U.S. patent number 3,650,708 [Application Number 05/023,967] was granted by the patent office on 1972-03-21 for metal plating of substrates.
This patent grant is currently assigned to Hooker Chemical Corporation. Invention is credited to William P. Gallagher.
United States Patent |
3,650,708 |
Gallagher |
March 21, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
METAL PLATING OF SUBSTRATES
Abstract
Substrates, particularly plastics, are plated with metals by
pretreatment of the substrate with phosphorus sesquisulfide in an
organic solvent to deposit phosphorus sesquisulfide at the surface,
followed by containing the treated surface with a metal salt or
complex thereof, to form a metal-phosphorus-sulfur compound. The
resulting treated surface is either conductive or is capable of
catalyzing the reduction of a metal salt to produce a conductive
surface. Such conductive surfaces are readily electroplated by
conventional techniques.
Inventors: |
Gallagher; William P.
(Monroeville, PA) |
Assignee: |
Hooker Chemical Corporation
(Niagara Falls, NY)
|
Family
ID: |
21818159 |
Appl.
No.: |
05/023,967 |
Filed: |
March 30, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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855037 |
Sep 3, 1969 |
|
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Current U.S.
Class: |
428/623; 205/169;
427/306; 427/419.1; 428/461; 428/463; 428/656; 428/936; 205/166;
427/123; 427/404; 427/438; 428/418; 428/462; 428/626; 428/935 |
Current CPC
Class: |
C23C
18/26 (20130101); C23C 18/30 (20130101); C23C
18/2086 (20130101); Y10T 428/12549 (20150115); Y10T
428/31696 (20150401); Y10T 428/31699 (20150401); Y10S
428/935 (20130101); Y10S 428/936 (20130101); Y10T
428/31692 (20150401); Y10T 428/12569 (20150115); Y10T
428/12778 (20150115); Y10T 428/31529 (20150401) |
Current International
Class: |
C23C
18/20 (20060101); C23C 18/26 (20060101); B23p
003/00 () |
Field of
Search: |
;117/47,130,160,71
;204/30 ;29/195 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3403035 |
September 1968 |
Schneble et al. |
3445350 |
May 1969 |
Klinger et al. |
|
Other References
Bayard, J. J. Electrodeposition on Plastic Materials in Metal
Industry, May 1970, p. 256..
|
Primary Examiner: Kendall; Ralph S.
Parent Case Text
REFERENCE TO PRIOR APPLICATION
This is a continuation-in-part of application Ser. No. 855,037,
filed Sept. 3, 1969, and now abandoned.
Claims
I claim:
1. A process which comprises subjecting a substrate to phosphorus
sesquisulfide to deposit phosphorus sesquisulfide at the surface of
the substrate and thereafter subjecting the phosphorus
sesquisulfide treated surface to a solution of a metal salt or
complex thereof so as to form a metal-phosphorus-sulfur coating,
wherein said metal is selected from the Groups IB, IIB, IVB, VB,
VIB, VIIB, and VIII of the Periodic Table.
2. A process wherein the treated substrate resulting from the
process of claim 1 is subjected to electroless metal plating to
deposit an electroless conductive coating on the treated
substrate.
3. A process wherein the substrate resulting from the process of
claim 2 is electroplated to deposit an adherent metal coating on
the electroless conductive coating.
4. A process wherein the treated substrate resulting from the
process of claim 1 is electroplated to deposit an adherent metal
coating on the treated substrate.
5. A process which comprises subjecting a plastic to phosphorus
sesquisulfide to deposit phosphorus sesquisulfide at the surface of
the plastic and thereafter subjecting the phosphorus sesquisulfide
treated substrate to a solution of metal salt or complex thereof
which so as to form a metal-phosphorus-sulfur coating, wherein said
metal is selected from Groups IB, IIB, IVB, VB, VIB, VIIB, and VIII
of the Periodic Table.
6. The process according to claim 5 wherein the plastic is
subjected to a solution of phosphorus sesquisulfide dissolved in a
solvent.
