US3661538A - Plastics materials having electrodeposited metal coatings - Google Patents
Plastics materials having electrodeposited metal coatings Download PDFInfo
- Publication number
- US3661538A US3661538A US826709A US3661538DA US3661538A US 3661538 A US3661538 A US 3661538A US 826709 A US826709 A US 826709A US 3661538D A US3661538D A US 3661538DA US 3661538 A US3661538 A US 3661538A
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- United States
- Prior art keywords
- nickel
- film
- article
- copper
- plastics material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/34—Applying different liquids or other fluent materials simultaneously
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9335—Product by special process
- Y10S428/934—Electrical process
- Y10S428/935—Electroplating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12556—Organic component
- Y10T428/12569—Synthetic resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12597—Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12687—Pb- and Sn-base components: alternative to or next to each other
- Y10T428/12694—Pb- and Sn-base components: alternative to or next to each other and next to Cu- or Fe-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12778—Alternative base metals from diverse categories
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
- Y10T428/12847—Cr-base component
- Y10T428/12854—Next to Co-, Fe-, or Ni-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12868—Group IB metal-base component alternative to platinum group metal-base component [e.g., precious metal, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12882—Cu-base component alternative to Ag-, Au-, or Ni-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12903—Cu-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
- Y10T428/24995—Two or more layers
- Y10T428/249951—Including a free metal or alloy constituent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
- Y10T428/2956—Glass or silicic fiber or filament with metal coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
Definitions
- ABSTRACT It is known to coat plastics materials, especially thermoplastics such as ABS, with metal by electrodeposition, typically with chromium on top of nickel. Conventional methods are often unsatisfactory when applied to thermosetting resin-based articles, the metal coating peelingor flaking off when the articles are subjected to repeated changes in temperature. It has now been found that copper or nickel coatings adhere well to surfaces, prepared in a conventional manner, of thermosetting plastics as well as of thermoplasts, provided that the coatings are electrodeposited in a manner such that they have an average stress in tension of at least 2,000 kg./sq. cm.
- a nickel coating is electrodeposited under conditions such that it had an average stress in tension of 2,440 to 6,460 kg./sq. cm.: this coating being dull, a bright, lightly stressed nickel coating was electrodeposited before the final layer, of chromium, was applied.
- the article is preconditioned, that is to say, its surfaces are etched with a substance to promote bonding with the coatings applied later.
- the substance used depends on the type of plastics material to be etched; commonly, a mixture of potassium dichromate, sulfuric acid and water, sodiumnaphthalene-tetrahydrofuran complexes, a mixture of sulfuric and phosphoric acids, nitric acid, or organic solvents.(such as acetone, generally with hydroquinone and pyrocatechol) are used.
- This chemical treatment may be supplemented with, or replaced by, a mechanical cleansing operation,'the surfaces being abraded by tumbling the article in an abrasive powder (sometimes with water) or by vapor blasting with very fine particles of abrasive material in a jet of air and water.
- an electrically-conducting layer of metal is applied to the article, sometimes by means of paints containing metal powders, by spraying on metal powders or by vacuum sputtering, but usually by depositing the metal from a solution of its salt by chemical reduction.
- a film of palladium or silver is deposited by immersing the article in a solution of stannous chloride or other source of stannous ions, and then in a solution of, e.g. palladium chloride or silver nitrate.
- the silver nitrate is used in aqueous ammoniacal solution in the presence ofan organic reducing agent such as an aldehyde, with or without prior treatment with stannous chloride.
- copper or nickel is applied by electroless deposition, then nickel is applied by electroplating, followed by, if required, chromium. Instead of applying nickel by electroplating, silver, palladium, or gold may be so deposited.
- the electroless deposition of copper or nickel can be dispensed with, the article being electroplated with .copper instead.
- the electroplated layers applied to plastics articles are only lightly stressed in tension, this stress being not more than about 1,500 kg./sq.cm.
