US3553085A - Method of preparing surfaces of plastic for electro-deposition - Google Patents

Method of preparing surfaces of plastic for electro-deposition Download PDF

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US3553085A
US3553085A US686310A US3553085DA US3553085A US 3553085 A US3553085 A US 3553085A US 686310 A US686310 A US 686310A US 3553085D A US3553085D A US 3553085DA US 3553085 A US3553085 A US 3553085A
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plastic
solution
sulfuric acid
roughening
concentrated sulfuric
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US686310A
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Kurt Heymann
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Bayer Pharma AG
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Schering AG
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    • 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
    • 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
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/924—Electrolytic coating substrate predominantly comprised of specified synthetic resin
    • Y10S205/928—ABS copolymer

Definitions

  • the invention relates to the pretreatment of plastic surfaces or the like by chemical roughening thereof with simultaneous activation for the purpose of subsequent electrodeposition.
  • Plastic surfaces are pretreated by chemical means to roughen the surface with coordinated activation by oxidation.
  • plastics particularly of acrylonitrile butadiene-styrene copolymers can be pretreated for electrodeposition in a much more advantageous manner by exposing their surface to a solution which combines chemical roughening or oxidative modification with simultaneous activation. This is achieved by adding to the roughening or oxidizing solution noble metal salts which are capable of penetrating the plastic by diffusion simultaneously with the modification of the surface by the action of this solution.
  • the method of the invention thus combines the roughening and activation in a single step, and is thus much simpler than processes heretofore known.
  • the nuclei formed during the reduction following this pretreatment are anchored relatively deeply in the surface of the plastic. They account for the good adhesion of the metal layers which are applied subsequently by chemical or electrolytic means.
  • the solutions employed for the method of the invention contain concentrated sulfuric acid and one or more noble metal salts, for example, salts of gold, silver or palladium, such as auric chloride, silver nitrate, silver sulfate, silver acetate, palladium chloride, palladium sulfate and salts of platinum, iridium and osmium, such as the chlorides in preferred amounts averaging from 0.010 to 10 g. of the metal salt per liter of concentrated sulfuric acid.
  • the minimum operative concentration of sulfuric acid may be 50% (by weight).
  • oxidizing agents preferably nitric acid, hydrogen peroxide, chromic acid, or persulfates and the like.
  • the method may be performed at temperatures from about 15 to about C.
  • the dwell time of the plastics in the pretreatment bath is variable and is selected from about 30 seconds up to two hours, depending on the amount of electrodeposition to be effected.
  • the plastic is rinsed after the treatment With the solution of the invention and is transferred to one of the conventional reducing baths.
  • the noble metal ions diffused into the plastic surface are thereby reduced to metal nuclei.
  • the plastic may be metallized chemically at once after this treatment and may be provided thereafter with any kind of metal coating by electrodeposition.
  • the pretreated plastics may be metallized directly in a chemical reduction bath. It is only necessary to thoroughly rinse the pretreated plastic and to increase slightly the concentration of the reducing agent in the metallizing bath.
  • Suitable chemical reducing solutions are the copper and nickel baths, for example, which contain formaldehyde or hypophosphite or borohydride as a reducing agent.
  • the method of the invention has the advantage that the surface of the plastic parts is much less roughened than in the mechanical pretreating processes. Copper, nickel and chromium may therefore be applied for decorative purposes in much thinner layers for producing a bright appearance.
  • the adhesion of the metal layers to the plastic achieved by this method corresponds to that obtained by mechanical roughening.
  • EXAMPLE 1 Composition of the solution: Concentrated sulfuric acid+5 g./1. of silver sulfate.
  • EXAMPLE 2 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver nitrate.
  • EXAMPLE 4 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver nitrate+60 g./1. of chromic acid anhydride.
  • EXAMPLE 5 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver sulfate-+50 ml./l. of 30% hydrogen peroxide.
  • EXAMPLE 6 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver nitrate+50 g./l. of ammonium persulfate.
  • EXAMPLE 7 Composition of the solution: Concentrated sulfuric aoid+5 g./l. of silver sulfate- ⁇ - g./1. of perchloric acid.
  • EXAMPLE 8 Composition of the solution: 70% concentrated sulfuric acid (by weight), 12% phosphoric acid, 0.7% potassium dichromate, 150 mg./l. pd++ in the form of palladium chloride, the balance being water.
  • Treating time from 3 minutes up.
  • EXAMPLE 9 Composition of the solution: 75% (weight) concentrated sulfuric acid, 12% phosphoric acid, 0.5% potassium dichromate, 100 mg./l. of Au+++ in the form of gold chloride, the balance water.
  • Treating time from 3 minutes up.
  • EXAMPLE 10 Composition of the solution: 75% (weight) concentrated sulfuric acid, 0.7% potassium dichromate, 100 mg./l. Au+++ in the form of gold chloride, the balance water.
  • plastic parts pretreated according to the invention may be metallized in the usual manner, for example, as follows:
  • Metal deposition is performed at a bath temperature of about 20 to 40 C. for 10 to 20 minutes, whereby copper coatings of about 0.3 to 1.3 microns are deposited depending on the temperature and time of treatment.
  • the deposited meal layer may subsequently be provided with any desired metal coating in the conventional electrolytic baths.
  • surfaces made of plastic materials notably acrylo-nitrile butadiene styrene copolymers can be readily pretreated or roughened superficially by chemical and oxidative means, so that such surfaces will be able to hold thereon metal surfaces by chemical plating and electrodeposition.
  • An electrodeposition process consisting essentially of roughening and activating an acrylonitrile-butadiene styrene copolymer plastic surface by contracting said surface with a solution consisting essentially of at least 50% by weight of sulfuric acid, 0.010 to 10 grams of noble metal salt per liter of concentrated sulfuric acid, and an amount of oxidizing agent from the group consisting of nitric acid, hydrogen peroxide and persulfates sufiieient to accelerate roughening and oxidation of said plastic surface; chemically metallizing said roughened, activated sur- I face; and subsequently providing any metal coating thereon by means of electrodeposition.
  • the noble metal salt is a salt of a metal selected from the group consisting of gold, silver, palladium, platinum, iridium, and osmium.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

