US3799794A - Process of metal plating - Google Patents

Abstract

A PROCESS COMPRISING SUBJECTING A SUBSTRATE TO A MEMBER OF THE GROUP OF ELEMENTAL PHOSPHORUS AND LOW OXIDATION STATE PHOSPHORUS COMPOUNDS, AND THEREAFTER TO A METAL SALT OR COMPLEX THEREOF IS EMPLOYED TO PROVIDE ELECTROSTATIC AND MAGNOSTATIC SHIELDING OF WIRES AND IN THE PRODUCTION OF ANTISTATIC TEXTILES. IMPROVEMENTS IN THE COATING OF FILAMENTS ARE PROVIDED BY SUBJECTION OF THE SUBSTRATE TO A SOLUTION OF ELEMENTAL PHOSPHORUS, MOLTEN ELEMENTAL PHOSPHORUS, AND THEREAFTER TO THE METAL SALT OF COMPLEX THEREOF, AND ALSO BY EMPLOYING A SECOND METAL SALT BATH.

Description

United States Patent ()1 fice 3,799,794 Patented Mar. 26, 1974 3,799,794 PROCESS OF METAL PLATING George T. Miller, Lewiston, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, NY. No Drawing. Filed Sept. 23, 1969, Ser. No. 860,424 Int. Cl. B44d 1/092; C23c 3/02 U.S. Cl. 117-47 A 14 Claims ABSTRACT OF THE DISCLOSURE complex thereof, and also by employing a second metal salt bath.

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 in the use of decorative containers and the like. The metallizing of filaments or substrates having minimal thickness has been particularly difiicult due to the difficulty of forming an adherent bond with the metallic coating. A further dii'ficulty with metallic coated filaments has been the lack of a combination of flexibility and the adhesion in the article. As a result, the utility of the coated filaments in any applica tion where they would be subject to stretching and/o1 flexing was diminished. The present invention provides a process which eliminates the previous difiiculties in the metallic coated filaments or substrates of minimal thickness and provides for electrostatic and magnostatic shielding of Wires and antistatic textiles.

It is the object of this invention to provide an improved process for the metallic coating of filaments and substrates of minimal thickness. It is also the object of the invention to provide an improved process for etallic coating of filaments wherein the resulting filaments can be stretched and/or flexed. A further object of this invention is to provide for the electrostatic and magnostatic shielding of wires. The invention also has the object of providing a process for rendering textiles antistatic. These and other objects will become apparent to one skilled in the art from the following disclosure.

SUMMARY OF THE INVENTION This invention relates to the uses of and improvements in the metallizing of substrates. More particularly, this invention relates to an improved process comprising sub jecting a substrate to a member of the group of elemental phosphorous and low oxidation state phosphorous cmpounds, and thereafter to a metal salt or complex thereof which is employed to provide electrostatic and magnostatic shielding of wire insulation and in the production of antistatic textiles. Improvements in the metallic coating of filaments are provided by subjection of the substrate to a solution of elemental phosphorus, molten elemental phosphorus, and thereafter to the metal salt or complex thereof, and also by employing a second metal salt bath.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The process of this invention is applicable to substrates, such as plastics and to other substantially non-metallic 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 a'nd aromatic hydrocarbons such as polyethylene, polypropylene, polybutene, ethylenepropylene copolymers; copolymers of ethylene or propylene or with other olefins, polybutadiene; polymers of butadiene, polyisoprene, both natural and synthetic, polystyrene and polymers of pentene, hexene, heptene, octene, Z-methylpropene, 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 polyindene, indenecoumarone resins; polymers or 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 resin; cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymeth yl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfuralketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes); melamine resins such as melamine-formaldehyde and melamine-urea-formaldehyde; oleo-resins; phenolic resins such as phenol-formaldehyde, phenolicelastomer, 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 dihydroxy compounds, and polyester elastomer and resorcinol resins such as resorcinol-formaldehyde, resorcinol-furfural, resorcinol-phenol-formaldehyde, resorcinol-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 butyral, 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 (tradenamed Phenoxy polymers); graft copolymers and polymers of unsaturated hydrocarbons and an unsaturated monomer, such as graft copolymers or polybutadiene, styrene and acrylonitrile, commonly called ABS resins; ABS-polyvinyl chloride polymers, recently introduced under the tradename of Cycovin; and acrylic polyvinyl chloride polymers, known by the tradename 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 in its various forms, dyes, pigments, waxes and the like. If a wax is used as a filler, it has been found that the harder the wax, the more adherent the metal will be bound to the substrate.

