US3865699A - Electrodeposition on non-conductive surfaces - Google Patents

Electrodeposition on non-conductive surfaces Download PDF

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Publication number
US3865699A
US3865699A US408410A US40841073A US3865699A US 3865699 A US3865699 A US 3865699A US 408410 A US408410 A US 408410A US 40841073 A US40841073 A US 40841073A US 3865699 A US3865699 A US 3865699A
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Prior art keywords
nickel
sulfur
metal
elastomer
carbon black
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US408410A
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English (en)
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Daniel Luch
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Huntington Alloys Corp
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International Nickel Co Inc
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Application filed by International Nickel Co Inc filed Critical International Nickel Co Inc
Priority to US408410A priority Critical patent/US3865699A/en
Priority to CA203,843A priority patent/CA1037896A/en
Priority to JP49100794A priority patent/JPS5067731A/ja
Priority to GB44629/74A priority patent/GB1480522A/en
Priority to AU74387/74A priority patent/AU488730B2/en
Priority to ZA00746656A priority patent/ZA746656B/xx
Priority to DE19742450069 priority patent/DE2450069A1/de
Priority to CH1411474A priority patent/CH592503A5/xx
Priority to IT53660/74A priority patent/IT1032105B/it
Priority to NL7413806A priority patent/NL7413806A/xx
Priority to ES431240A priority patent/ES431240A1/es
Priority to SE7413267A priority patent/SE410627B/xx
Priority to BE149797A priority patent/BE821382A/xx
Priority to AT853474A priority patent/AT334150B/de
Priority to FR7435534A priority patent/FR2248339B1/fr
Priority to IN2402/CAL/74A priority patent/IN142485B/en
Priority to US05/527,532 priority patent/US4009093A/en
Application granted granted Critical
Publication of US3865699A publication Critical patent/US3865699A/en
Priority to CA302,771A priority patent/CA1070939A/en
Priority to JP57094655A priority patent/JPS585378A/ja
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating

Definitions

  • ABSTRACT A process for metalizing a non-conductive substrate wherein the substrate is coated with an organic polymer-carbon black mixture, having a volume resistivity of less than about 1,000 ohm-centimeters, the surface of the mixture is caused to contain sulfur and the thus treated substrate is placed as a cathode in a nicke1, cobalt or viron plating bath to cause a rapid spread of metal across the thus treated surface.
  • the present invention is concerned with electrodeposition and more particularly with electroplating of a non-electrically conductive substrate.
  • the first process involves the coating of the non-conductive object with an electrically conductive lacquer followed by electroplating.
  • the second process involves sensitizing the non-conductive object, chemically depositing a metal on the sensitized surface and thereafter electroplating the thus metallized surface.
  • the second process as generally practiced by the prior art can achieve good results but only at a cost of employing a large number of individual processing operations carried out with very great care by skilled per sonnel. Furthermore, because the underlying chainically deposited metal can be different from metalsubsequently electrochemically deposited, there is a good chance of forming an electrochemical couple between the two even when, nominally the metals are the same. Thus the possibility of accelerated, localized corrosion exists wherever and whenever the outer electrodeposited layer is not continuous.
  • Minklei proposed to treat a plastic surface with an aqueous solution of alkali metal sulfide followed by contacting the treated surface with a metal salt prior to electroplating.
  • Brown et al. proposed contacting a plastic surface with a solu-. tion or dispersion of sulfur in an organic medium and contacting the treated surface with an aqueous solution of cuprous salt prior to plating.
  • the proposals involve the formation of a metal sulfide on the plastic surface and not the type of metal-polymer bond, which, as will become apparent from the subsequent description, is formed by virtue of'the process of the present invention.
  • FIG. 1 depicts electrodeposit growth obtained in accordance with the present invention
  • FIG. 2 depicts undesirable electrodeposit growth obtained when an essential requirement of the process of the present invention is omitted.
  • the present invention contemplates a process wherein at least part of a substrate for electrodeposition comprises or is coated with an adherent layer of a mixture of an organic polymer and an electrically conductive carbon black of such proportion so as to have an electrical resistivity of less than about 1,000 ohm-centimeter; at least the exposed surface of the layer is caused to contain an effective amount of sulfur, and the thus coated object is then introduced into a nickel, cobalt, or iron plating bath as the cathode to cause rapid deposition of metal across the coated surface. Thereafter the metal coated object can be subjected to further electrodeposition in ways well known to those skilled in the art.