7. The process according to claim 6 wherein the solvent is a
halogenated hydrocarbon.
8. The process according to claim 7 wherein the solvent is
trichloroethylene.
9. The process according to claim 7 wherein the solvent is
methylene chloride.
10. The process of claim 6 wherein the metal of said metal salt is
selected from the group consisting of nickel and copper.
11. The process of claim 6 wherein the metal salt complex is a
complex of ammonia, amines, quinolines or pyridines.
12. The process of claim 6 wherein the plastic is polypropylene,
the phosphorus sesquisulfide is employed as a solution of
phosphorus sesquisulfide dissolved in trichloroethylene, and the
metal salt complex is a complex of nickel.
13. The process of claim 6 wherein the plastic is an epoxy resin,
the phosphorus sesquisulfide is employed as a solution of
phosphorus sesquisulfide dissolved in a mixture of
trichloroethylene and methylene chloride, and the metal of the
metal salt complex is nickel.
14. A process wherein the treated plastic surface resulting from
the process of claim 6 is subjected to electroless metal plating to
deposit an electroless conductive coating on the treated plastic
surface.
15. A process wherein the plastic surface resulting from the
process of claim 14 is electroplated to deposit an adherent metal
coating on the electroless conductive coating.
16. A process wherein the treated plastic surface resulting from
the process of claim 6 is electroplated to deposit an adherent
metal coating on the treated plastic surface.
17. An article having a metal-phosphorus-sulfur coating adherently
formed at the surface of a plastic, wherein said metal is selected
from the Groups IB, IIB, IVB, VB, VIB, VIIB, and VIII of the
Periodic Table.
18. The plastic articles of claim 17 wherein at least one component
of the plastic is a thermoplastic polymer.
19. The plastic article of claim 17 wherein at least one component
of the plastic is polyproylene.
20. The plastic article of claim 17 wherein at least one component
of the plastic is polyethylene.
21. The plastic article of claim 17 wherein at least one component
of the plastic is polyvinyl chloride.
22. The plastic article of claim 17 wherein at least one component
of the plastic is a graft copolymer of polybutadiene, styrene and
acrylonitrile.
23. The article of claim 17 having an adherent electroless
conductive coating deposited on the metal-phosphorus-sulfur
coating.
24. The article of claim 23 having an adherent metal coating
electrolytically deposited on the electroless conductive
coating.
25. The plastic article of claim 24 wherein at least one component
of the plastic is a thermoplastic polymer.
26. The plastic article of claim 24 wherein at least one component
of the plastic is polypropylene.
27. The plastic article of claim 24 wherein at least one component
of the plastic is polyethylene.
28. The plastic article of claim 24 wherein at least one component
of the plastic is polyvinyl chloride.
29. The plastic article of claim 24 wherein at least one component
of the plastic is a graft copolymer of polybutadiene, styrene and
acrylonitrile.
30. The article of claim 17 having an adherent metal coating
electrolytically deposited on the metal-phosphorus-sulfur
coating.
31. The plastic article of claim 30 wherein at least one component
of the plastic is a thermoplastic polymer.
32. The plastic article of claim 30 wherein at least one component
of the plastic is polypropylene.
33. The plastic article of claim 30 wherein at least one component
of the plastic is polyethylene.
34. The plastic article of claim 30 wherein at least one component
of the plastic is polyvinyl chloride.
35. The plastic article of claim 30 wherein at least one component
of the plastic is a graft copolymer of polybutadiene, styrene and
acrylonitrile.
36. A process wherein a plastic is subjected to a solvent and
thereafter treated by the process of claim 5.
37. The process of claim 36 wherein the solvent is
trichloroethylene and the plastic is polypropylene.
38. The process of claim 36 wherein the solvent is
perchloroethylene and the plastic is a graft copolymer of
polybutadiene, styrene and acrylonitrile.
39. The process of claim 1 wherein the metal salt complex is an
ethylene diamine complex of a copper salt.
40. The process of claim 5 wherein the metal salt complex is an
ethylene diamine complex of a copper salt.