- Thermoplastics materials which have been electroplated include chiefly acrylonitrile-butadiene-styrene copolymers (ABS), but also polyolefines, polymethacrylates and polycarbonates.
- ABS acrylonitrile-butadiene-styrene copolymers
- thermoset plastic materials which, unlike many thermoplastics materials, do not soften and flow at moderately high temperatures.
- methods which, when applied to thermoplastics materials, give rise to electroplated nickel or copper having adequate adhesion to the substrate are often unsatisfactory when applied to thermoset plastics materials, the electroplated nickel, copper, or certain other metals adhering insufficiently to withstand the dimensional changes that occur on repeated heating and cooling, while if the coating is accidentally perforated the electroplated metal around the perforation peels off. Because the electroplated nickel or copper fails to adhere, the overlying chromium plating readily peels off with it.
- metal coatings which are electrolytically deposited on plastics materials, particularly poly-(oxymethylenes), adhere firmly and withstand repeated large changes in temperature provided that these metal coatings have a ductility and a tensile strength (i.e. the minimum force applied in tension necessary to rupture the film) which are above certain values, and that the coated articles have a compressive stress within a specified range.
- Stress in tension is associated with a metal coating being deposited in a condition such that, providing the substrate can be distorted, the coating contracts, whereas compressive stress is associated with the contrary condition, the coating having a tendency to expand.
- the present invention provides-an article of plastics material coated with an adherent, highly stressed, electrolytically deposited film of copper, nickel, silver, palladium or gold, which film has an average stress in tension of at least 2,000 kg./sq.cm. and preferably of between 2,300 kg./sq.cm. and 10,000 kg./sq.cm.
- the highly stressed film may be of copper, and advantageously immediately overlie a film, applied by electroless deposition, of palladium or silver.
- the highly stressed film may be of silver, palladium, orgold, and especially nickel; such a film is conveniently applied onto a film, applied by electroless deposition, of nickel or copper. It is generally more convenient that such a film is of nickel, since electroless copper baths tend to be less stable than are electroless nickel baths.
- These films of nickel or copper, applied by electroless deposition in turn preferably immediately overlie a film, applied by electroless deposition, of palladium or silver.
- Highly stressed films are sometimes dull.
- a lightly stressed, bright film of nickel, copper, silver, palladium, or gold i.e. one having an average stress in tension of not more than 1,500 kg./sq.cm., preferably between 1,050 kg./sq.cm. and 1,400 kg./sq.cm., may be electrolytically deposited onto such films.
- the average thickness of this lightly stressed film, together with any subsequent, electrolytically deposited films of metal should not greatly exceed, say ten times, that of the highly stressed film, or the advantages of theinvention may be forfeited.
- the lightly stressed film is of nickel
- a film of cadmium, tin, silver, gold, lead, or particularly chromium may be electrolytically deposited thereon.
- the nickel, copper, silver, palladium or gold may be deposited in the two conditions, viz highly stressed and lightly stressed, by using plating baths of differing composition and/or pH.
- nickel baths usually contain nickel chloride and nickel sulfate, and different ratios of chloride to sulfate ions favor formation of nickel in a more highly, or less highly, stressed condition other things being equal, when chloride ions preponderate, the nickel is more highly stressed, and when sulfate ions are in the majority, the nickel is less highly stressed.
- Use of a less acidic plating solution typically having a pH of between 5 and 6.8 also favors formation of a more highly stressed layer than does use of one having a pH below 5.
- the plated shim steel is removed, and the change in radius of curvature due to the tensile stress of the film of electrode'posited metal is measured.
- the average stress in tension, 5, can be found by means of the relationship where t is the thickness of the base, d is the thickness of the .deposit, E is Youngs modulus for the base, and r, and r,, are
- the plastics material should contain a filler; the filler should, of course, be inert, i.e. resistant to attack by the various solutions employed. It is further desirable that the tiller be present in a substantial amount, the plastics material containing at least 20 percent, and better at least 50 percent, by volume of the filler.