This invention is particularly adapted to substrates which have a minimal thickness or are in the form of a filament, fiber, film, and the like. These substrates have a thickness up to about mils and generally in the range of about 0.5 to about 14 mils.

In the process of this invention, the substrate is subjected to a member of the group of elemental white phosphorus and low oxidation state phosphorus compounds, and thereafter to a metal salt or complex thereof. This process is described in copending applications Ser. No. 683,793, filed Nov. 17, 1967, now abandoned, Ser. No. 750,488, filed Aug. 6, 1968 and in Ser. No. 750,477, filed Aug. 6, 1968, now abandoned, which disclosures are hereby incorporated by reference.

The subjection to elemental white phosphorus, which includes the various impure or commercial grades sometimes referred to as yellow phosphorus, can be effected when the phosphorus is in the vapor phase, is a liquid, or is dissolved in a solvent. Suitable solvents or diluents for the elemental phosphorus are solvents which dissolve elemental phosphorus and which preferably swell the surface of a plastic without detrimentally aflecting the surface of the plastic. Such solvents include the halogenated hydrocarbons and halocarbons such as chloroform, methylchloroform, dichloroethylene, trichloroethylene, perchloroethylene, and the like; aromatic hydrocarbons such as benzene, toluene, xylene, and the like. The solution concentration is generally in the range from about 0.0001 weight percent of phosphorus based on the weight of the solution up to a saturated solution, and preferably from about 0.1 to about 2.5 percent. Generally the temperature is in the range of about to 135 degrees centigrade, but preferably in the range of about to 100 degrees centrigrade. 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 10 minutes.

Alternatively, the substrate can be subjected to at least one low oxidation state phosphorus compound, i.e., wherein the phosphorus has a valence of less than 5, preferably in a solvent. Suitable low oxidation state compounds are trihydroxymethyl phosphine; phosphorus sesquisulfide; P H phosphine; diphospine, hypophosphorus acid and salts thereof of the metals of Groups I, II and III; phosphorus acid and the salts thereof of the metals of Groups I, II and III, and low oxidation state phosphorus compounds prepared by reacting elemental phosphorus with a suitable nucleophilic reagent or organo metallic compound (including Grignard reagents). Suitable nucleophilic reagents include basic compounds having an unshared pair of electrons on a carbon, oxygen, nitrogen, sulfur or phosphorus atom. The preferred nucleophilic reagents have the formula MZ wherein M is an alkali metal or alkaline earth metal and Z is hydroxide, alkoxide, amide, sulfite, thiosulfate, mercaptide, cyanate, thiocyanate, cyanide, azide, and the like. The substrate can, if desired, be subjected to the solvent prior to subjection to the phosphorus or low oxidation state phosphorus compound in order to improve the quality of the resulting metal coatmg.

As a result of treatment with phosphorus or low oxidation state phosphorus compounds, the phosphorus or low oxidation state phosphorus compounds are deposited at the surface of the substrate. By this is meant that they can be located on the surface, embedded in the surface and embedded beneath the surface of the substrate. The location of the elemental phosphorus or phosphorus compound is somewhat dependent on the action of the solvent on the surface if one is used.

Following the treatment with elemental phosphorus or low oxidation state phosphorus compound, the substrate can be rinsed with a solvent and can then 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, and preferably 5 to 120 seconds. The rinsing and drying steps are optional.