  • the polymer used along with conductive carbon black in the coating layer (and which. may also constitute the substrate) is, advantageously a member of the group of organic polymers which readily react with molecular sulfur or a sulfur donor of the type described herein.
  • Advantageous polymers for use in the process of the present invention include hydrocarbonaceous and substituted hydrocarbonaceouselastomers such as natural rubber, a polychloroprene, butyl rubber, chlorinated butyl rubber, polybutadiene rubber, acryloni trile-butacliene rubber, styrene-butadiene rubber, etc.
  • elastomers- are unsaturated and readily combine with molecular sulfur through either unsaturated linkages in the carbon skeletal structure of the polymer or through activated sites on the polymer structure associated with unsaturated linkages or pendant substituent atoms.
  • Another advantageous type of polymer for use in the process of the present invention is an ethylenepropylene terpolymer comprising a saturated poly-ethylene-propylene main chain having unsaturated groups derived from non-conjugated dienes, e.g., hexadiene, dicyclopentadiene etc., pendant from the main chain.
  • Such a terpolymer is readily vulcanized with sulfur.
  • polymersusefull in the process of the present invention include essentially saturated polymers such as polystyrene, polyvinyl chloride, polyurethane etc., which apparently possess active sites for reaction with sulfur. While polyethylene (and similar polymers of limited solubility) are not readily suited for use in coating formulations, it has been found that milled and molded polyethylene compositions containing carbon black and a sulfur donor can advantageously be employed in the process of the present invention. Undoubtedly some organic polymers, for example, perhaps, polytetrafluoroethylene are too inert to react with sulfur and these polymers are excluded from the ambit of the present invention. However, the great bulk of normally used organic polymeric materials appears to be useable in the process of the present invention.
  • those having elastomeric characteristics e.g., rubbers, elastomeric polyurethane etc.
  • an elastomer has the ability to dampen stress concentrations which can result in failure of the deposited coating upon exposure to applied stress or thermal cycling.
  • the carbon black included for the purpose of providing a proper degree of electrical conductivity acts as a reinforcement agent to improve the physical characteristics of the elastomer. Further factors which make elastomers most advantageous include rapidity of metal coverage and relatively low cost of materials.
  • the unsaturated elastomers are deemed to be the most advantageous.
  • the exposed surface ofthe polymer-conductive carbon black composition is caused to contain sulfur it is possible that the sulfur initially attacks the polymer chain at activated positions, to provide activated sites for bonding of nickel to the polymer.
  • nickel deposits are made in accordance with the teachings of the present invention very strong, highly useful metal to organic bonds are formed very strong, highly useful metal to organic bonds are formed very rapidly on polymer-carbon black surfaces. It is important to avoid overcuring of a polymer with sulfur (or other curative) prior to plating. It appears that a polymer-sulfur-metal bond can occur with most polymers as long as activated sites on the polymer chain exist. Heavy curing, especially in sulfur monochloride will remove these sites from an unsaturated elastomer causing poor plating both as to speed of coverage and as to adherence of the metal. I
  • the exposed surface of the polymer-carbon black plating substrate can contain sulfur by inclusion of sulfur in the whole mass of the plating substrate or by enriching the exposed surface with sulfur.
  • a plating substrate containing an unsaturated polymeric elastomer will contain about 0.5% to about 5% of sulfur based upon weight of elastomer in order to permit curing of the elastomer.
  • agents other than sulfur or sulfur compounds are used for curing the exposed surface of the elastomer can be enriched in sulfur by contacting the surface with a solution containing elemental sulfur or by exposing the surfaces to a sulfur-containing vapor e.g., the vapor of sulfur monochloride (S Cl).
  • S Cl sulfur monochloride
  • the plating substrate will normally contain ingredients other than sulfur, elastomer and conductive carbon black such are normally included in rubber compositions.
  • Such other ingredients include vulcanization accelerators and modifiers, antioxidants and similar types of materials which have been found to be useful in rubber technology.
  • vulcanization accelerators and modifiers include vulcanization accelerators and modifiers, antioxidants and similar types of materials which have been found to be useful in rubber technology.
  • all ingredients should be limited in amount to amounts which will be permanently soluble in the cured elastomer at normal temperatures i.e., about 25C.
