US20040222103A1 - Process for the direct metal-plating of a plastic substrate - Google Patents

Process for the direct metal-plating of a plastic substrate Download PDF

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Publication number
US20040222103A1
US20040222103A1 US10/240,972 US24097202A US2004222103A1 US 20040222103 A1 US20040222103 A1 US 20040222103A1 US 24097202 A US24097202 A US 24097202A US 2004222103 A1 US2004222103 A1 US 2004222103A1
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Prior art keywords
active surface
carbonyl
substrate
metal
carbon atoms
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US10/240,972
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English (en)
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Andrea Marsales
William Armstrong
Gary Chevalier
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Decoma Exterior Trim Inc
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Decoma Exterior Trim Inc
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Priority to US10/240,972 priority Critical patent/US20040222103A1/en
Assigned to DECOMA EXTERIOR TRIM INC. reassignment DECOMA EXTERIOR TRIM INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ARMSTRONG, WILLIAM E., MARSALES, ANDREA, CHEVALIER, GARY
Publication of US20040222103A1 publication Critical patent/US20040222103A1/en
Abandoned 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/2033—Heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper

Definitions

  • the present invention relates to a process for direct metal-plating of a plastic substrate.
  • Metal-plating of substrate materials is known.
  • chrome-plating of automobile trim components is periodically popular.
  • U.S. Pat. No. 5,468,518 [Lein et al. (Lein)] teaches a combined primer/basecoat island coating system for manufacturing a metallized part.
  • the process relates to metallizing a substrate material selected from the group comprising thermoplastic urethane (TPU), TPU alloys, polyester alloys, nylon, thermoplastic olefins (TPO) and aluminum.
  • a protective layer (primer/basecoat) is spray deposited, flashed and cured over the substrate.
  • the protective layer comprises clear urethane resin, black pigment paste, a solvent blend and a catalyst solution.
  • U.S. Pat. No. 5,591,488 [Schäfer et al. (Schäfer)] teaches a process for treatment of polymer-containing workpiece surfaces and to an aqueous non-ageing solution.
  • the focus of Schulfer is in a preconditioning process and materials for use therein to prepare a substrate material for application of a metal plating layer.
  • the substrate is a polymeric material—e.g., polycarbonate, optionally in admixture with acrylonitrile-butadiene-styrene copolymer.
  • the substrate is not particularly concerned with direct coating of a specific type of polymer substrate with a metal-plating layer.
  • U.S. Pat. No. 5,693,209 teaches a process for direct metallization of a circuit board having nonconductive surfaces.
  • the process comprises reacting the nonconductive surface with an alkaline permanganate solution to form manganese dioxide chemically adsorbed on the nonconductive surface. Thereafter, an aqueous solution of a weak acid and of a pyrrole or a pyrrole derivative and soluble oligomers is formed and contacted with the nonconductive surface to deposit an adherent, electrically conducting, insoluble polymer product on the nonconductive surface. Thereafter, a metal is directly electrodeposited onto the nonconductive surface.
  • the process is principally directed to the process useful in the production of circuit boards.
  • U.S. Pat. No. 5,882,736 [Stein et al. (Stein)] teaches a process for deposition of a palladium layer on a metal surface. Specifically, the process is for the deposition of highly adhesive, permanently glossy palladium layers having very few pores on the metal surface. This is achieved by immersing the metal surface in a formaldehyde-free chemical bath, with or without pretreatment.
  • U.S. Pat. No. 5,985,418 [Lein et al. (Lein)] teaches a process for manufacturing a metallized substrate using a so-called island coating method. Particularly adapted for application of a metal layer to a substrate used in the apparel industry.
  • the process comprises depositing a first coating layer containing a radiation curable non-volatile film former.
  • the coated substrate is then vacuum metallized to form the metal islands of the invention and thereafter, a layer of clear resinous protective dielectric top coat containing a radiation curable non-volatile film former is deposited to completely cover the layer of “metal islands”.
  • the substrate can be polymeric or metallic.
  • TPO Thermoplastic Olefin
  • vehicles are commonly fitted with a front and rear fascia which cover or conceal a front and rear bumper beam assembly.
  • Molded TPO rocker panels and fenders are also commonly utilized on vehicles.
  • the trim panels are molded and then painted to match the color of the remaining portion of the vehicle.
  • TPO thermoplastic olefin
  • the present invention provides a process for direct metal-plating of a plastic substrate comprising the steps of:
  • thermoplastic olefin (TPO) substrate i.e., the active surface of the substrate
  • the active surface of the substrate comprise carbon atoms of which at least about 7% are in the form of carbonyl in order to produce a durable, good quality metal plate coating on the substrate. If the active surface of the substrate comprises carbon atoms of which is less than about 7% in the form of carbonyl, the metal-plate coating will be inferior and subject to detachment from the thermoplastic olefin substrate.
  • active surface is intended in denote a surface layer of the TPO substrate having a thickness of from about 3 to about 5 nm.
  • modified TPO is intended to mean polypropylene-based materials such as polyolefin modified with a first elastomeric material such ethylene propylene diene monomer (EPDM) and further modified with a second elastomer including a diene and triene type polymer.
  • first elastomeric material such as ethylene propylene diene monomer (EPDM)