The thus-treated substrate is thereafter subjected to a solution of a metal salt or a complex of a metal salt which is capable of reacting with the elementary phosphorus to form a metal phosphide, or capable of reacting with the low oxidation state metal phosphorus compound to form a metal-phosphorus coating. The term metal phosphide, as used herein, means the metal-phosphorus coating which is formed at the surface of the substrate, and the term metal-phosphorus coating means the coating which is formed at the surface of the substrate. The metals generally employed are those of Groups I-B, II-B, IV-B, V-B, VI-B, VI-I-B and VIII of the Periodic Table appearing on pages 60-61 of Langes Handbook of Chemistry (revised 10th, ed.). The preferred metals are copper, chromium, manganese, cobalt, nickel, titanium, zirconium, vanadium, tantalum, cadmium, tungsten, molybdenum, and the like.

The metal salts that are used can contain a wide variety of anions. Suitable anions include the anions of mineral acids such as sulfate, chloride, nitrate, phosphate, chlorate, perchlorate, and the like. Also useful are the anions of organic acids such as formate, acetate, citrate, stearate, and the like. Generally, the anions of organic acids contain 1 to 18 carbon atoms. Some useful metal salts include copper sulfate, copper chloride, nickel sulfate, nickel chloride, and nickel cyanide.

The metal salts can be complexed with a complexing agent that produces a solution having a basic pH 7). Particularly useful are the ammoniacal complexes of the metal salts in which 1 to 6 ammonium molecules are complexed with the foregoing metal salts. Typical examples include NiSO46NH3, NiCl2'6NH3, CuSO -6NH CuCl -6NH NiSO -3NH CuSO -4NH and the like. Other useful complexing agents include quinoline, amines, and pyridine.

The foregoing metal salts and their complexes are used in ionic media, preferably in aqeous solutions. However, non-aqueous media can be employed such as alcohols, for example, methanol, ethanol, butanol, and the like. Mixtures of alcohol and water can be used and ionic mixtures of alcohol with other miscible solvents of the types disclosed herein before are also useful. 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. Generally, the contact temperature is in the range of about 0 to 110 degrees centrigrade, preferably from about 20 to degrees 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 from about 5 to 10 minutes.

When the substrate is a filament or is of minimal thickness, it has been found that the quality of the resulting metallic phosphide can be improved by subjecting the substrate first to a solution of elemental white phosphorus as hereinbefore described and thereafter to molten elemental 'white phosphorus. Generally, the substrate is subjected to the solution of elemental phosphorus for about 1 second to about 1 hour, preferably 1 to about 10 minutes, and thereafter subjected to the molten phosphorus for about 1 second to about 1 hour, preferably 0.5 to about 10 minutes. The resulting substrate is thereafter subjected to a metal salt or complex thereof as described hereinbefore.

Surprisingly, it has been found that when a substrate which has been treated as described hereinbefore is thereafter subjected to a second solution of a metal salt or complex thereof wherein the metal lies between silver and platinum inclusive in the electromotive series, the treated substrates can be stretched or flexed without losing their conductivity. The metals of the second solution are silver, gold, palladium and platinum. The second metal salt bath can contain the metals as salts of the anions disclosed hereinbefore and can be complexed by the complexing agents described hereinbefore. Typical metal salts or complexes thereof employed in the second metal salt bath include silver nitrate, silver acetate, silver salicylate, silver perchlorate, Au O Au(CN) -3H O, PtCl PtBr platinum sulfate, chloroplatinic acid, and the like. The solution concentrations, subjection temperatures and contact times are as described hereinbefore with respect to the first metal salt bath. The metal of the second metal salt or complex thereof is different from the metal of the first metal salt or complex thereof.

The treated articles provided by the processes hereinbefore described can be employed to provide electrostatic and magnostatic shielding of cables and wires. Heretofore, such applications were restricted because of the rigidity of the metal plated substrate or required specially designed cables such as the recently developed cable having a continuous helical groove scored into the surface of a polyethylene dielectric sheath. By wires or cables is meant a conductor such as a copper wire which is encased in a dielectric sheath of a substrate hereinbefore described or having a layer of such substrate upon the dielectric sheath. The wire or cable is subjected to the process hereinbefore described so as to provide a coating of about 1 micron to about 5 mils on the surface of the wire or cable, preferably about 2 microns to about 1 mil. The coating provides electrostatic and magnostatic shielding which is equal to or better than conventional shielding such as, e.g., a copper wire braided shield.