Description
BACKGROUND OF THE INVENTION
There is a rapidly increasing demand for metal plated articles, for
example, in the production of low cost plastic articles that have a
simulated metal appearance. Such articles are in demand in such
industries as automotive, home appliance, radio and television and
for use in decorative containers and the like. Heretofore, the
metal plating of plastics and the like has required many process
steps, and generally such processes have been applicable to only
one or a few related substrates. It was particularly surprising to
find that plastics and the like could be plated with metal through
the use of phosphorus sesquisulfide.
It is an object of this invention to provide a simple process for
the metal plating of plastics. Another object of the invention is
to provide a process that is applicable to the plating of many
different substrates. A further object of the invention is to
provide articles having an adherent metal coating that is resistant
to peeling, temperature cycling and corrosion. Such coatings are
electrically conductive whereby static charges may be readily
dissipated from the surfaces. The metal coatings further serve to
protect the articles from abrasion, scratching and marring, reduce
their porosity and improve their thermal conductivity. The process
of this invention can be used for unidirectional mirrors and the
like; water and liquid collecting devices and the like; protective
coatings on houses, cars, boats, power line poles, street lights
and the like; and in thermal control of clothing, houses and the
like; and the like.
SUMMARY OF THE INVENTION
This invention provides a process which comprises forming a
metal-phosphorus-sulfur compound at the surface of a substrate to
render the surface susceptible to conventional electroless plating
and/or electrolytic plating. More particularly, this invention
provides a process which comprises subjecting a substrate to
phosphorus sesquisulfide so as to deposit phosphorus sesquisulfide
at the surface and thereafter contacting the thus-treated surface
with a solution of a metal salt or complex thereof to form a
metal-phosphorus-sulfur compound. In one aspect of the invention,
the treated surface is subjected to electroless metal plating to
deposit an electroless conductive coating on the surface.
Thereafter, the article is electroplated so as to deposit an
adherent metal coating of the desired thickness on the electroless
conductive coating.
Also in accordance with the invention, there is provided an article
having a metal-phosphorus-sulfur compound adherently formed at the
surface of the substrate.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The process of this invention is applicable to substrates, such as
plastics and to other substantially nonmetallic substrates.
Suitable substrates include, but are not limited to, cellulosic and
ceramic materials such as cloth, paper, wood, cork, cardboard,
clay, porcelain, leather, porous glass, asbestos, cement, and the
like.
Typical plastics to which the process of this invention is
applicable include the homopolymers and copolymers of ethylenically
unsaturated aliphatic, alicyclic and aromatic hydrocarbons such as
polyethylene, polypropylene, polybutene, ethylenepropylene
copolymers; copolymers of ethylene or propylene with other olefins,
polybutadiene; polymers of butadiene, polyisoprene, both natural
and synthetic, polystyrene and polymers of pentene, hexene,
heptene, octene, 2-methyl-propene, 4-methyl-hexene-1, bicyclo
(2.2.1.)-2-heptene, pentadiene, hexadiene,
2,3-dimethylbutadiene-1,3,4-vinylcyclohexene, cyclopentadiene,
methylstyrene, and the like. Other polymers useful in the invention
include polyidene, indenecoumarone resins; polymers of acrylate
esters and polymers of methacrylate esters, acrylate and
methacrylate resins such as ethyl acrylate, n-butyl methacrylate,
isobutyl methacrylate, ethyl methacrylate and methyl methacrylate;
alkyd resins; cellulose derivatives such as cellulose acetate,
cellulose acetate butyrate, cellulose nitrate, ethyl cellulose,
hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl
cellulose; epoxy resins; furan resins (furfuryl alcohol or furfural
ketone); hydrocarbon resins from petroleum; isobutylene resins
(polyisobutylene); isocyanate resins (polyurethanes); melamine
resins such as melamine-formaldehyde and