- Suitable fillers include china clay, which may be calcined (molochite) and titanium dioxide, but glass fibers or fibers of a textile such as a polyester are particularly preferred.
- the plastics article should be etched, preferably by chemical means because the surface finish of mechanically etched plastics material may be poor unless a very thick layer of metal is applied by electroplating to apply such layers is uneconomic, and further, they do not adhere as well as those of conventional thickness.
- Chromic acid mixtures potassium dichromate-sulphuric acid-water are usually suitable.
- thermoplasts such as a polyolefine, a polymethacrylate, a polycarbonate, an acrylonitrile butadiene-styrene copolymer, or a polysulfone
- thermoset plastics material may be, for example, a cured epoxy resin, i.e.
- thermoset plastics material may be a glass fiber laminate. Such laminates, electroplated with silver, palladium, or gold, are useful for printed circuits.
- glass fibers silane-treated (filler) In place of the OP wax, other release agents such as calcium stearate, glycerol monostearate, stearic acid, or carnauba wax could be used.
- the articles were formed by transfer molding, the molding time being 3 minutes and the temperature 165 C. Radio frequency preheating was used.
- Etching Moldings so prepared were etched by immersion for to minutes at room temperature, or better at 65 C., in a mixture of 1 lg. of potassium dichromate, 250 ml. of distilled water and 750 ml. of concentrated sulfuric acid.
- Nickel chloride NiCl .(ili g Hydrazino sulphate (N ll,.lI bO,), g-
- NiSO '6H O nickel sulfate
- 10 g. of sodium citrate Na,c,n, O -2H O 10 g. of sodium acetate (NaC,l-l O,-3H,O)
- 15 g. of sodium hypophosphite Nau,Po,-u,o 20 g. of magnesium sulfate (MgSO '7l-I O) and 1 liter of distilled water.
- MgSO '7l-I O magnesium sulfate
- NiSO -6H,O nickel sulfate
- NiCl -6l-l O nickel chloride
- boric acid 18 g. of sodium formate
- 8 g. of cobalt sulfate CoSO -7H O
- the pH of this solution was 5.3; in some experiments the pH was adjusted before plating to 5.6 or 6.1 by adding nickel carbonate or to 4.2 by adding concentrated sulfuric acid.
- the coating was on average 0.02 mm. thick. As determined by the GrahamSoderberg method, the tensile stresses of nickel plated at the different pH values were:
- EFCO Bright Nickel (a proprietary formulation available from Electra-Chemical Engineering Co. Ltd., Woking, Surrey, England) the bath being kept at 45 to 55 C. and having a pH of 3.9, and the current density being 3.2 to 5.4 amps/sq. dcm.; or
- the current density was 1 1 to 13 amps/sq. dcm., and the maximum voltage at strike was 5.
- the plating time was 2 minutes.
- a bath containing 250 g. per liter of chromic oxide (CrO and 2 g. per liter of concentrated sulfuric acid this bath was kept at 50 C. and the currentdensity was to 20 amps/sq. dcm.
- moldings prepared from the same epoxy resin formulation were plated as described above except that the electrodeposition of the nickel was efiected under conventional conditions.
- the bath was similar to that employed to deposit the highly stressed coating, but it contained 50 g. of sodium formate per liter of distilled water instead of 18 g., and no cobalt sulfate; its pH was 4.5 and its temperature 40 C., while the current density was 2.7 to 3.2 amps/sq. dcm.
- the nickel so deposited had essentially the same average thickness as the combined average thicknesses of the two layers of nickel electrodeposited as described above, i.e. an average of 0.05 mm. compared with the average total of 0.04 mm. for the two layers electrodeposited in accordance with this invention.
- the tensile stress of the single, conventionally electrodeposited layer was 1,400 kg./sq.cm. Chromium was then applied by electroplating in a conventional manner.