  • Plating substrates used in the present invention usually contain carbon black and polymer in weight ratios of about 0.2 to about 1.5 (conductive carbon black to polymer) although somewhat higher or lower weight ratios can be used. It is usually more advantageous to employ weight ratios of conductive carbon black to polymer in the range of about 0.5 to L0. It has been noted with coatings on non-electrically conductive substrates that speed of coverage of polymer-carbon black surfaces becomes very low at very high loadings of carbon black indicating that a minimum surface concentration of polymer is necessary not only for attaining mechanical strength but also forpurposes of facilitating the metal spreading mechanism of the invention. Because carbon blacks vary greatly depending upon sources and methods of manufacture, it is not practical to specify with more precision the relative amounts of polymer and carbon black required in accordance with the present invention.
  • the criterion of operability of a particular polymer-carbon black mixture is the electrical volume resistivity.
  • the volume resistivity must be less than about l,000 ohm-centimeters and more advantageously is less than about 10 ohmcentimeters.
  • Optimum results have been obtained using conductive carbon blacks made from acetylene such as sold by Shawingan Products Corporation under the trade designation Acetylene Carbon Black.
  • conductive carbon black which possesses relatively high resistance to mechanical breakdown during milling with a polymer is sold by Cabot Corporation under the trade designation of Vulcan XC72.
  • mixtures of conductive and non-conductive carbon blacks can be used provided that the final polymer-carbon black product has a volume resistivity in the range set forth hereinbefore.
  • the proper volume re sistivity can be achieved in polymer-carbon black compositions which are made entirely with non-conductive carbon blacks for example, furnace blacks.
  • Such compositions ordinarily do not have adequate electrical characteritics when used as coatings and dried on a substrate. However, these compositions may have adequate characteristics for use as molded, extruded or like-formed shapes which can be treated electrochemically in accordance with the present invention without a separate preliminary coating step.
  • the rate of coverage of nickel cobalt or iron on a cathode having a surface of polymer-carbon black mixture in accordance with the present invention extending from a point of contact with an electronic conductor (e.g., a metal) is dependent at least upon the resistivity of the mixture, the sulfur content at the mixture surface, the applied voltage across the anodeelectrolyte-cathode circuit; and the nature of the polymer.
  • an electronic conductor e.g., a metal
  • the minimum rate at which nickel spreads across the cathode surface at a voltage of 3.0 volts is about 0.5 centimeter per minute (cm/min).
  • a series of polymer-acetylene black compositions were made containing 100 parts by weight of polymer and 50 parts by weight of the carbon black.
  • compositions devoid of sulfur were coated on an ABS panel having a metal contact point at one end.
  • the panels were immersed in a Watts type nickel plating bath as cathodes at a voltage of 3.0. The rate of nickel coverage was measured.
  • the panels were dipped in a solution of 1% (by weight) of sulfur in cyclohexane, removed and the cyclohexane allowed to evaporate prior to electrolytic treatment in exactly the same manner as was the first series. The results of these tests are set forth in Table I.
  • Table I shows that a very small amount of sulfur incorporated in the exposed surface of the polymer increases nickel coverage rates by a factor of at least about 2.5.
  • rates of nickel coverage can be much higher. For example, with a composition containing 100 parts by weight nitrile rubber, 50 parts by weight acetylene black and 4 parts by weight sulfur, nickel coverage rates at 3.0 volts of over 6 cm/min. can be obtained. The rate of nickel coverage increases linearly with increases in voltage.
  • a nickel coverage rate of about 9.5 cm/min. was obtained at a voltage of 3.0 and a rate of about 14.7 cm/min. at a voltage of 4.5. It is important that the sulfur present in the polymer-carbon black compositions be in the form of non-ionic sulfur, i.e., that. it not be tied up as a metal sulfide or in a stable ion such as the sulfate ion.
  • sulfur in the form of a sulfur donor such as sulfur chloride, 2-mercapto-benzothiazole, N- cyclohexyl-2-benzothiozole sulfonomide, dibutyl xanthogen disulfide and tetramethyl thiuram disulfide or combinations of these and sulfur can also be employed.
  • sulfur donors are the materials which have been used or have been proposed for use as vulcanizing agents or accelerators.
  • FIGS. 1 and 2 depict indentical acrylonitrile-butadienestyrene plaques 11 coated with polymer-carbon black coating 12 containing 20 parts by weight of neoprene and 10 parts by weight of acetylene black and having a wire contact 13.
  • the coating 12 of FIG. I initially contained a small amount of thiuram and was treated with a 1% by weight solution of sulfur in cyclohexane prior to plating so as to incorporate a small effective amount of sulfur in the coating.