melamine-urea-formaldehyde; oleoresins; phenolic resins such as
formaldehyde, phenolic-elastomer, phenolic-epoxy,
phenolic-polyamide, and phenolic-vinyl acetals; polyamide polymers,
such as polyamides, polyamide-epoxy and particularly long chain
synthetic polymeric amides containing recurring carbonamide groups
as an integral part of the main polymer chain; polyester resins
such as unsaturated polyesters of dibasic acids and dihyroxy
compounds, and polyester elastomer and resorcinol resins such as
resorcinol-formaldehyde, resorcinol-furfural,
resorcinol-phenol-formaldehyde, resorcinal-polyamide and
resorcinol-urea; rubbers such as natural rubber, synthetic
polyisoprene, reclaimed rubber, chlorinated rubber, polybutadiene,
cyclized rubber, butadiene-acrylonitrile rubber, butadiene-styrene
rubber, and butyl rubber; neoprene rubber (polychloroprene);
polysulfides (Thiokol); terpene resins; urea resins; vinyl resins
such as polymers of vinyl acetal, vinyl acetate or vinyl
alcohol-acetate copolymer, vinyl alcohol, vinyl chloride, vinyl
butryal, vinyl chloride-acetate copolymer, vinyl pyrrolidone and
vinylidene chloride copolymer; polyformaldehyde; polyphenylene
oxide; polymers of diallyl phthalates and phthalates;
polycarbonates of phosgene or thiophosgene and dihydroxy compounds
such as bisphenols, thermoplastic polymers of bisphenols and
epichlorohydrin (trade named Phenoxy polymers); graft copolymers
and polymers of unsaturated hydrocarbons and an unsaturated
monomer, such as graft copolymers of polybutadiene, styrene, and
acrylonitrile, commonly called ABS resins, ABS-polyvinyl chloride
polymers, recently introduced under the trade name of Cycovin; and
acrylic polyvinyl chloride polymers, known by the trade name of
Kydex 100.
The polymers of the invention can be used in the unfilled
condition, or with fillers such as glass fiber, glass powder, glass
beads, asbestos, talc and other mineral fillers, wood flour and
other vegetable fillers, carbon it its various forms, dyes,
pigments, waxes and the like.
The substrates of the invention can be in various physical forms,
such as shaped articles, for example, moldings, sheets, rods, and
the like; fibers, films and fabrics, and the like.
In the first step of the preferred process of the invention, the
substrate is treated with phosphorus sesquisulfide. The phosphorous
sesquisulfide can be utilized as a liquid or dissolved in a
solvent. Suitable solvents or diluents for the phosphorus
sesquisuflide are solvents that dissolve the phosphorus
sesquisulfide and which preferably swell the surface of a plastic
without detrimentally affecting the surface of the plastic. Such
solvents include the halogenated hydrocarbons and halocarbons such
as chloroform, methyl chloroform, phenyl chloroform,
dichloroethylene, trichloroethylene, perchloroethylene,
trichloroethane, dichloropropane, ethyl dibromide, ethyl
chlorobromide, propylene dibromide, monochlorobenzene,
monochlorotoluene and the like; aromatic hydrocarbons such as
benzene, toluene, xylene, ethyl benzene, naphthalene and the like;
ketones such as acetone, methyl ethyl ketone, and the like; acetic
acid; acetic acid-trichloroethylene mixtures; carbon disulfide; and
the like.
When a solution of phosphorus sesquisulfide is employed in the
process, the solution concentration is generally in the range from
about 0.0001 weight percent of phosphorus sesquisulfide based on
the weight of the solution up to a saturated solution, and
preferably from about 0.5 to about 2.5 percent. Prior to contacting
the substrate with the phosphorus sesquisulfide, liquid or
solution, the surface of the substrate should be clean. When a
solution is used, the solvent generally serves to clean the
surface. A solvent wash may be desirable when liquid phosphorus
sesquisulfide is employed. The phosphorus sesquisulfide treatment
is generally conducted at a temperature below the softening point
of the substrate, and below the boiling point of the solvent, if
the solvent is used. Generally, the temperature is in the range of
about 0.degree. to 135.degree. Centigrade, but preferably in the
range of about 15.degree. to 75.degree. Centigrade. The contact
time varies depending on the nature of the substrate, the solvent
and temperature, but is generally in the range of about 1 second to
1 hour or more, preferably in the range of about 1 to 20
minutes.
