EP1268880B1 - Procede de galvanoplastie directe d'un substrat plastique - Google Patents

Procede de galvanoplastie directe d'un substrat plastique Download PDF

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Publication number
EP1268880B1
EP1268880B1 EP01921064A EP01921064A EP1268880B1 EP 1268880 B1 EP1268880 B1 EP 1268880B1 EP 01921064 A EP01921064 A EP 01921064A EP 01921064 A EP01921064 A EP 01921064A EP 1268880 B1 EP1268880 B1 EP 1268880B1
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EP
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Prior art keywords
active surface
substrate
carbonyl
palladium
carbon atoms
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Expired - Lifetime
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EP01921064A
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German (de)
English (en)
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EP1268880A2 (fr
Inventor
Andrea Marsales
William E. Armstrong
Gary F. Chevalier
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Decoma Exterior Trim Inc
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Decoma Exterior Trim Inc
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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.
  • chrome-plating was achieved by plating a metal substrate (e.g., a bumper).
  • chrome-plating of metal substrates for use in automobile trim parts has been reduced for a variety of reasons, including: the need to reduce the weight of the vehicle, corrosion problems with the metal substrate, the advance of other systems for energy absorption if the substrate was being used as a bumper and the like.
  • the state of the art has advanced over the years in the general subject matter area of metal-plating of substrates (both metal and non-metal).
  • United States patent 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.
  • a layer of corrosion prone metal is vacuum deposited to form a discontinuous film covering the combined primer/basecoat layer.
  • United States patent 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:
  • an activate 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 carbonvl 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 mm.
  • 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.
  • 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 subjected to chromic acid reduction to reduce any residual chromic acid left in the pores of the substrate from Cr 6+ to Cr 3+ (the reason for this is that Cr 6+ is detrimental if present during later steps in the process).
  • the active surface of the modified TPO substrate is contacted with an acid.
  • a non-limiting useful such 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.
  • 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 ( ⁇ 100ppm 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 16 of the TPO substrate 14. This can be done in a conventional manner.
  • a modified TPO obtained from Solvay Engineered Polymers was activated, treated and electrolytically metallized in the following 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 (0,0929 m 2 ) to achieve 40+/- 5 microns (40+/-5.10 -6 m) 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.
  • the peel test results illustrate that significantly improved adhesion of the metal plating layer is achieved in Examples 2 and 3 (carbonyl content of at least 7%) compared with that achieved in Example 1 (carbonyl content less than 7%).

Claims (25)