  • Coating 12 of FIG. 2 was made with a neoprene free of thiruam, was not exposed to a sulfur solu tion and therefore contained no sulfur.
  • Both plaques were made cathodic under identical voltage conditions (3 volts closed circuit cell potential) in the same nickel plating bath. After 1 /2 minutes the area 15 above line 14 in FIG. 1 was uniformly coated with a highly adherent nickel deposit. At this time the plaque .was removed from the plating bath.
  • the cathodic electrolytic treatment used according to the present invention to induce nickel coverage across the expanse of polymer-carbon black mixture surface is carried out in an electrolyte bath from which nickel can be deposited and which, ordinarily is aqueous and contains about to about grams per liter (gpl) of nickel ion, complementing anion from the group of sulfate, chloride, sulfamate, fluoborate and mixtures thereof and exhibits a pH of about 2.8 to about 4.5 stabilized by inclusion of a buffer such as boric acid in the bath.
  • An ordinary Watts bath is quite satisfactory for use both as'the initial bath for nickel coverage and for subsequentt plating.
  • nickel coverage after nickel coverage has been established, one can plate in a nickel bath containing any kind of additive, e.g., levelling agents or brightening agents, etc., known to the art. Further, after nickel coverage is established one can plate not only with nickel but also with any other electrodepositable metal compatible with nickel, e.g., chromium, copper. zinc, tin, silver, gold, platinum, palladium, cadmium etc.
  • any kind of additive e.g., levelling agents or brightening agents, etc.
  • the cathodic treatments in accordance with the invention to induce the growth of iron or cobalt across the polymer carbon-black surface can be carried out in any electroplating bath from which these metals can be deposited.
  • the process of the invention has been carried out using an aqueous ferrous chloride bath to deposit iron and an aqueous cobalt chloridecobalt sulfate bath to deposit cobalt. Details of operation for these and other iron, cobalt and nickel baths can be obtained from any text on electroplating, for example, Electoplating Engineering Handbook, edited by A. Kenneth Graham, Reinhold Publishing Corporation, Copyright 1955. Those skilled in the art will appreciate that for particular purposes it may be advantageous to deposit alloys of nickel, cobalt and iron such as ironnickel alloys, nickel-cobalt alloys etc.
  • the present invention is especially concerned with electrodeposition of metal on a wide variety of plastic and other non-conductors (and on other materials which are not generally amenable to ordinary electroplating techniques) using a coating technique involving an essentially solid polymer carbon-blacksulfur-containig coating adhered directly or through an intermediate layer onto a base
  • the invention is also applicable to bases having the requisite carbon blackpolymer-sulfur composition.
  • a sample of EPDM synthetic rubber having a volume resistivity of about 235 ohm-centimeters and containing reinforc ing type, furnace carbon black and sulfur is directly plateable in a Watts-type nickel bath to provide a highly adherent, rapidly formed overall deposit of nickel.
  • the spreading of the deposit from a point of metallic conduction differs somewhat in the case of a solid base of polymer-carbon black-sulfur from the spreading depicted in FIG. 1 of the drawing which is typical of metal spreading using coatings.
  • a solid polymer-carbon black-sulfur base With a solid polymer-carbon black-sulfur base the electrodeposited metals tends to rapidly film over the entire surface of the object blurring to a certain extent the metal deposition front depicted in FIG. 1 of the drawing.
  • the aforedescribed coating formulation was sprayed on an acrylonitrile-butadiene-styrene (ABS) surface to provide a dried coating about 0.0025 cm. thick.
  • ABS acrylonitrile-butadiene-styrene
  • the coated and dried ABS surface was then exposed for 40 seconds to the vapor above sulfur monochloride held at room temperature (about 25C).
  • the surface having a single metal contact was'then placed in a Watts-type nickel plating bath as a cathode with a driving voltage of about 3 volts in opposition to a nickel anode.
  • the nickel deposit grew rapidly across the coated ABS surface and deposition was continued until the deposited nickel had a substantially uniform thickness of about 0.0025 cm.
  • the electrodeposit showed a 90 peel strength of about 1.88 kilogram per centimeter (kg/cm) width (10.5 lb/in width) when pulled at 2.54 cm/minute.
  • Coating A was applied by brushing onto a poly-(vinyl chloride) (PVC) plaque, and then coating B was applied in similar fashion over the dried coating A. After curing in an air oven for 3 hours at 90C. the plaque was dipped into a l w/o solution of sulfur in cyclohexane, then plated to a thickness of about 0.001 inch with Watts nickel. Initially the nickel deposit grew rapidly across the surface of the plaque from a single metal contact. A 90 peel strength of 2.5 kg/cm l 2 lb/in) was achieved for the electrodeposit.