It has been found that subjection of the substrate to the solvent
hereinbefore disclosed prior to subjection to the phosphorus
sesquisulfide has a very marked effect on the adhesion of the final
metal plated article. The temperature of the solvent is directly
related to the adhesion realized. Generally, the temperature is in
the range of about 30.degree. Centigrade to the boiling point of
the solvent, preferably about 50.degree. to 100.degree. and higher
than the temperature of the solution of phosphorus sesquisulfide,
if a solution is used. The contact time varies depending on the
nature of the substrate, solvent and temperature but preferably is
1 to 15 minutes.
As a result of the first treatment step, the phosphorus
sesquisulfide is deposited at the surface of the substrate. By this
is meant that the phosphorus sequisulfide can be located on the
surface, embedded in the surface and embedded beneath the surface
of the substrate. The location of the phosphorus sesquisulfide is
somewhat dependent on the action of the solvent on the surface if
one is used.
Following the first treatment step, the substrate can be rinsed
with a solvent, and then can be dried by merely exposing the
substrate to the atmosphere or to inert atmospheres such as
nitrogen, carbon dioxide, and the like, or by drying the surface
with radiant heaters or in a conventional oven. Drying times can
vary considerably, for example, from 1 second to 30 minutes or
more, preferably 5 seconds to 10 minutes, more preferably 5 to 120
seconds. The rinsing and drying steps are optional.
In the second treatment step of the process of the invention, the
phosphorus sesquisulfide treated substrate is contacted with a
solution of a metal salt or a complex of a metal salt, which is
capable of reacting with the phosphorus to form a
metal-phosphorus-sulfur compound. The term metal-phosphorus-sulfur
compound used herein, means the metal-phosphorus-sulfur coating
which is formed at the surface of the substrate. Without being
limited to theory, the metal-phosphorus-sulfur compound may be an
ionic compound or a solution (alloy). The metals generally employed
are those of Groups IB, IIB, IVB, VB, VIB, VIIB, and VIII of the
Periodic Table. The preferred metals are copper, silver, gold,
chromium, vanadium, tantalum, cadmium, tungsten, molybdenum, and
the like.
The metal salts that are used in the invention can contain a wide
variety of anions. Suitable anions include the anions of mineral
acids such as sulfate, chloride, bromide, iodide, fluoride,
nitrate, phosphate, chlorate, perchlorate, borate, carbonate,
cyanide, and the like. Also useful are the anions of organic acids
such as formate, acetate, citrate, butyrate, valerate, caproate,
stearate, oleate, palmitate, dimethylglyoxime, and the like.
Generally, the anions of organic acids contain one to 18 carbon
atoms.
Some useful metal salts include copper sulfate, copper chloride,
silver nitrate, nickel chloride and nickel sulfate.
The metal salts can be complexed with a complexing agent that
produces a solution having the basic pH (>7). Particularly
useful are the ammonical complexes of the metal salts, in which one
to six ammonia molecules are complexed with the foregoing metal
salts. Typical examples include NiSO.sub.4 .sup.. 6NH.sub.3,
Ni(C.sub.2 H.sub.3 OO).sub.2.sup. . 6NH.sub.3, CuSO.sub.4.sup. .
6NH.sub.3, CuCl.sub.2.sup. . 6NH.sub.3, AgNO.sub.3.sup. .
6NH.sub.3, NiSO.sub.4.sup. . 3NH.sub.3, CuSO.sub.4.sup. .
4NH.sub.3, NiCl.sup.. 6NH.sub.3 Ni(NO.sub.3).sub.2.sup. .