- the Jaquet peel test could not be carried out with the chromium-plated moldings having coatings of nickel electrodeposited as described in accordance with the process of this invention; the adhesion was so great that the coating could not be pried off. On the other hand, the chromium could readily be peeled off from the castings prepared in the conventional manner.
- the coatings produced as described by the process of this invention were distinguished by their resistance to repeated extreme changes in temperature. Samples of the chromiumplated moldings were held at 72 C. or at 85 C. for 1 hour, then immediately placed in an oven heated to 145 C. for 1 hour next, the samples were immediately cooled to 72 C. or -85 C. and the process repeated. After six, or even eight, cycles of cooling and heating, the coatings still adhered to the underlying plastics material, whereas the chromium on moldings plated in a conventional manner could be peeled off before fewer than six such cycles had been completed.
- thermoplastic resin viz. a polysulfone available from Union Carbide Corporation under the designation Polysulfone P 1700, containing 10 percent by weight of molochite
- EXAMPLE III A laminate was prepared by a wet lay-up technique from eight layers of glasscloth, and as the thermoset material, a mixture of 100 parts by weight of an epoxide resin, a polyglycidyl ether of bisphenol A (i.e. 2,2-bis(4-hydroxyphenyl)propane) having a 1,2-epoxide content of 5.2 equivalents per kilogram, and 27 parts by weight of 4,4-diaminodiphenylmethane. The assembly was heated at 150 C. for 1 hour under a pressure of 7 kg./sq.cm., and the resin was post-cured at 180 C. for 3 hours.
- the thermoset material a mixture of 100 parts by weight of an epoxide resin, a polyglycidyl ether of bisphenol A (i.e. 2,2-bis(4-hydroxyphenyl)propane) having a 1,2-epoxide content of 5.2 equivalents per kilogram, and 27 parts by weight of 4,4-diamino
- Laminates were also made by a prepreg" technique layers of glasscloth were impregnated with a solution in ethyl methyl ketone of the same mixture of epoxide resin and curing agent, and the mixture was advanced to a B-stage resin by heating for 30 minutes at C. The resin was cured by heating as before, i.e. for 1 hour at C. under a pressure of 7 kg./sq.cm. and then for 3 hours at C.
- the laminates were etched, sensitized and coated with nickel by electroless deposition as described in Example 1.
- a highly-stressed coating of copper was applied from a bath containing, per liter, 19 g. of cuprous cyanide, 45 g. of sodium cyanide, and 4 g. of sodium hydroxide.
- the bath was kept at 40 to 45 C. and the current density was 2.15 amps/sq.dcm.
- Coatings of silver likewise showing good adhesion and being highly stressed in tension, were electrodeposited on similar glasscloth laminates bearing nickel applied by electroless deposition.
- said highly stressed film of a metal selected from the group consisting of copper and nickel immediately underlies a lightly stressed, electrolytically deposited film of a metal selected from the group consisting of nickel and copper having an average stress in tension of not more than 1,500 kg./sq.cm., the average thickness of said lightly stressed film, together with any subsequent, electrolytically deposited, films of metal, does not exceed ten times that of the said highly stressed film.
- the said lightly stressed film is of nickel and immediately underlies an electrolytically deposited film of chromium, cadmium, tin, silver, gold or lead.
- plastics material contains at least 50 percent by volume of filler.
- filler is selected from the group consisting of glass fibers and textile fibers.
- thermoset material is a material that is thermoset material.