THE SPECIFICATION DISCLOSES A METHOD AND COMPOSITIONS FOR PREPARING PLASTIC SURFACES TO RECEIVE A METALLIC DEPOSIT. A SOLUTION COMPRISING A NOBLE METAL SALT AND SULFURIC ACID IS USED TO ACHIEVE SIMULTANEOUS ROUGHENING AND ACTIVATION OF THE SURFACE. IN A PREFERRED EMBODIMENT, THE SOLUTION ALSO CONTAINS AN OXIDIZING AGENT.

Description

United States Patent Office 3,553,085 Patented Jan. 5, 1971 3,553,085 METHOD OF PREPARING SURFACES F PLASTIC FOR ELECTRO-DEPOSITION Kurt Heymann, Berlin, Germany, assignor to Schering AG, Berlin and Bergkamen, Germany No Drawing. Filed Nov. 28, 1967, Ser. No. 686,310 Int. Cl. C23b 5/60 US. Cl. 20430 3 Claims ABSTRACT OF THE DISCLOSURE The specification discloses a method and compositions for preparing plastic surfaces to receive a metallic deposit. A solution comprising a noble metal salt and sulfuric acid is used to achieve simultaneous roughening and activation of the surface. In a preferred embodiment, the solution also contains an oxidizing agent.
The invention relates to the pretreatment of plastic surfaces or the like by chemical roughening thereof with simultaneous activation for the purpose of subsequent electrodeposition.
Plastic surfaces are pretreated by chemical means to roughen the surface with coordinated activation by oxidation.
It is known that the electroplating of plastics requires a pretreatment of the surface to be plated. The processes known heretofore are mainly of a mechanical nature. The injection molded plastic objects are roughened, for example, by tumbling with abrasives, then rinsed, immersed in a solution containing a reducing agent, usually stannous chloride, and are subsequently transferred to an activating solution which contains noble metal salts, mostly silver nitrate or palladium chloride. The portion of the reducing agent adhering from the first bath to the plastic surface reduces the noble metal ions to metal nuclei which stick to the roughened surface by adhesion. Furthermore, it will be noted that such pretreated parts can be metallized further by chemical means. This proc ess requires appreciable time, material and labor, particularly because of the mechanical roughening treatment.
Chemical pretreatment methods, for example using solutions, have also become known in which the plastic surface is roughened or swelled by chemical action. The plastic is activated after such a treatment in the same known manner as in the above-described mechanical roughening process. These chemical processes thus only replace the mechanical roughening of the plastics because it is necessary separately to perform the activating treatment which is necessary for the subsequent electrodeposition.
It has now been found that plastics, particularly of acrylonitrile butadiene-styrene copolymers can be pretreated for electrodeposition in a much more advantageous manner by exposing their surface to a solution which combines chemical roughening or oxidative modification with simultaneous activation. This is achieved by adding to the roughening or oxidizing solution noble metal salts which are capable of penetrating the plastic by diffusion simultaneously with the modification of the surface by the action of this solution. The method of the invention thus combines the roughening and activation in a single step, and is thus much simpler than processes heretofore known. The nuclei formed during the reduction following this pretreatment are anchored relatively deeply in the surface of the plastic. They account for the good adhesion of the metal layers which are applied subsequently by chemical or electrolytic means.
The solutions employed for the method of the invention contain concentrated sulfuric acid and one or more noble metal salts, for example, salts of gold, silver or palladium, such as auric chloride, silver nitrate, silver sulfate, silver acetate, palladium chloride, palladium sulfate and salts of platinum, iridium and osmium, such as the chlorides in preferred amounts averaging from 0.010 to 10 g. of the metal salt per liter of concentrated sulfuric acid. However, the minimum operative concentration of sulfuric acid may be 50% (by weight).