4NH.sub.3, and the like. Other useful complexing agents include
quinoline, amines and pyridine. Useful complexes include compounds
of the formula MX.sub.2 Q.sub.2 wherein M is the metal ion, X is
chlorine or bromine and Q is quinoline. Typical examples include:
CoCl.sub.2 Q.sub.2, CoBr.sub.2 Q.sub.2, NiCl.sub.2 Q.sub.2,
NiBr.sub.2 Q.sub.2, CuCl.sub.2 Q.sub.2, CuBr.sub.2 Q.sub.2 and
ZnCl.sub.2 Q.sub.2. Useful amine complexes include the
mono-(ethylenediamine). bis-(ethylenedamine)-,
tris(ethylenediamine)-, bis(1,2-propane diamine)-, and
bis-(1,3-propanediamine)-complexes of salts such as copper sulfate.
Typical pyridine complexes include NiCl.sub.2 (py).sub.2 and
CuCl.sub.2 (py).sub.2 where py is pyridine.
The foregoing metal salts and their alcohol, are used in ionic
media, preferably in aqueous solutions. However, nonaqueous media
can be employed such as alcohols, for example, methyl alcohol,
ethyl alcohol, butyl alcohol, heptyl alcohol, decyl alcohol and the
like. Mixtures of alcohol and water can be used. Also useful are
ionic mixtures of alcohol with other miscible solvents of the types
disclosed hereinbefore. The solution concentration is generally in
the range from about 0.1 weight percent metal salt or complex based
on the total weight of the solution up to a saturated solution,
preferably from about 1 to about 10 weight percent metal salt or
complex. The pH of the metal salt or complex solution can range
from about 4 to 14, but is generally maintained in the basic range,
i.e., greater than 7, and preferably from about 10 to about 13.
The step of contacting the phosphorus sesquisulfide treated
substrate with the solution of metal salt is generally conducted at
a temperature below the softening point of the substrate, and below
the boiling point of the solvent, if one is used. Generally, the
temperature is in the range of about 30.degree. to 110.degree.
Centigrade, preferably from about 50.degree. to 100.degree.
Centigrade. The time of contact can vary considerably, depending on
the nature of the substrate, the characteristics of the metal salts
employed and the contact temperature. However, the time of contact
is generally in the range of about 0.1 to 30 minutes, preferably
about 5 to 10 minutes.
Depending on the conditions employed in the two treatment steps,
the duration of the treatments, and the nature of the substrate
treated, the resulting treated surface may be either (1)
conductive, such that the surface can be readily electroplated by
conventional techniques, or (2) non conductive. In the latter
instance the treated surface contains active or catalytic sites
that render the surface susceptible to further treatment by
electroless plating process that produce a conductive coating on
the plastic surface. Such a conductive coating is then capable of
being plated by conventional electrolytic processes.
The treated substrates that result from contacting the
phosphorus-sesquisulfide treated surface with a metal salt solution
can be subjected to a process that has become known in the art as
electroless plating or chemical plating. In a typical electroless
plating process, a catalytic surface is contacted with a solution
of metal salt under conditions in which the metallic ion of the
metal salt is reduced to the metallic state and deposited on the
catalytic surface. The use of this process with the products of
this invention relies upon the catalytic metal sites deposited on
the surface as a result of the treatment with the solution of metal
salt or complex of this invention. A suitable chemical treating
bath for the deposition of a nickel coating on the catalytic
surface produced in accordance with the process of the invention
can comprise, for example, a solution of nickel salt in an aqueous
hypophosphite solution. Suitable hypophosphites include the alkali
metal hypophosphites such as sodium hypophosphite and potassium
hypophosphite, and the alkaline earth metal hypophosphites such as
calcium hypophosphite and barium hypophosphite. Other suitable
metal salts for use in the chemical treating bath include the metal
salts described hereinbefore with respect to the metal salt
treatment of the phosphorus-treated substrate of the invention.
Other reducing media include formaldehyde, hydroquinone and
hydrazine. Other agents, such as buffering agents, complexing
agents, and other additives are included in the chemical plating
solutions or baths.