The process hereinbefore described also allows antistatic fabrics to be prepared. The coated filaments are conductive. A continuous coated filament or filaments can be woven through the fabric or can be combined with the yarn during the weaving of the fabric or can be combined into the yarn. The treated filaments are incorporated into the fabric in an antistatic amount, i.e., in an amount suflicient to allow dissipation of static buildup. Generally, the treated filaments comprise about 0.01 to about 50 weight percent based on the total weight of the fabric, preferably from about 0.05 to about percent.

The following examples illustrate certain preferred embodiments of the present invention. Unless otherwise indicated in this specification and claims, all parts and percentages used herein are by weight and all temperatures are in degrees centigrade.

Example 1 A denier polypropylene monofilament (1.8 mils in diameter) was subjected for 2 minutes to molten phosphorus at 60-65 degrees centigrade and thereafter for 5 minutes to a 5 percent solution of nickelous acetate, also containing ammonium hydroxide and sodium hydroxide, at 70 degrees centigrade. A conductive metal phosphide was produced on the monofilament, however, the deposit was somewhat uneven.

Example 2 Example 1 was repeated except that the molten phosphorus was replaced by a 2 percent solution of white phosphorus in trichloroethylene. A conductive metal phosphide was produced on the monofilament, however, the coverage of the filament was slightly uneven.

6 Example 3 A 15 denier polypropylene monofilament was subjected for 5 minutes at 50-65 degrees centigrade to a 2 percent solution of white phosphorus in trichloroethylene and then for seconds to molten phosphorus. Thereafter, the monofilament was transferred to an ammoniacal solution containing 5 percent nickelous acetate for 5 minutes at 75 degrees centigrade. The resulting treated monofilament had a conductive metal phosphide formed at its surface which was adherent and uniform.

The foregoing process was repeated except that the treatment time to the molten phosphorus was decreased to 30 seconds. A conductive, adherent uniform metal phosphide was formed at the surface of the monofilament.

Example 4 A 15 denier polypropylene monofilament was subjected for 1 /2 minutes to a 2 percent solution of white phosphorus in trichloroethylene at 65 degrees centigrade and thereafter for 1 /2 minutes to molten phosphorus at 65 degrees centigrade. The monofilament was then subjected for 5 minutes to a solution containing 5 percent nickelous acetate, 5 percent ammonium hydroxide and 1 percent sodium hydroxide at 75 degrees centigrade. A conductive, adherent, uniform nickel phosphide was produced at the surface of the substrate.

Comparison of Example 1-4 show that the metal phosphide obtained when a combination of molten phosphorus and a solution of phosphorus is employed the metal phosphide obtained is superior to that obtained when either treatment is employed individually.

Example 5 A sample of Alpha #3053 wire (copper encased in polyvinyl chloride) was subjected to a 2 percent solution of white phosphorus in trichloroethylene at 65 degrees centigrade for 1 minute. Thereafter the wire was subjected for 4 minutes to an ammoniacal solution of nickelous acetate containing excess ammonium hydroxide at 70 degrees centigrade and then for 15 seconds to an ammoniacal solution containing 7 percent silver nitrate at room temperature. A inch length of the treated wire was tested by removing the conductor from the treated insulation and the contacts of an ohm meter were held at the ends of the treated insulation. The insulation was then stretched and released several times and the resistance in ohms recorded. The results are given in Table I.

The figures recorded when the insulation was returned to its original length were taken after the resistance attained a steady figure. The insulation was also stretched beyond its yield point and upon release of the pressure relaxed to a length of inch. The wire then had a resistance of K ohms for a /2 inch long portion of the insulation.

Example 6 The untreated wire of Example 5 was subjected to a 2 percent solution of phosphorus in trichloroethylene at 65 degrees centigrade and thereafter to a 5 percent ammoniacal solution of nickel acetate at 75 degrees centigrade. It was found that upon stretching the insulation as described in Example 5, the conductivity of the metal phosphide was lost.