- thermoset plastics material is a glass fiber laminate.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB25253/68A GB1249309A (en) | 1968-05-27 | 1968-05-27 | Plastics materials having electrodeposited metal coatings |
Publications (1)
Publication Number | Publication Date |
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US3661538A true US3661538A (en) | 1972-05-09 |
Family
ID=10224690
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US826709A Expired - Lifetime US3661538A (en) | 1968-05-27 | 1969-05-21 | Plastics materials having electrodeposited metal coatings |
Country Status (11)
Country | Link |
---|---|
US (1) | US3661538A (fr) |
AT (1) | AT290239B (fr) |
BE (1) | BE733614A (fr) |
CA (1) | CA932694A (fr) |
CH (1) | CH512993A (fr) |
DE (1) | DE1925103C3 (fr) |
ES (1) | ES367664A1 (fr) |
FR (1) | FR2009376A1 (fr) |
GB (1) | GB1249309A (fr) |
NL (1) | NL6907965A (fr) |
SE (1) | SE350640B (fr) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3771977A (en) * | 1971-12-27 | 1973-11-13 | Hooker Chemical Corp | Bearing surface |
US3865558A (en) * | 1972-06-01 | 1975-02-11 | Saint Gobain | Window |
US3868229A (en) * | 1974-06-10 | 1975-02-25 | Int Nickel Co | Decorative electroplates for plastics |
US3915809A (en) * | 1974-05-24 | 1975-10-28 | Gen Motors Corp | Plating adherent metal coatings onto polymethyl methacrylate materials |
US3930807A (en) * | 1973-04-25 | 1976-01-06 | Canon Kabushiki Kaisha | Plastic molding having satin finish type metallic luster |
US4082621A (en) * | 1977-01-03 | 1978-04-04 | Allied Chemical Corporation | Plating method with lead or tin sublayer |
US4234648A (en) * | 1979-01-29 | 1980-11-18 | Hexcel Corporation | Electrically conductive prepreg materials |
EP0056986A1 (fr) * | 1981-01-22 | 1982-08-04 | Toyo Boseki Kabushiki Kaisha | Méthode de fabrication d'un objet moulé metallisé |
US4486490A (en) * | 1979-01-29 | 1984-12-04 | Hexcel Corporation | Electrically conductive prepreg materials |
US4770751A (en) * | 1986-12-30 | 1988-09-13 | Okuno Chemical Industry Co., Ltd. | Method for forming on a nonconductor a shielding layer against electromagnetic radiation |
US5008157A (en) * | 1989-11-22 | 1991-04-16 | Paxos Michael N | Metallized article and process for metallizing a non-conductive article |
US20060086620A1 (en) * | 2004-10-21 | 2006-04-27 | Chase Lee A | Textured decorative plating on plastic components |
US20100159268A1 (en) * | 2005-06-21 | 2010-06-24 | Andreas Fath | Method for producing decorative surface structures |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3040300A1 (de) * | 1979-10-30 | 1981-05-14 | Mitsubishi Keikinzoku Kokyo K.K., Tokyo | Spiegel und verfahren zur herstellung derselben |
DE3421123A1 (de) * | 1984-06-07 | 1985-12-12 | Bayer Ag, 5090 Leverkusen | Verbundmaterial |
GB2161836B (en) * | 1984-07-21 | 1987-12-31 | Bg Electrical Accessories Limi | Plastics electrical plug coated with decorative material having matallic appearance |
CN103757677B (zh) * | 2013-11-29 | 2017-01-25 | 云南云天化股份有限公司 | 聚甲醛制件表面处理方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3523874A (en) * | 1967-03-16 | 1970-08-11 | Hooker Chemical Corp | Metal coating of aromatic polymers |
US3527579A (en) * | 1967-01-19 | 1970-09-08 | Phillips Petroleum Co | Electroplated preformed polymeric articles of manufacture |
-
1968
- 1968-05-27 GB GB25253/68A patent/GB1249309A/en not_active Expired
-
1969
- 1969-05-16 DE DE1925103A patent/DE1925103C3/de not_active Expired