  1. Procédé pour le placage métallique direct d'un substrat plastique comprenant les étapes consistant à :
    (i) modifier une oléfine thermoplastique à base de polypropylène (TPO) en ajoutant une quantité efficace d'un premier élastomère tel qu'un élastomère d'éthylène-propylène diène monomère (EPDM), et un second élastomère comprenant des polymères de type diène et triène ;
    (ii) activer une surface d'un substrat TPO pour produire une surface active, la surface active comprenant au moins 7 % des atomes de carbone présents au niveau de la surface active sous la forme d'un groupe carbonyle ; et
    (iii) déposer de façon électrochimique une couche métallique sur ladite surface activée.
  2. Procédé selon la revendication 1, dans lequel de 7 % à 25 % des atomes de carbone présents au niveau de la surface active sont sous la forme d'un groupe carbonyle.
  3. Procédé selon la revendication 1, dans lequel de 7 % à 20 % des atomes de carbone présents au niveau de la surface active sont sous la forme d'un groupe carbonyle.
  4. Procédé selon la revendication 1, dans lequel de 7 % à 15 % des atomes de carbone présents au niveau de la surface active sont sous la forme d'un groupe carbonyle.
  5. Procédé selon la revendication 1, comprenant, avant l'étape (iii), l'étape supplémentaire consistant à déposer une couche de palladium sur la surface active.
  6. Procédé selon la revendication 1, comprenant, avant l'étape (iii), l'étape supplémentaire consistant à réduire un sel de palladium sur la surface active.
  7. Procédé selon la revendication 6, dans lequel le sel de palladium est choisi dans le groupe comprenant le sulfate de palladium, le nitrate de palladium, le perchlorate de palladium et des mélanges de ceux-ci.
  8. Procédé selon la revendication 6, comprenant l'immersion de la surface active dans un bain comprenant le sel de palladium.
  9. Procédé selon la revendication 8, dans lequel le sel de palladium est présent dans le bain en une concentration de 0,005 à 20 g/l.
  10. Procédé selon la revendication 8, dans lequel le sel de palladium est présent dans le bain en une concentration de 0,02 à 2,0 g/l.
  11. Procédé selon la revendication 8, dans lequel le sel de palladium est présent dans le bain en une concentration de 0,02 à 0,3 g/l.
  12. Procédé selon la revendication 8, dans lequel le sel de palladium est présent dans le bain en une concentration de 0,02 à 0,25 g/l.
  13. Procédé selon l'une quelconque des revendications 5 à 12, dans lequel, juste avant l'étape (iii), ledit procédé comprend une étape consistant à déposer une couche d'un métal sur ladite surface active, ledit métal étant choisi dans le groupe comprenant le nickel et le cuivre.
  14. Procédé selon la revendication 13, dans lequel ladite étape de dépôt comprend la réduction d'un sel de métal respectif sur la surface active par un dépôt non électrolytique.
  15. Procédé selon la revendication 1, dans lequel lesdits polymères de type diène et triène comprennent l'acrylonitrile et le butadiène.
  16. Procédé selon l'une des revendications 1 ou 15 dans lequel, avant ladite étape (ii), ledit procédé comprend une pré-étape de moulage dudit TPO modifié dans ledit substrat.
  17. Procédé selon l'une quelconque des revendications précédentes dans lequel ladite étape (ii) d'activation comprend l'attaque chimique de ladite surface à l'aide d'une solution d'attaque choisie dans le groupe comprenant l'acide chromique et un mélange d'acide chromique et d'acide sulfurique.
  18. Procédé selon la revendication 17 dans lequel ledit pourcentage d'atomes de carbone au niveau de ladite surface active sous la forme d'un carbonyle est contrôlée par la durée totale pendant laquelle ladite surface active est attaquée par ladite solution d'attaque.
  19. Procédé selon la revendication 18 dans lequel ledit pourcentage d'atomes de carbone au niveau de ladite surface active sous la forme d'un carbonyle est contrôlée par la variation de la température de la solution d'attaque.
  20. Procédé selon la revendication 18 dans lequel ledit pourcentage d'atomes de carbone au niveau de ladite surface active sous la forme d'un carbonyle est contrôlée par la variation d'une concentration de produits chimiques utilisés dans la solution d'attaque.
  21. Procédé selon l'une quelconque des revendications 17 à 20, dans lequel ladite étape (ii) d'activation comprend le fait de soumettre ladite surface à une réduction de l'acide chromique en vue de réduire tout acide chromique résiduel sur ladite surface de Cr6+ à Cr3+.
  22. Procédé selon la revendication 21 dans lequel ladite étape (ii) d'activation comprend une pré-immersion du substrat dans un acide de pré-immersion.
  23. Procédé selon la revendication 22, dans lequel ledit acide de pré-immersion comprend l'acide chlorhydrique.
  24. Procédé selon l'une quelconque des revendications 1 à 14, dans lequel ladite étape (ii) d'activation comprend le flammage, le plasma sous vide et la décharge électrique.
  25. Procédé selon l'une quelconque des revendications précédentes, dans lequel ladite surface active présente une épaisseur de 3 à 5 nm.
EP01921064A 2000-04-05 2001-04-05 Procede de galvanoplastie directe d'un substrat plastique Expired - Lifetime EP1268880B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US19469300P 2000-04-05 2000-04-05
US194693P 2000-04-05
PCT/CA2001/000463 WO2001077419A2 (fr) 2000-04-05 2001-04-05 Procede de galvanoplastie directe d'un substrat plastique

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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
WO2015006438A1 (fr) 2013-07-09 2015-01-15 United Technologies Corporation Compresseur polymère plaqué
WO2015053832A2 (fr) 2013-07-09 2015-04-16 United Technologies Corporation Revêtement à module élevé pour le raidissement local de bords de fuite d'un plan de sustentation
EP3019710A4 (fr) 2013-07-09 2017-05-10 United Technologies Corporation Ventilateur en polymère plaqué
WO2015006488A1 (fr) * 2013-07-09 2015-01-15 United Technologies Corporation Placage d'un composite pour renforcer le collage d'éléments métalliques
WO2015006421A1 (fr) 2013-07-09 2015-01-15 United Technologies Corporation Article polymère sous encapsulation métallique
WO2015017095A2 (fr) 2013-07-09 2015-02-05 United Technologies Corporation Coiffe polymère plaquée
US10214824B2 (en) 2013-07-09 2019-02-26 United Technologies Corporation Erosion and wear protection for composites and plated polymers
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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EP1268880A2 (fr) 2003-01-02
AU2001248179A1 (en) 2001-10-23
WO2001077419A3 (fr) 2002-09-12
BR0109887A (pt) 2003-06-03
DE60109432T2 (de) 2006-04-06
US20040222103A1 (en) 2004-11-11
CA2404946A1 (fr) 2001-10-18
WO2001077419A2 (fr) 2001-10-18
MXPA02009785A (es) 2004-09-06
DE60109432D1 (de) 2005-04-21

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