  • second elastomer including a diene and triene type polymer.
  • FIG. 1 is a perspective view of an automotive trim piece of the present invention.
  • FIG. 2 is a cross sectional view of the automotive trim price of FIG. 1.
  • the process of the present invention is useful to directly metallize a TPO substrate.
  • the TPO substrate is a modified TPO comprising a polyolefin material modified with a first elastomer, such as EPDM and then modified with a second elastomer, including diene and triene type polymers, such as acrylonitrile and butadiene.
  • the elastomers are added in effective amounts providing a basis for an active surface as discussed below.
  • the TPO is molded in a conventional manner into a substrate 10 .
  • the substrate is in the form of an automotive component such as a grill.
  • other components such as fascia, trim panels, rocker panels, fenders, trim strips are also contemplated in the present invention.
  • a surface of the TPO substrate 14 is activated by one of the methods described below to provide an active surface 16 .
  • the active surface 16 is a presentation or exterior-facing surface of the molded part on which a metal layer 18 is deposited.
  • the active surface 16 of the TPO substrate 14 comprises carbon atoms of which at least about 7% are in the form of carbonyl. Preferably from about 7% to about 25% of carbon atoms at the active surface are in the form of carbonyl. More preferably, from about 7% to about 20% of carbon atoms at the active surface are in the form of carbonyl. Most preferably, about 7% to about 15% of carbon atoms at the active surface are in the form of carbonyl.
  • the presence of the carbonyl groups at the active surface may be confirmed by conventional techniques—e.g., FTIR (Fourier Transform Infrared spectroscopy).
  • the concentration of carbonyl groups at the active surface may be confirmed by conventional techniques—e.g., XPS (X-ray photoelectron spectroscopy).
  • a modified TPO is utilized and the desired amount of carbonyl content can be conferred to the surface of a modified TPO substrate by controlling preferred pretreatment steps in the process.
  • the etching technique comprises contacting the modified TPO substrate with an etching solution comprising chromic acid or a mixture of chromic acid and sulfuric acid. During this etching step the active surface is formed. It is believed that chromic acid is reduced on the surface of the modified TPO substrate to provide oxygen containing moieties (e.g., hydroxyl, ether and the like), including the desired carbonyl groups. The amount of desired carbonyl groups may be controlled by the time period during which the substrate is immersed in the etching solution.
  • the chemical(s) used in the above-mentioned etching step may be obtained commercially from Atotech Canada Ltd. under the tradename FuturonTM.
  • the active surface of the modified TPO substrate is contacted with an acid.
  • an acid is hydrochloric acid.
  • the active surface of the modified TPO substrate is then ready for further activation wherein a surface thereof is fully activated for electrolytic metallization.
  • the solution comprises palladium chloride and stannous chloride.
  • stannic palladium in a concentration of from about 5 to about 20,000 ppm (0.005 to 20 g/L), preferably 20 to about 300 ppm (0.02 to 0.3 g/L), more preferably from about 20 to about 250 ppm (0.02 to 0.25 g/L) for a period of at least about one minute, preferably from about one minute to about ten minutes, more preferably from about two minutes to about four minutes.
  • This activation step serves to anchor the palladium/tin complex to the surface of the TPO substrate.
  • a desirable level of palladium/tin complex is dispersed over the surface of the substrate.
  • the next step in the process is to exchange the tin in the palladium/tin complex with copper. This is done in a conventional manner.
  • the chemical(s) used in the above-mentioned electrolytic metallization steps may be obtained commercially from Atotech Canada Ltd. under the tradename FuturonTM.
  • a layer of nickel or copper can be deposited on the active surface in a conventional manner, including electroless deposition whereby nickel or copper salt is reduced onto the active surface of the TPO substrate.
  • Advantages of the nickel or copper layer include increased conductivity, reduced bath time and lower palladium concentrations ( ⁇ 100 ppm or 0.1 g/L) in the palladium bath discussed above.
  • Step (ii) of the present process comprises electrochemically depositing a metal layer 18 on the active surface 14 of the TPO substrate 14 . This can be done in a conventional manner.
  • the FuturonTM pre-plating process comprises the following general steps: (i) cleaner (optional); (ii) etching (typically with chromic sulfuric acid); (iii) reduction (typically with Cr (VI), (iv) pre-dip solution; (v) Pd/Sn activation and (vi) Cu-link.
  • the modified TPO substrate was treated according to the particulars set out in Tables 1 and 2.
  • Etch time was varied as set out in Table 3 below.
  • Pre-plate tank conditions (dwell times, concentrations, temperatures) are reported below. All panels were plated using a conventional acid copper-electroplating bath, followed by conventional electroplating nickel and chrome baths. Panels were plated for 60 minutes at 30 amps/ft 2 to achieve 40+/ ⁇ 5 microns of copper thickness for peel testing as defined in ASTM B533.
  • test panels were stripped of palladium and copper using a solution of Aqua Regia (1:1). Solutions were analysed for metal content using Atomic Adsorption spectrophotometry. Samples were tested for peel strength using the 90° tensile test, on an InstronTM instrument in accordance with ASTM B533. Each sample panel was cut into three strips and each strip tested. The overall average of the strips for each Example is reported as the peel strength of the panel.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
US10/240,972 2000-04-05 2001-04-05 Process for the direct metal-plating of a plastic substrate Abandoned US20040222103A1 (en)