Example 7 A polypropylene disk was subjected to a 2 percent solution of white phosphorus in trichloroethylene for 3 minutes at 65 degrees centigrade and thereafter to a solution containing nickel sulfate, ammonium hydroxide and ethylene glycol for 5 minutes at 80 degrees centigrade. The plastic was thereafter washed for 1 minute in water and then subjected to a solution containing 5 percent silver nitrate to which ammonium hydroxide had been added until the solution was clear in appearance and then adjusted to a pH of about 7.5 with 50 percent by volume nitric acid. The silver nitrate solution was maintained at 25 degrees centigrade. After "90 seconds, the polypropylene disk was removed and found to have obtained a shiny, silvery, adherent layer.

Example 8 Wire, which was coated with polyvinylchloride, was subjected to a 2 percent solution of white phosphorus in trichloroethylene at 62-63 degrees centigrade for one minute and dried in air for 10 seconds. The treated substrate was then subjected to a 5 percent nickel solution for five minutes at 70-73 degrees centigrade. Thereafter the substrate was subjected for 2 minutes to a room temperature solution which had been prepared by adding ammonium hydroxide to a mixture of 40 grams of water and 2 grams of silver nitrate until the solution was clear and then adding nitric acid dropwise until the pH was 7.5-8. The resulting adherently bound metal phosphide coating had a resistance of 50-200K ohms.

Example 9 Two denier polypropylene monofilaments (1.8 mils in diameter) were subjected for 2 minutes to a 2 percent solution of white phosphorus in trichloroethylene at 63 degrees centigrade and then for 2 minutes to molten phosphorus at 63 degrees centigrade. The thus-treated substrate was subjected for 6 minutes to a solution containing nickelous acetate, ammonium hydroxide, and sodium hydroxide maintained at 75 degrees centigrade. Thereafter one sample was subjected for 15 seconds to a solution of silver nitrate which had been adjusted to a pH of 7 by nitric acid and ammonium hydroxide. Both samples were electroplated with bright nickel at a current density of 10 ma./cm. The conductivity of the samples was then determined to be 10K ohms for the sample treated with the silver nitrate and 300K ohms for the sample which was not treated with a silver nitrate (conductivity was measured over the entire length of the monofilaments). The samples were set aside to age and after about 24 hours the conductivities were redetermined over a 3V2 inch length. The sample treated with silver nitrate exhibited a resistance of 1000K ohms and the sample which was not treated with silver nitrate exhibited a resistance of 500K ohms. However, it was found that the handling during this measurement was sufficient to break the conductivity of the deposit on the untreated sample causing it to be non-conductive while the conductivity of the sample treated with silver was not affected.

Example 10 The polyvinylchloride jacket and wire braid shield were removed from a length of Alpha #1706 wire. The core of polyethylene insulated copper was subjected to a 2 percent solution of white phosphorus in trichloroethylene for 5 minutes at 70 degrees centigrade, air-dried for 30 seconds at room temperature, subjected to a 10 percent solution of nickelous acetate and excess ammonium hydroxide for 12 minutes at 70 degrees centigrade, washed with distilled water and dried. An oscilloscope was used to test the shielding qualities of the resulting conductive surface against the interference of a high-voltage transformer. The treated substrate was about 3 times more effective than the original wire shield.

8 Example 11 A length of military type RG-5 8 c/u wire was treated as in Example 10 except that the subjection to the phosphorus solution was 8 minutes at 61 degrees centigrade and the subjection to the nickel solution was 25 minutes at 65 degrees centigrade. A 22 gauge copper wire was then wound spirally around the treated plastic to act as a drain wire. The treated wire was tested with an audiogenerator, coil and oscilloscope and compared with 2 lengths of RG- 58 c/ u Wire. Table II shows the disturbing current, and the induced potential in millivolts of the grounded wire. The lengths tested are indicated in the headings.