The treated substrate of the invention that are conductive can be
electroplated by the processes known in the art. The article is
generally used as the cathode. The metal desired to be plated is
generally dissolved in an aqueous plating bath, although other
media can be employed. Generally, a soluble metal anode of the
metal to be plated can be employed. In some instances, however, a
carbon anode or other inert anode is used. Suitable metals,
solutions and condition for electroplating are described in Metal
Finishing Guidebook Directory for 1967, published by Metals and
Plastics Publications, Inc. Westwood, N. J.
The following examples serve to illustrate the invention but are
not intended to limit it. Unless specified otherwise, all
temperatures are in degrees centigrade and parts are understood to
be expressed in parts by weight.
EXAMPLE I
A sample of polypropylene sheet was immersed for 2 minutes in a
solution containing 2 percent by weight phosphorus sesquisulfide in
a mixture of 700 milliliters of trichloroethylene, 700 milliliters
of perchloroethylene and 14 milliliters of ethanol at 70.degree.
Centigrade. The sample was thereafter immersed for 10 minutes in a
solution of copper pyrophosphate at 60.degree. Centigrade. The
copper pyrophosphate solution was prepared by adding the following
ingredients to water followed by dilution to 6 liters of solution
and filtering: 223 grams copper oxide, 2,660 grams tetrapotassium
pyrophosphate trihydrate, 123 grams oxalic acid, 40 grams of 30
volume percent aqueous ammonia, and 61.2 grams of 70 percent by
volume aqueous nitric acid. A red conductive
copper-phosphorus-sulfur coating was produced on the surface of the
polypropylene. Thereafter, layers of nickel and chrome were
adherently bound to the polypropylene by electrodeposition as
follows: The article was plated in a bath of semi-bright nickel
(Harshaw Co.) employed a current density of 50 amperes per square
foot, followed by plating in a bath of bright nickel (Harshaw Co.)
at 50 amperes per square foot current density and then plating in a
chrome bath (Udylite Corp.) at 150 amperes per square foot current
density.
EXAMPLES 2-14
Following the procedure of Example 1, a metal-phosphorus-sulfur
coating was obtained on the following specified plastics by
employing a 2 percent solution of phosphorus sesquisulfide in
trichloroethylene and perchloroethylene followed by subjection of
the thus-treated plastic to the specified metal salt baths. Table I
specifies the plastic, metal salt bath and the appearance of the
resulting metal-phosphorus-sulfur coating. ##SPC1##
EXAMPLE 15
A molded polypropylene plaque was immersed for 5 minutes in a 1
percent solution of phosphorus sesquisulfide in trichloroethylene
at room temperature, rinsed with water and immediately subjected
for 10 minutes in an aqueous solution containing nickel sulfate
(0.063 mole per liter) and ammonia (2.5 moles per liter) maintained
at 60.degree. Centigrade. After drying, the black plastic surface
had a resistance of 10,000 ohms per centimeter.
EXAMPLE 16
A polypropylene plaque was immersed in a 50.degree. bath containing
trichloroethylene for 15 minutes and then treated as in Example 15.
The resistance of the resulting treated plastic surface was 3,000
ohms per centimeter. The sample was electroplated to give a 0.3-mil
semi-bright nickel strike and 1.7-mil thickness of acid copper
thereon. The adhesion was determined to be 10.0 pounds per
inch.
EXAMPLE 17
An epoxy resin-glass fiber resin laminate was immersed for 5
minutes in a 1.3 percent solution of phosphorus sesquisulfide in
methylene chloride at room temperature, dried in air for 10 seconds
and then immersed for 10 minutes in an ammoniacal solution of
nickel sulfate at 60.degree. Centigrade. The resistance of the
black preplate was 5,000 ohms per centimeter. The laminate was
thereafter electroplated.