Priority Applications (1)

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US10/240,972 US20040222103A1 (en) 2000-04-05 2001-04-05 Process for the direct metal-plating of a plastic substrate

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US19469300P 2000-04-05 2000-04-05
US10/240,972 US20040222103A1 (en) 2000-04-05 2001-04-05 Process for the direct metal-plating of a plastic substrate
PCT/CA2001/000463 WO2001077419A2 (fr) 2000-04-05 2001-04-05 Procede de galvanoplastie directe d'un substrat plastique

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US (1) US20040222103A1 (fr)
EP (1) EP1268880B1 (fr)
AU (1) AU2001248179A1 (fr)
BR (1) BR0109887A (fr)
CA (1) CA2404946A1 (fr)
DE (1) DE60109432T2 (fr)
MX (1) MXPA02009785A (fr)
WO (1) WO2001077419A2 (fr)

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US20060104074A1 (en) * 2004-09-10 2006-05-18 Boniface Robert E Vehicle body
US20070224346A1 (en) * 2006-03-22 2007-09-27 Mark Wojtaszek Polyimide substrate and method of manufacturing printed wiring board using the same
WO2015006488A1 (fr) * 2013-07-09 2015-01-15 United Technologies Corporation Placage d'un composite pour renforcer le collage d'éléments métalliques
CN105112971A (zh) * 2015-09-22 2015-12-02 太仓市金鹿电镀有限公司 一种汽车散热格栅沙镍电镀工艺
US10214824B2 (en) 2013-07-09 2019-02-26 United Technologies Corporation Erosion and wear protection for composites and plated polymers
US10227704B2 (en) 2013-07-09 2019-03-12 United Technologies Corporation High-modulus coating for local stiffening of airfoil trailing edges
US10927843B2 (en) 2013-07-09 2021-02-23 Raytheon Technologies Corporation Plated polymer compressor
US11267576B2 (en) 2013-07-09 2022-03-08 Raytheon Technologies Corporation Plated polymer nosecone
US11268526B2 (en) 2013-07-09 2022-03-08 Raytheon Technologies Corporation Plated polymer fan
US11691388B2 (en) 2013-07-09 2023-07-04 Raytheon Technologies Corporation Metal-encapsulated polymeric article