In order to enhance and accelerate the roughening or oxidation of the plastic surface, it is preferred to add oxidizing agents, preferably nitric acid, hydrogen peroxide, chromic acid, or persulfates and the like. Depending on the desired degree of roughening, the method may be performed at temperatures from about 15 to about C. The dwell time of the plastics in the pretreatment bath is variable and is selected from about 30 seconds up to two hours, depending on the amount of electrodeposition to be effected.
The plastic is rinsed after the treatment With the solution of the invention and is transferred to one of the conventional reducing baths. The noble metal ions diffused into the plastic surface are thereby reduced to metal nuclei. The plastic may be metallized chemically at once after this treatment and may be provided thereafter with any kind of metal coating by electrodeposition.
It is not necessary in all instances to reduce the noble metal ions present on the plastic surface in a separate operation, but the pretreated plastics may be metallized directly in a chemical reduction bath. It is only necessary to thoroughly rinse the pretreated plastic and to increase slightly the concentration of the reducing agent in the metallizing bath. Suitable chemical reducing solutions are the copper and nickel baths, for example, which contain formaldehyde or hypophosphite or borohydride as a reducing agent.
Aside from its simplicity, the method of the invention has the advantage that the surface of the plastic parts is much less roughened than in the mechanical pretreating processes. Copper, nickel and chromium may therefore be applied for decorative purposes in much thinner layers for producing a bright appearance. The adhesion of the metal layers to the plastic achieved by this method corresponds to that obtained by mechanical roughening.
The following examples further illustrate, but without limitation, the method of the invention. Parts made of acrylonitrile butadiene-styrene copolymer were treated in the solutions described hereinafter, subsequently rinsed in running water for one minute, and then transferred for one minute to ,a reducing solution consisting of 50 ml. 40% formaldehyde and 50 g. sodium hydroxide per liter, or of 50 g./l. potassium hypophosphite dissolved in 2% to 5% sulfuric acid. The parts so pretreated could be metallized at once by chemical means. The roughening of the plastic surfaces achieved by the solutions described in Examples 3 to 10 was stronger than in the solutions of Examples 1 and 2.
EXAMPLE 1 Composition of the solution: Concentrated sulfuric acid+5 g./1. of silver sulfate.
Temperature: 25 C. Treating time: 3 minutes.
EXAMPLE 2 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver nitrate.
Temperature: 25 C. Treating time: 3 minutes.
3 EXAMPLE 3 Composition of the solution: Concentrated sulfuric acid+ g./l. of silver acetate+20 ml./l. of concentrated nitric acid.
Temperature: 25 C. Treating time: 3 minutes.
EXAMPLE 4 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver nitrate+60 g./1. of chromic acid anhydride.
Temperature: 50 C. Treating time: 3 minutes.
EXAMPLE 5 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver sulfate-+50 ml./l. of 30% hydrogen peroxide.
Temperature: 25 C. Treating time: 3 minutes.
EXAMPLE 6 Composition of the solution: Concentrated sulfuric acid+5 g./l. of silver nitrate+50 g./l. of ammonium persulfate.
Temperature. 25 C. Treating time: 3 minutes.
EXAMPLE 7 Composition of the solution: Concentrated sulfuric aoid+5 g./l. of silver sulfate-{- g./1. of perchloric acid.
Temperature: 25 C. Treating time: 3 minutes.
EXAMPLE 8 Composition of the solution: 70% concentrated sulfuric acid (by weight), 12% phosphoric acid, 0.7% potassium dichromate, 150 mg./l. pd++ in the form of palladium chloride, the balance being water.
Temperature: 65 C. Treating time: from 3 minutes up.
EXAMPLE 9 Composition of the solution: 75% (weight) concentrated sulfuric acid, 12% phosphoric acid, 0.5% potassium dichromate, 100 mg./l. of Au+++ in the form of gold chloride, the balance water.
Temperature: 65 C. Treating time: from 3 minutes up.
EXAMPLE 10 Composition of the solution: 75% (weight) concentrated sulfuric acid, 0.7% potassium dichromate, 100 mg./l. Au+++ in the form of gold chloride, the balance water.
4 Temperature: C. Treating time: from 3 minutes up.
The plastic parts pretreated according to the invention may be metallized in the usual manner, for example, as follows:
The sufficiently rinsed parts are transferred to a bath of the following composition:
Metal deposition is performed at a bath temperature of about 20 to 40 C. for 10 to 20 minutes, whereby copper coatings of about 0.3 to 1.3 microns are deposited depending on the temperature and time of treatment. The deposited meal layer may subsequently be provided with any desired metal coating in the conventional electrolytic baths.
From the foregoing, it will be noted that surfaces made of plastic materials, notably acrylo-nitrile butadiene styrene copolymers can be readily pretreated or roughened superficially by chemical and oxidative means, so that such surfaces will be able to hold thereon metal surfaces by chemical plating and electrodeposition.
What is claimed is:
1. An electrodeposition process consisting essentially of roughening and activating an acrylonitrile-butadiene styrene copolymer plastic surface by contracting said surface with a solution consisting essentially of at least 50% by weight of sulfuric acid, 0.010 to 10 grams of noble metal salt per liter of concentrated sulfuric acid, and an amount of oxidizing agent from the group consisting of nitric acid, hydrogen peroxide and persulfates sufiieient to accelerate roughening and oxidation of said plastic surface; chemically metallizing said roughened, activated sur- I face; and subsequently providing any metal coating thereon by means of electrodeposition.
2. The process of claim 1, wherein the noble metal salt is a salt of a metal selected from the group consisting of gold, silver, palladium, platinum, iridium, and osmium.
3. The process of claim 1, wherein said plastic surface is contacted by said roughening and activating solution at a temperature of from about 15 C. to about C.
References Cited UNITED STATES PATENTS 2,690,402 9/ 1954 Crehan 117-47 3,370,974 2/ 1968 Hepfer 106-1X 3,437,507 4/ 1969 Jensen 106-1X 3,442,683 5/ 1969 Lenoble et al. 117-47 DANIEL E. WYMAN, Primary 'Examiner P. E. KONOPKA, Assistant Examiner US. Cl. X.R.
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867174A (en) * 1965-08-06 1975-02-18 Giichi Okuno Baths for activating the surface of plastics to be chemically metal-plated
US3880580A (en) * 1971-01-11 1975-04-29 Polymer Research Corp Of Ameri Method of activating polymeric materials
US4086128A (en) * 1976-03-04 1978-04-25 Mitsubishi Gas Chemical Company, Inc. Process for roughening surface of epoxy resin
US4835016A (en) * 1988-03-28 1989-05-30 The United States Of America As Represented By The Secretary Of The Army Adhesive bonding
US5160600A (en) * 1990-03-05 1992-11-03 Patel Gordhanbai N Chromic acid free etching of polymers for electroless plating
US6077913A (en) * 1998-03-26 2000-06-20 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US6100343A (en) * 1998-11-03 2000-08-08 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US20020150840A1 (en) * 2001-02-05 2002-10-17 Pioneer Corporation Stamper-forming electrode material, stamper-forming thin film, and method of manufacturing optical disk
US6645557B2 (en) 2001-10-17 2003-11-11 Atotech Deutschland Gmbh Metallization of non-conductive surfaces with silver catalyst and electroless metal compositions
US20040132300A1 (en) * 2002-12-18 2004-07-08 Enthone Inc. Procedure for activation of substrates for plastic galvanizing
US7901603B1 (en) 2004-06-21 2011-03-08 Lars Guenter Beholz Process for producing adhesive polymeric articles from expanded foam materials
US20110256413A1 (en) * 2010-04-19 2011-10-20 Pegastech Process for coating a surface of a substrate made of nonmetallic material with a metal layer
CN102644065A (en) * 2012-03-30 2012-08-22 山东建筑大学 Plastic metalizing method
US20120282417A1 (en) * 2009-12-10 2012-11-08 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for preparing a metallized polymer substrate
CN102912326A (en) * 2012-10-25 2013-02-06 南京大地冷冻食品有限公司 Method for maintaining chemical-plating dispergation working fluid made from solid powder
EP2853619A1 (en) * 2013-09-25 2015-04-01 ATOTECH Deutschland GmbH Method for treatment of recessed structures in dielectric materials for smear removal
WO2023069041A1 (en) * 2021-10-21 2023-04-27 A-Plas Genel Otomotiv Mamulleri Sanayi Ve Ticaret Anonim Sirketi A chrome-free approach to chemical etching of the surfaces of plastic materials to be coated with metal