EXAMPLES 18-26
A 2 percent solution of phosphorus sesquisulfide was prepared in
the following specified solvents. Thereafter, samples of
polypropylene, ABS, phenolic resin, epoxy resin, and polyvinyl
chloride were immersed in the phosphorus sesquisulfide solution for
3 minutes at 50.degree. Centigrade and transferred to an ammoniacal
nickel sulfate bath at 65.degree. Centigrade for 30 minutes. Each
of the experiments were repeated replacing the nickel with a bath
containing an ammoniacal solution of 5 percent of copper sulfate.
In every instance, a metal-phosphorus-sulfur compound was
formed.
Example Solvent
__________________________________________________________________________
18 Trichloromethane 19 Carbon tetrachloride 20 Trichloroethane 21
Benzene 22 Toluene 23 Turpentine 24 Decalin 25 Dimethylformamide 26
Dimethylsulfoxide
__________________________________________________________________________
EXAMPLE 27
Following the procedure of Example 18, the following metal salts
were employed in the metal salt bath to obtain a
metal-phosphorus-sulfur compound: nickel chloride, nickel nitrate,
nickel acetate, nickel formate, nickel citrate, silver nitrate,
iron chloride and cobalt chloride.
EXAMPLE 28
Following the procedure of Example 18, the following substrates
were provided with an adherent metal coating: novolac resin, cotton
string, Teflon, cardboard, leather, rubber, masonite, ceramics,
wood, Lexan (polycarbonate), nylon, polyacetyl, acrylics
(plexiglass), and polystyrene.
EXAMPLE 29
An epoxy resin-glass fiber laminate was immersed for 5 minutes at
room temperature in a 1 percent solution of phosphorus
sesquisulfide dissolved in a 2:1 (by volume) solvent mixture of
trichloroethylene and methylene chloride. After being rinsed in a
water bath, the laminate was immersed for 15 minutes in an aqueous
solution, at 65.degree. Centigrade, containing nickel sulfate
(0.063 mole per liter) and ammonia (2.5 mole per liter). The sample
was rinsed with water and then immersed in an aqueous electroless
copper bath for 10 minutes at room temperature. The electroless
copper bath had the following composition.
CuNO.sub.3 .sup.. 3H.sub.2 O 15 g. per liter NaHCO.sub.3 10 g. per
liter Rochelle salt 30 g. per liter NaOH 20 g. per liter
Formaldehyde (37%) 100 ml. per liter
After drying the sample was electroplated with 0.3-mil semi-bright
nickel and 1.7 mil acid copper.
EXAMPLE 30
An epoxy resin-glass fiber laminate was treated as in Example 29
except that an electroless nickel bath instead of electroless
copper was used. The electroless nickel bath had the following
composition.
NiSO.sub.4 28.9 g. Sodium citrate 8.9 g. Sodium hypophosphite 12.0
g. Magnesium sulfate 7.8 g. Water 800 ml.
The sample was immersed in the bath at 85.degree. Centigrade for 10
minutes, and then electroplated as described in Example 29.
EXAMPLE 31
A set of four polypropylene discs were immersed in a 1 percent
solution of phosphorus sesquisulfide in perchloroethylene for 15
minutes at about 32.5.degree. C. and then for 15 minutes in a
70.degree. C. aqueous copper chloride-ethylene diamine solution. A
second set of four discs was subjected to the same procedure except
that they were immersed for 2 minutes in perchloroethylene at
65.degree. C. before subjection to the phosphorus sesquisulfide.
Both sets of treated discs were thereafter identically washed,
dried and electroplated to provide 3 mils of Watt's nickel thereon.
The average maximum adhesion of the first set of discs was
determined to be 4.4 pounds per inch and the average maximum
adhesion of the second set was found to be 32.8 pounds per
inch.
Similar results are obtained when other solvents such as benzene,
acetone and the like are employed as a treatment step prior to
subjection to the phosphorus sesquisulfide,
EXAMPLE 32
Example 16 was repeated except that ABS was employed in place of
the polypropylene and perchloroethylene was employed in place of
the trichloroethylene.
Various changes and modifications can be made in the process and
products of this invention without departing from the spirit and
scope of the invention. Various embodiments of the invention
disclosed herein serve to further illustrate the invention but are
not intended to limit it.
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