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Publication number Priority date Publication date Assignee Title
FR2930180B1 (fr) * 2008-04-22 2010-12-17 Inst Superieur De Plasturgie D Alencon Entpr S Procede de metallisation d'un substrat non conducteur en matiere plastique

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US4002595A (en) * 1973-12-27 1977-01-11 E. I. Du Pont De Nemours And Company Electroplatable polypropylene compositions
US4298424A (en) * 1980-06-19 1981-11-03 Vbe Industries, Ltd. Method for etching polyamide shaped articles
US5340451A (en) * 1990-10-04 1994-08-23 International Business Machines Corporation Process for producing a metal organic polymer combination
US5908543A (en) * 1997-02-03 1999-06-01 Okuno Chemical Industries Co., Ltd. Method of electroplating non-conductive materials

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JPS63247376A (ja) * 1987-04-03 1988-10-14 Citizen Watch Co Ltd プラスチツク成形品への無電解メツキの前処理方法
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US3562790A (en) * 1965-08-03 1971-02-09 Eastman Kodak Co Tri-component poly-propylene blend and method
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US20060104074A1 (en) * 2004-09-10 2006-05-18 Boniface Robert E Vehicle body
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WO2007111671A1 (fr) * 2006-03-22 2007-10-04 Macdermid, Incorporated Subtrat polyimide et procede de fabrication d'une carte de circuit imprime l'utilisant
EP2007931A1 (fr) * 2006-03-22 2008-12-31 MacDermid, Incorporated Subtrat polyimide et procede de fabrication d'une carte de circuit imprime l'utilisant
US7666471B2 (en) * 2006-03-22 2010-02-23 Mark Wojtaszek Polyimide substrate and method of manufacturing printed wiring board using the same
EP2007931A4 (fr) * 2006-03-22 2010-03-10 Macdermid Inc Subtrat polyimide et procede de fabrication d'une carte de circuit imprime l'utilisant
US20070224346A1 (en) * 2006-03-22 2007-09-27 Mark Wojtaszek Polyimide substrate and method of manufacturing printed wiring board using the same
US10927843B2 (en) 2013-07-09 2021-02-23 Raytheon Technologies Corporation Plated polymer compressor
US10214824B2 (en) 2013-07-09 2019-02-26 United Technologies Corporation Erosion and wear protection for composites and plated polymers
US10227704B2 (en) 2013-07-09 2019-03-12 United Technologies Corporation High-modulus coating for local stiffening of airfoil trailing edges
WO2015006488A1 (fr) * 2013-07-09 2015-01-15 United Technologies Corporation Placage d'un composite pour renforcer le collage d'éléments métalliques
US11267576B2 (en) 2013-07-09 2022-03-08 Raytheon Technologies Corporation Plated polymer nosecone
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US11691388B2 (en) 2013-07-09 2023-07-04 Raytheon Technologies Corporation Metal-encapsulated polymeric article
CN105112971A (zh) * 2015-09-22 2015-12-02 太仓市金鹿电镀有限公司 一种汽车散热格栅沙镍电镀工艺

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MXPA02009785A (es) 2004-09-06
EP1268880B1 (fr) 2005-03-16
WO2001077419A3 (fr) 2002-09-12
EP1268880A2 (fr) 2003-01-02
BR0109887A (pt) 2003-06-03
AU2001248179A1 (en) 2001-10-23
CA2404946A1 (fr) 2001-10-18
DE60109432D1 (de) 2005-04-21
WO2001077419A2 (fr) 2001-10-18
DE60109432T2 (de) 2006-04-06

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