobalt.
EXAMPLE VIII
One hundred parts by weight of a low-density, general purpose
polyethylene were milled in a Banbury type mixer at a temperature
of about 178.degree.C. along with 50 parts by weight of Vulcan XC72
carbon black (supplied by Cabot Corporation) and Tetrone A brand
dipentamethylenethiuram hexasulfide. The milled composition was
then molded and the molding thus produced was inserted as a cathode
in a nickel plating bath. Nickel rapidly spread over the surface
from a metallic point of contact and plating was continued to
provide a firm, adherent nickel electrodeposit having a 90.degree.
peel strength of about 1.8 kg/cm of width.
Although the present invention has been described and illustrated
in conjunction with preferred embodiments, it is to be understood
that modifications and variations may be resorted to without
departing from the spirit and scope of the invention. For example,
those skilled in the art will appreciate that the molding
composition upon which nickel was deposited in Example VIII is
illustrative of a broader range of polyethylene, polypropylene and
mixtures and copolymers thereof having blended therein about 15% to
about 60% by weight (of the total composition) of carbon black, to
give a volume resistivity of less than about 1,000 ohm-centimeters,
along with sulfur or a sulfur donor for example of the
dipentamethylenethiuran hexasulfide type in an amount equivalent in
sulfur content to about 1% to about 10% by weight (of the total
composition) of dipentamethylenethiuram hexasulfide. In plating
massive polymer bodies as in Example VIII an interesting phenomenon
has been noted, that is, the bond strength of nickel
electrodeposited on the polymer surface improves with aging at room
temperature. Thus the 90.degree. peel strength set forth in Example
VIII is the peel strength observed immediately after plating. After
a few days aging the observed bond strength is often double (or
more) of that strength as set forth in Example VIII. Such
compositional and processing modifications and variations are
considered to be within the purview and scope of the invention and
appended claims.
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