- 1969-05-21 CH CH773569A patent/CH512993A/de not_active IP Right Cessation
- 1969-05-21 US US826709A patent/US3661538A/en not_active Expired - Lifetime
- 1969-05-22 FR FR6916729A patent/FR2009376A1/fr not_active Withdrawn
- 1969-05-23 SE SE07333/69A patent/SE350640B/xx unknown
- 1969-05-23 NL NL6907965A patent/NL6907965A/xx unknown
- 1969-05-26 ES ES367664A patent/ES367664A1/es not_active Expired
- 1969-05-26 CA CA052495A patent/CA932694A/en not_active Expired
- 1969-05-27 BE BE733614D patent/BE733614A/xx unknown
- 1969-05-27 AT AT500969A patent/AT290239B/de not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3527579A (en) * | 1967-01-19 | 1970-09-08 | Phillips Petroleum Co | Electroplated preformed polymeric articles of manufacture |
US3523874A (en) * | 1967-03-16 | 1970-08-11 | Hooker Chemical Corp | Metal coating of aromatic polymers |
Non-Patent Citations (6)
Title |
---|
50TH Annual Technical Proceedings, Amer. Electroplaters Society, 1963, pgs 44 46. * |
Chemical and Engineering News (C & EN) March 25, 1963, pages 48 49 * |
Electroplating and Electroforming, by Blum et al., 1949, page 368 * |
Modern Electroplating by Lowenheim, 1968, page 262 * |
Stress in Electrodeposited Coatings, by Kushner, Metal Finishing, April 1956, pps 48 50 * |
Technology of Electrodeposition by Vagramyan et al., Robert Draper Ltd., 1961, pps. 269 270 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3771977A (en) * | 1971-12-27 | 1973-11-13 | Hooker Chemical Corp | Bearing surface |
US3865558A (en) * | 1972-06-01 | 1975-02-11 | Saint Gobain | Window |
US3930807A (en) * | 1973-04-25 | 1976-01-06 | Canon Kabushiki Kaisha | Plastic molding having satin finish type metallic luster |
US3915809A (en) * | 1974-05-24 | 1975-10-28 | Gen Motors Corp | Plating adherent metal coatings onto polymethyl methacrylate materials |
US3868229A (en) * | 1974-06-10 | 1975-02-25 | Int Nickel Co | Decorative electroplates for plastics |
US4082621A (en) * | 1977-01-03 | 1978-04-04 | Allied Chemical Corporation | Plating method with lead or tin sublayer |
US4234648A (en) * | 1979-01-29 | 1980-11-18 | Hexcel Corporation | Electrically conductive prepreg materials |
US4486490A (en) * | 1979-01-29 | 1984-12-04 | Hexcel Corporation | Electrically conductive prepreg materials |
EP0056986A1 (fr) * | 1981-01-22 | 1982-08-04 | Toyo Boseki Kabushiki Kaisha | Méthode de fabrication d'un objet moulé metallisé |
US4770751A (en) * | 1986-12-30 | 1988-09-13 | Okuno Chemical Industry Co., Ltd. | Method for forming on a nonconductor a shielding layer against electromagnetic radiation |
US5008157A (en) * | 1989-11-22 | 1991-04-16 | Paxos Michael N | Metallized article and process for metallizing a non-conductive article |
US20060086620A1 (en) * | 2004-10-21 | 2006-04-27 | Chase Lee A | Textured decorative plating on plastic components |
US20100159268A1 (en) * | 2005-06-21 | 2010-06-24 | Andreas Fath | Method for producing decorative surface structures |
Also Published As
Publication number | Publication date |
---|---|
DE1925103C3 (de) | 1974-05-02 |
CH512993A (de) | 1971-09-30 |
SE350640B (fr) | 1972-10-30 |
NL6907965A (fr) | 1969-12-01 |
BE733614A (fr) | 1969-11-27 |
DE1925103A1 (de) | 1969-12-11 |
CA932694A (en) | 1973-08-28 |
AT290239B (de) | 1971-05-25 |
GB1249309A (en) | 1971-10-13 |
DE1925103B2 (de) | 1973-09-13 |
FR2009376A1 (fr) | 1970-02-06 |
ES367664A1 (es) | 1971-04-16 |
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