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3867174A (en) * 1965-08-06 1975-02-18 Giichi Okuno Baths for activating the surface of plastics to be chemically metal-plated
US3880580A (en) * 1971-01-11 1975-04-29 Polymer Research Corp Of Ameri Method of activating polymeric materials
US4086128A (en) * 1976-03-04 1978-04-25 Mitsubishi Gas Chemical Company, Inc. Process for roughening surface of epoxy resin
US4835016A (en) * 1988-03-28 1989-05-30 The United States Of America As Represented By The Secretary Of The Army Adhesive bonding
US5160600A (en) * 1990-03-05 1992-11-03 Patel Gordhanbai N Chromic acid free etching of polymers for electroless plating
US6077913A (en) * 1998-03-26 2000-06-20 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US6100343A (en) * 1998-11-03 2000-08-08 Beholz Technology, L.L.C. Process for producing paintable polymeric articles
US6849390B2 (en) * 2001-02-05 2005-02-01 Pioneer Corporation Stamper-forming electrode material, stamper-forming thin film, and method of manufacturing optical disk
US20020150840A1 (en) * 2001-02-05 2002-10-17 Pioneer Corporation Stamper-forming electrode material, stamper-forming thin film, and method of manufacturing optical disk
US6645557B2 (en) 2001-10-17 2003-11-11 Atotech Deutschland Gmbh Metallization of non-conductive surfaces with silver catalyst and electroless metal compositions
US20040132300A1 (en) * 2002-12-18 2004-07-08 Enthone Inc. Procedure for activation of substrates for plastic galvanizing
US7901603B1 (en) 2004-06-21 2011-03-08 Lars Guenter Beholz Process for producing adhesive polymeric articles from expanded foam materials
US20120282417A1 (en) * 2009-12-10 2012-11-08 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method for preparing a metallized polymer substrate
US20110256413A1 (en) * 2010-04-19 2011-10-20 Pegastech Process for coating a surface of a substrate made of nonmetallic material with a metal layer
US8962086B2 (en) * 2010-04-19 2015-02-24 Pegastech Process for coating a surface of a substrate made of nonmetallic material with a metal layer
US9249512B2 (en) 2010-04-19 2016-02-02 Pegastech Process for coating a surface of a substrate made of nonmetallic material with a metal layer
CN102644065A (en) * 2012-03-30 2012-08-22 山东建筑大学 Plastic metalizing method
CN102912326A (en) * 2012-10-25 2013-02-06 南京大地冷冻食品有限公司 Method for maintaining chemical-plating dispergation working fluid made from solid powder
EP2853619A1 (en) * 2013-09-25 2015-04-01 ATOTECH Deutschland GmbH Method for treatment of recessed structures in dielectric materials for smear removal
WO2023069041A1 (en) * 2021-10-21 2023-04-27 A-Plas Genel Otomotiv Mamulleri Sanayi Ve Ticaret Anonim Sirketi A chrome-free approach to chemical etching of the surfaces of plastic materials to be coated with metal

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