  • PVC poly-(vinyl chloride)
  • Neoprene AF 50 Neozone D l
  • EXAMPLE IV Coatings A and B from Example 11 were modified so that the concentration of curatives (CP-B, Ethazate, D-B-A and sulfur) was doubled.
  • MEK was added to coating A such that its final weight equaled that of the xylene (i.e., from 11.3 to 77.5).
  • An ABS panel was successively dipped in modified coating A, then into modified coating B. The panel was cured at 85C for 1 /2 hours, during which time a noticeable sulfur bloom appeared on the surface. The panel was then directly electroplated with Watts nickel with a rapid initial rate of coverage. The resulting metal deposit exhibited a 90 peel adhesion of about 3.58 kg/c m of width lb/in).
  • EXAMPLE V An ABS panel (Cycolac standard test plaque) was coated by successively dipping in first coating A, then coating B of Example 11. After curing 15 hours in air at 85C, the panel was dipped into a l w/o solution of sulfur in cyclohexane. It was then plated with a Watts FLASH, 0.0009 inch of semibright (Perflow) nickel, 0.0003 inch of bright (Udylite) nickel and 15 p. in conventional chromium. The plated panel was given a thermal cycle of 90C for 2 hours, room temperature for 1 hour, 40C for 2 hours, and then given a 16-hour exposure to CASS testing. No detectable failure resulted on the panel from this treatment.
  • ABS plastic plaques were used, the process of the present invention is equally as well adapted to the electroplating of utilitarian and decorative objects made of other plastics such as polystyrene, phenol formaldehyde resins, ureaformaldehyde resins, polyacrylates and methacrytates, polyurethane, silicones, vinyls, vinylidenes, epoxys, polyolefins and similar thermoplastic and thermosetting resinous materials.
  • the process of the present invention can also be used to plate metals which are coated with non-metallic, non-electrically conductive coatings, e.g., varnished aluminum and the like.
  • Example VI A sample plastic treated and coated as in Example 111 was immersed as a cathode in an aqueous plating bath containing 300 gpl of ferrous chloride, 150 gpl of calcium chloride adjusted to a pH of 1.2 to 1.8 and held at a temperature of about 87C. Upon passage of current through the bathat a voltage of 6 volts, the surface of the sample became covered with a smooth adherent coating of iron.
  • Example VII The sample of Example V] was. immersed as a cathode in an aqueous cobalt plating bath containing about 335 gpl of cobalt sulfate, about 74 gpl of cobalt chlo ride, about 46.5 gpl of boric acid and about 1.2 gpl of sodium fluoborate. Upon passage of current through the bath, the sample rapidly filmed over with cobalt.
  • EXAMPLE Vlll One hundred parts by weight of a low-density, general purpose polyethylene were milled in a Banbury type mixer at a temperature of about 178C. along with 50 parts by weight of Vulcan XC72 carbon black (supplied by Cabot Corporation) and Tetrone A brand dipentamethylenethiuram hexasulfide. The milled composition was then molded and the molding thus produced was inserted as a cathode in a nickel plating bath. Nickel rapidly spread over the surface from a metallic point of contact and plating was continued to provide a firm, adherent nickel electrodeposit having a peel strength of about 1.8 kg/cm of width.
  • Example Vlll is illustrative of a broader range of polyethylene, polypropylene and mixtures and copolymers thereof having blended therein about 15% to about 60% by weight (of the total composition) of carbon black, to give a volume resistivity of less than about 1,000 ohm-centimeters, along with sulfur or a sulfur donor for example of the dipentamethylenethiuran hexasulfide type in an amount equivalent in sulfur content to about 1% to about 10% by weight (of the total composition) of dipentamethylenethiuram hexasulfide.
  • Example VIII the bond strength of nickel'electrodeposited on the polymer surface improves with aging at room temperature.
  • the 90 peel strength set forth in Example VIII is the peel strength observed immediately after plating. After a few days aging the observed bond strength is often double (or more) of that strength as set forth in Example VIII.
  • a process for metallizing comprising (1) introducing an essentially solid surface in contact with a metallic conductor into an electroplating bath from which a metal from the Group VIII of the periodictable and alloys thereof can be plated; (2) said essentially solid surface comprising an intimate mixture of an organic polymer reactive with sulfur, a carbon black and a substance from the group of sulfur and sulfur donors and having a volume resistivity of less than about 1,000 ohm-centimeters and (3) applying a potential to said surface through said metallic conductor to cause metal from said group to deposit upon said surface in an essentially uniform manner from the locus of said metallic conductor.