TABLE II RG-58 e/u RG-58 c/n Treated Cycles 21% inch 26% inch 27% inch Example 12 A length of Alpha #3035 wire was subjected for 1 minute to a 2 percent solution of yellow phosphorus in trichloroethylene at 65 degrees centigrade, 4 minutes to a 5 percent solution of nickelous acetate, sodium hydroxide and excess ammonium hydroxide at degrees Centigrade and 15 seconds in a 7 percent ammoniacal silver nitrate solution at room temperature. The treated wire was washed in distilled water, dried and then tested for its electrostatic and magnostatic shielding capabilities in accordance with the shielding tests described in Gooding et al., Shielding Of Communication Cables, which appeared as Paper 55-198 in the July 1955 issue of the AIEE Journal on page 378. The testing apparatus described therein was modified to the extent that the shielding was applied to each test wire separately. Table III contains the results of the magnostatic test and shows the voltage pickup in milli volts of the treated Wire and five commercial wires when the disturbing current was 42 millivolts at various frequencies. Table IV shows the voltage pickup in millivolts of the treated wire and five commercial wires in the electrostatic tests when the shielding was grounded and the disturbing voltage was 35 volts at several frequencies. Table V shows the voltage pickup in volts of the electrostatic tests when the shielding was not grounded and the disturbing voltage was 35 volts.

TAB LE III Un- Treated treated Alpha Alpha Alpha. Alpha Alpha Military Cycles #3053 #3053 #1706 #1741 #2412 R G-58 c/u 200K.--. 3.0 7.0 1.5 1.0 2.0 1.5 20K 0.8 1. 0 0.8 0. 7 0.6 0. 4 2K 0. 2 0. 2 0. 2 Nil Nil 0. 2 0.2K Nil Nil Nil Nil Nil Nil TABLE IV Un- Treated treated Alpha Alpha Alpha Alpha Alpha Milita Cycles #3053 #3053 B #1706 #1741 #2412 RG-58 c/u 200K 1.0 4.0 7.0 1.0 1.5 20K 0. 2 3. 9 5. 0 1. 2 O. 5 2K Nil 3 9 5.0 1. 3 0. 6 0.2K Nil 1 5 6.0 1. 3 0. 4

Could not be grounded.

TABLE V Un Treated treated Alpha Alpha Alpha Alpha Alpha Military #3053 #3053 #1706 #1741 #2412 R G-58 e/u These tests show that the treated wires were superior in their electrostatic shielding capabilities and compared favorably in their magnostatic shielding capabilities to the commercial wires tested.

Example 13 Several yards of nylon monofilament were subjected for 1 minute to a saturated solution of trihydroxymethylphosphine in a 1:1 benzeneethanol solution at 25 degrees centigrade and then pressed dry. The treated monofilaments was thereafter subjected for 2 minutes to a 5 percent silver nitrate and ammonium hydroxide solution at 55-60 degrees centigrade, rinsed and electroless nickel plated. The treated filament was combined with nylon yarn and used to make a 6" x 12" hook rug on a polypropylene base. The rug was laid on a grounded metal plate and the top of the carpet was rubbed with a glass rod. The rate of charge leakage was measured with an electrostatic meter. The meter showed that the rug containing the treated nylon monofilament dissipated the static charges which built-up.

Example 14 The polyvinyl chloride jacket and wire braid are removed from a length of Alpha #1706 wire and the polyethylene coated wire was immersed in a solution prepared by mixing one mole of white phosphorus and one mole of lithium ethoxide in 600 milliliters of ethanol. After 30 seconds in the low oxidation state phosphorus solution at room temperature, the treated article is washed with water for 30 seconds and immersed in a 5% ammoniacal solution of nickel chloride at room temperature for minutes to form an electrostatic and magnostatic shield on the treated substrate.

Example 15 The filaments of Example 2 are combined with nylon yarn which is used to make a 6" x 12" hook rug on a polypropylene base. The rug has anti-static properties.

This example is repeated except that prior to combination with the yarn, the treated filaments are immersed in a ammoniacal solution containing 7 percent silver nitrate at room temperature for 90 seconds. A rug with anti-static properties is produced.

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. The various embodiments of the invention disclosed herein serve to further illustrate the invention but are not intended to limit it.

I claim:

1. A process which comprises subjecting a substrate, first, to a solution of elemental phosphorus, secondly, to molten elemental phosphorus and thereafter to a metal salt or complex thereof wherein said metal is selected from Groups -I-B, II-B, IV-B, V-B, VI-B, VII-B, and VIH of the Periodic Table.

2. The process of claim 1 wherein the substrate is a plastic.

3. The process of claim 2 wherein the plastic is a thermoplastic polymer.

4. The process of claim 2 wherein at least one component of the plastic is polypropylene.

5. The process of claim 1 wherein said metal is nickel.

6. The process of claim 1 the substrate is a filament.

7. A process which comprises (1) subjecting a nonmetallic substrate to a solution of a member of the group consisting of elemental phosphorous and low oxidation state phosphorous compounds, wherein the solvent of said solution is at least one solvent selected from chloroform, methyl chloroform, dichloroethylene, trichloroethylene, perchloroethylene, benzene, toluene, and xylene (2) subjecting the thus-treated substrate to an ammoniacal solution of a first metal salt or complex thereof, and (3) subjecting the treated substrate to an ammoniacal solution of a second metal salt or complex thereof, wherein said first metal is selected from Groups I-B, IIB, IV-B, V-B, VI-B, VII-B and VIH of the Periodic Table, said second metal is selected from the group consisting of silver, gold, platinum and palladium, said second metal is different from said first metal and wherein both said first and second metal salts or complexes are substantially free of reducing agents.

8. The process of claim 7 wherein the substrate is a plastic and is subjected to a solution of elemental phosphorus.

9. The process of claim 8 wherein said first metal is nickel and said second metal is silver.

10. The process of claim 9 wherein said plastic is a thermoplastic polymer.

11. The process of claim 9 wherein at least one component of said plastic is polypropylene.

12. The process of claim 9 wherein at least one component of said plastic is polyvinyl chloride.

13. A process as claimed in claim 7 wherein the nonmetallic substrate treated is the insulation of an electric conductor, thereby forming an electrostatic and magnetostatic shield on the insulation of said electric conductor.

14. An article having 21 treated substrate produced by the process of claim 7.

References Cited UNITED STATES PATENTS 333,697 1/ 1886 Thiery 204-30 3,607,351 9/1971 Lee 204-30 3,616,295 10/ 1971 Lee 204-30 3,617,320 11/1971 Lee 204-30 3,642,585 2/1972 Lin 117-47 A 3,650,803 3/1972 Lin ll747 A 3,655,531 4/1972 Quinn ll747 A 3,681,511 8/1972 Miller ll747 A 2,708,215 5/1955 Kaganotf 1l7l28.4 X 3,235,473 2/ 1966 LeDuc ll747 A 3,293,066 12/ 1966 Haincs ll7235 3,075,856 l/1963 Lukes 117160 R 3,582,445 6/ 1971 Okahashi 1'6l174 3,445,350 5/1969 Klinger 156-2 OTHER REFERENCES Langford, K. 13.: Analysis of Electroplating and Related Solutions, 3rd ed., Middlesex, England, 1962, p. 147, TS670L34, 1962.

Bayard, J. J.: Electrodeposition on Plastic Materials in Metal Industry, May 1940, p. 256.

WILLIAM D. MARTIN, Primary Examiner J. A. BELL, Assistant Examiner US. Cl. X.R.

ll747 R, 128.4, 160 R, 227; 20430 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 1,799,794 Dated March 1974 Invent George T Miller It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Eolumn 3 line 14, "1968 and" should read --l968, now abandone and- Column 8 in Table III, under heading Alpha "0.?" should read ---0.8--.

Signed and sealed this 16th day of July 1974.

(SEAL) Attest:

McCOY M. GIBSOIN, VJR. c. MARSHALL "DANN Attesting Officer Commissioner of Patents