  • metal is from the group of iron, nickel and cobalt.
  • a process as in claim 2 wherein the metal deposited is from the group of nickel and cobalt.
  • composition used to form the coating contains sulfur.
  • composition used to form the coating is treated subsequent to coating formation to enrich the surface thereof with sulfur.
  • a process as in claim 11 wherein the material of the coating has a volume resistivity in the range of about 1 to about 10 ohm-centimeters.
  • a process as in claim 10 wherein the metal deposited is from the group of cobalt and nickel.
  • a process as in claim 24 wherein the uniform composition includes polyethylene or polypropylene.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
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US408410A 1973-10-23 1973-10-23 Electrodeposition on non-conductive surfaces Expired - Lifetime US3865699A (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
US408410A US3865699A (en) 1973-10-23 1973-10-23 Electrodeposition on non-conductive surfaces
CA203,843A CA1037896A (en) 1973-10-23 1974-07-02 Electrodeposition of non-conductive surfaces
JP49100794A JPS5067731A (enrdf_load_stackoverflow) 1973-10-23 1974-09-02
GB44629/74A GB1480522A (en) 1973-10-23 1974-10-15 Electrodeposition on organic-polymer-containing surfaces
AU74387/74A AU488730B2 (en) 1973-10-23 1974-10-16 Electrodispostion on non-conductive surfaces
ZA00746656A ZA746656B (en) 1973-10-23 1974-10-21 Electrodeposition on non-conductive surfaces
ES431240A ES431240A1 (es) 1973-10-23 1974-10-22 Un procedimiento de electrodeposicion.
CH1411474A CH592503A5 (enrdf_load_stackoverflow) 1973-10-23 1974-10-22
IT53660/74A IT1032105B (it) 1973-10-23 1974-10-22 Procedimento di deposizione elettrolitica su superfici non conduttive
NL7413806A NL7413806A (nl) 1973-10-23 1974-10-22 Werkwijze voor het elektrolytisch afzetten van een metaal op een substraat.
DE19742450069 DE2450069A1 (de) 1973-10-23 1974-10-22 Verfahren zum galvanischen abscheiden von metallen
SE7413267A SE410627B (sv) 1973-10-23 1974-10-22 Sett att elektropletera en yta pa ett foremal och komposition for genomforande av detta sett
BE149797A BE821382A (fr) 1973-10-23 1974-10-23 Electrodeposition de metal sur un substrat non conducteur
AT853474A AT334150B (de) 1973-10-23 1974-10-23 Verfahren zum elektroplattieren von nichtleitendem material
FR7435534A FR2248339B1 (enrdf_load_stackoverflow) 1973-10-23 1974-10-23
IN2402/CAL/74A IN142485B (enrdf_load_stackoverflow) 1973-10-23 1974-11-02
US05/527,532 US4009093A (en) 1973-10-23 1974-11-27 Platable polymeric composition
CA302,771A CA1070939A (en) 1973-10-23 1978-05-08 Electrodeposition of non-conductive surfaces
JP57094655A JPS585378A (ja) 1973-10-23 1982-06-02 電着用重合体組成物

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US408410A US3865699A (en) 1973-10-23 1973-10-23 Electrodeposition on non-conductive surfaces

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US05/527,532 Division US4009093A (en) 1973-10-23 1974-11-27 Platable polymeric composition

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JP (2) JPS5067731A (enrdf_load_stackoverflow)
AT (1) AT334150B (enrdf_load_stackoverflow)
BE (1) BE821382A (enrdf_load_stackoverflow)
CA (1) CA1037896A (enrdf_load_stackoverflow)
CH (1) CH592503A5 (enrdf_load_stackoverflow)
DE (1) DE2450069A1 (enrdf_load_stackoverflow)
ES (1) ES431240A1 (enrdf_load_stackoverflow)
FR (1) FR2248339B1 (enrdf_load_stackoverflow)
GB (1) GB1480522A (enrdf_load_stackoverflow)
IN (1) IN142485B (enrdf_load_stackoverflow)
IT (1) IT1032105B (enrdf_load_stackoverflow)
NL (1) NL7413806A (enrdf_load_stackoverflow)
SE (1) SE410627B (enrdf_load_stackoverflow)
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Cited By (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101385A (en) * 1977-03-21 1978-07-18 International Nickel Company Process for making a metal plastic structure
FR2393859A1 (fr) * 1977-06-10 1979-01-05 Sumitomo Naugatuck Procede de preparation d'un article metallise par placage
US4158612A (en) * 1977-12-27 1979-06-19 The International Nickel Company, Inc. Polymeric mandrel for electroforming and method of electroforming
US4191617A (en) * 1979-03-30 1980-03-04 The International Nickel Company, Inc. Process for electroplating directly plateable plastic with cobalt alloy strike and article thereof
US4195117A (en) * 1979-03-09 1980-03-25 The International Nickel Company, Inc. Process for electroplating directly plateable plastic with nickel-iron alloy strike and article thereof
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DE3529302A1 (de) * 1985-08-16 1987-02-19 Volker Betz Verfahren zum herstellen von elektrisch leitenden oberflaechen auf nichtleitern
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US4101385A (en) * 1977-03-21 1978-07-18 International Nickel Company Process for making a metal plastic structure
FR2393859A1 (fr) * 1977-06-10 1979-01-05 Sumitomo Naugatuck Procede de preparation d'un article metallise par placage
US4179341A (en) * 1977-06-10 1979-12-18 Sumitomo Naugatuck Co., Ltd. Method for preparation of a plated product
US4158612A (en) * 1977-12-27 1979-06-19 The International Nickel Company, Inc. Polymeric mandrel for electroforming and method of electroforming
US4195117A (en) * 1979-03-09 1980-03-25 The International Nickel Company, Inc. Process for electroplating directly plateable plastic with nickel-iron alloy strike and article thereof
EP0015765A3 (en) * 1979-03-09 1981-04-08 MPD Technology Limited An electroplated plastics object and a process for the manufacture thereof
US4191617A (en) * 1979-03-30 1980-03-04 The International Nickel Company, Inc. Process for electroplating directly plateable plastic with cobalt alloy strike and article thereof
US4278510A (en) * 1980-03-31 1981-07-14 Gulf Oil Corporation Platable propylene polymer compositions
US4429020A (en) 1980-05-22 1984-01-31 Daniel Luch Metal-polymer composite and method of making said composite
US4590115A (en) * 1981-12-14 1986-05-20 Rhone-Poulenc Specialites Chimiques Metallizing of plastic substrata
US4463054A (en) * 1982-09-17 1984-07-31 A. Schulman, Inc. Plastic-metal laminate, process, and composition
US4714653A (en) * 1983-10-28 1987-12-22 Rhone-Poulenc Recherches Metallizable substrate composites and printed circuits produced therefrom
US5476580A (en) * 1993-05-17 1995-12-19 Electrochemicals Inc. Processes for preparing a non-conductive substrate for electroplating
US20040084321A1 (en) * 1993-05-17 2004-05-06 Thorn Charles Edwin Printed wiring boards and methods for making them
US5690805A (en) * 1993-05-17 1997-11-25 Electrochemicals Inc. Direct metallization process
US5725807A (en) * 1993-05-17 1998-03-10 Electrochemicals Inc. Carbon containing composition for electroplating
US6710259B2 (en) 1993-05-17 2004-03-23 Electrochemicals, Inc. Printed wiring boards and methods for making them
US6171468B1 (en) 1993-05-17 2001-01-09 Electrochemicals Inc. Direct metallization process
US6303181B1 (en) 1993-05-17 2001-10-16 Electrochemicals Inc. Direct metallization process employing a cationic conditioner and a binder
US7186923B2 (en) 1993-05-17 2007-03-06 Electrochemicals, Inc. Printed wiring boards and methods for making them
US5545429A (en) * 1994-07-01 1996-08-13 International Business Machines Corporation Fabrication of double side fully metallized plated thru-holes, in polymer structures, without seeding or photoprocess
US5709586A (en) * 1995-05-08 1998-01-20 Xerox Corporation Honed mandrel
US5547516A (en) * 1995-05-15 1996-08-20 Luch; Daniel Substrate structures for integrated series connected photovoltaic arrays and process of manufacture of such arrays
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US20050112388A1 (en) * 1998-12-17 2005-05-26 Tadashi Watanabe Coated metal plate
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US6468672B1 (en) 2000-06-29 2002-10-22 Lacks Enterprises, Inc. Decorative chrome electroplate on plastics
US20040219376A1 (en) * 2000-12-20 2004-11-04 Fuji Xerox Co., Ltd. Heat resistant resin film with metal thin film, manufacturing method of the resin film, endless belt, manufacturing method of the belt, and image forming apparatus
US7431816B2 (en) * 2000-12-20 2008-10-07 Fuji Xerox Co., Ltd. Method of manufacturing heat resistant resin film with metal thin film
US6697248B1 (en) 2001-02-06 2004-02-24 Daniel Luch Electromagnetic interference shields and methods of manufacture
US7309411B2 (en) * 2001-03-13 2007-12-18 Herdman Roderick D Electrolyte media for the deposition of tin alloys and methods for depositing tin alloys
US20040065558A1 (en) * 2001-03-13 2004-04-08 Herdman Roderick D. Electrolyte media for the deposition of tin alloys and methods for depositing tin alloys
US6582887B2 (en) 2001-03-26 2003-06-24 Daniel Luch Electrically conductive patterns, antennas and methods of manufacture
US20060017623A1 (en) * 2001-03-26 2006-01-26 Daniel Luch Electrically conductive patterns, antennas and methods of manufacture
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US20030232214A1 (en) * 2002-06-18 2003-12-18 Veerasamy Vijayen S. Method of making automotive trim with chromium inclusive coating thereon, and corresponding automotive trim product
US6861105B2 (en) 2002-06-18 2005-03-01 Guardian Industries Corp. Method of making automotive trim with chromium inclusive coating thereon, and corresponding automotive trim product
US20050199502A1 (en) * 2002-10-15 2005-09-15 International Business Machines Corporation Method for electroplating on resistive substrates
US20060032752A1 (en) * 2004-02-11 2006-02-16 Daniel Luch Methods and structures for the production of electrically treated items and electrical connections
US20100193367A1 (en) * 2004-02-11 2010-08-05 Daniel Luch Methods and structures for the production of electrically treated items and electrical connections
US20060275553A1 (en) * 2005-06-03 2006-12-07 Siemens Westinghouse Power Corporation Electrically conductive thermal barrier coatings capable for use in electrode discharge machining
US20070040686A1 (en) * 2005-08-16 2007-02-22 X-Cyte, Inc., A California Corporation RFID inlays and methods of their manufacture
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US9006563B2 (en) 2006-04-13 2015-04-14 Solannex, Inc. Collector grid and interconnect structures for photovoltaic arrays and modules
US9236512B2 (en) 2006-04-13 2016-01-12 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US20100006442A1 (en) * 2006-08-03 2010-01-14 Basf Se Process for application of a metal layer on a substrate
US20090107538A1 (en) * 2007-10-29 2009-04-30 Daniel Luch Collector grid and interconnect structures for photovoltaic arrays and modules
US20200010583A1 (en) * 2009-11-11 2020-01-09 Borealis Ag Polymer composition comprising a polyolefin produced in a high pressure process, a high pressure process and an article
US10875939B2 (en) * 2009-11-11 2020-12-29 Borealis Ag Polymer composition comprising a polyolefin produced in a high pressure process, a high pressure process and an article
US9852826B2 (en) * 2010-06-10 2017-12-26 Borealis Ag Cable with semiconductive layer made of polypropylene composition and improved long term thermal stability
CN106525536A (zh) * 2016-11-30 2017-03-22 江西洪都航空工业集团有限责任公司 一种用于制备测试热粘结金属包胶件拉伸强度的菌状试样的方法
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Also Published As

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CH592503A5 (enrdf_load_stackoverflow) 1977-10-31
NL7413806A (nl) 1975-04-25
JPS5067731A (enrdf_load_stackoverflow) 1975-06-06
AT334150B (de) 1976-12-27
FR2248339B1 (enrdf_load_stackoverflow) 1978-06-09
IN142485B (enrdf_load_stackoverflow) 1977-07-16
ATA853474A (de) 1976-04-15
BE821382A (fr) 1975-04-23
GB1480522A (en) 1977-07-20
ES431240A1 (es) 1976-10-16
DE2450069A1 (de) 1975-04-24
SE7413267L (enrdf_load_stackoverflow) 1975-04-24
SE410627B (sv) 1979-10-22
IT1032105B (it) 1979-05-30
JPS585378A (ja) 1983-01-12
FR2248339A1 (enrdf_load_stackoverflow) 1975-05-16
CA1037896A (en) 1978-09-05
AU7438774A (en) 1976-04-29
ZA746656B (en) 1976-06-30

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