[go: up one dir, main page]

WO2024054122A1 - Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice - Google Patents

Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice Download PDF

Info

Publication number
WO2024054122A1
WO2024054122A1 PCT/NZ2023/050092 NZ2023050092W WO2024054122A1 WO 2024054122 A1 WO2024054122 A1 WO 2024054122A1 NZ 2023050092 W NZ2023050092 W NZ 2023050092W WO 2024054122 A1 WO2024054122 A1 WO 2024054122A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
substrate
electroless
conductive
activated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NZ2023/050092
Other languages
English (en)
Inventor
Zhendi YANG
Fengyan HOU
Ian MARDON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cirrus Materials Science Ltd
Original Assignee
Cirrus Materials Science Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cirrus Materials Science Ltd filed Critical Cirrus Materials Science Ltd
Priority to JP2025514281A priority Critical patent/JP2025529349A/ja
Priority to CN202380063717.8A priority patent/CN119836490A/zh
Priority to CA3265932A priority patent/CA3265932A1/fr
Priority to EP23863570.0A priority patent/EP4584421A1/fr
Priority to KR1020257006845A priority patent/KR20250067125A/ko
Priority to AU2023338599A priority patent/AU2023338599A1/en
Publication of WO2024054122A1 publication Critical patent/WO2024054122A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • 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
    • C23C18/2006—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
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, 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
    • 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
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • 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
    • 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
    • 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
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating

Definitions

  • the disclosure relates to a method for providing a conductive surface on a non- conductive surface, in particular a polymeric surface.
  • the method relates to attaching silver ions to a polymeric surface to facilitate the adhesion of a metallic layer to the polymeric surface.
  • the conventional approach to metalize a non-conductive polymer substrate comprises four main steps, including etching, catalysation, electroless plating and finishing with electroplated metal of choice.
  • etching creates a rough hydrophilic surface comprising micro/nano pores.
  • This step not only prepares the polymer substrates for subsequent wet processes, but also essential to create pores which promote coating adhesion using mechanical interlock.
  • the widely used etchant contains chromium trioxide (a hexavalent chromium species) and sulphuric acid.
  • chromium trioxide a hexavalent chromium species
  • sulphuric acid a non-chromic etchant is preferred and there are numerous patents protecting the formulation and processes for non-chromic etches.
  • Permanganate is a strong oxidizing agent and non-toxic, thus is an ideal alternative to chromic acid etchant.
  • the polymer substrate is catalysed for subsequent electroless plating.
  • the art contains numerous catalysation processes and methods, where typically palladium, is adopted as a catalyst. Palladium is expensive and conventional processes frequently adopt the three sub-steps of sensitization, catalysation and activation. Even though the catalysing process was improved to a two-step process by using colloidal palladium, rinsing is still required between steps and the unstable catalysation bath requires careful maintenance, making the process less sustainable.
  • Silver (Ag) is a well-known, less expensive, alternative to palladium (Pd), but the existing art conventionally requires a Sn sensitization step prior to Ag activation.
  • a silver ionic catalyst to the etching step, such as proposed in EP09013498B1 , however this process still requires a subsequent chemical step to activate the catalyst.
  • WO2018208177A1 proposes a method to directly introduce silver nanoparticles into polymers using the polymer chemical energy to reduce the silver ions to silver metal in the absence of an external reducing agent. This method primarily pertains to polymer precursors and does not provide a method to reactivate polymerised materials.
  • the present disclosure provides a conductive surface on a nonconductive substrate comprising the steps of: a. providing a nonconductive substrate; b. conditioning the nonconductive substrate with a hydrophilizing agent to render the substrate hydrophilic; c. contacting the nonconductive substrate with an aqueous solution comprising a metal ion; d. covalently bonding the metal ion to the conditioned nonconducting substrate by the application of energy to form an activated substrate surface comprising metal ion seeds; and e.
  • an electroless plating solution comprising a plating metal salt and a reducing agent, the reducing agent being suitable for reducing both the plating metal salt and the metal ion seeds on the activated substrate surface to thereby form a conductive surface on the non- conductive substrate.
  • the nonconductive substrate is a polymeric substrate.
  • the conditioned chemical bonds on the surface of the nonconducting substrate includes a percentage of carbon-carbon double bonds of between about 10 to about 50% of the carbon backbone of the substrate.
  • the hydrophilizing agent is a solution comprising one permanganate salt, one acid and one complexing agent sourced from phosphorus containing species, having a phosphorus containing anion group of between about 0.01 and about 1 mol/L.
  • the conditioning step with the hydrophilization agent is performed between about 5 and about 20 minutes.
  • the aqueous solution comprising a metal ion further includes a complexing agent, and optionally a surfactant.
  • the complexing agent may be an ammonium ion.
  • the surfactant may be polyvinylpyrrolidone (PVP).
  • PVP polyvinylpyrrolidone
  • the aqueous solution comprising a metal ion is maintained at a temperature of between about 10 and about 40 degrees Celsius.
  • the non-conducting substrate is contacted with the aqueous solution comprising a metal ion.
  • the contact time between the substrate and aqueous solution is between about 1 and about 10 minutes.
  • the aqueous solution comprising a metal ion is sprayed on the nonconducting substrate.
  • the aqueous solution comprising a metal ion comprises one or more of AgNOs, CuSC , NiSC , or CuCh in a concentration between about 0.005 and about 0.1 mol/L.
  • energy source is heat and the temperature is between about 60 and about 90 degrees Celsius.
  • the energy source is applied as a hot air stream or a hot air environment. [0025] In one example, the energy source is applied for a contact time of between about 2 and about 10 minutes.
  • the metal is Ag
  • the electroless plating solution comprises electroless nickel boron and the reducing agent amine borane.
  • the metal is Ag and the electroless plating solution comprises copper and the reducing agent is selected from formaldehyde or amine borane.
  • the present disclosure provides a conductive metal surface comprising a hydrophilic conditioned nonconductive substrate, activated metal seeds, an electroless metal deposited metal surface, and an electroplated metal surface.
  • the density of activated metal seeds on the nonconductive substrate is sufficient to produce a bonding strength of 10 N/cm or higher when tested according to ASTM B533.
  • the conductive metal surface comprising a hydrophilic conditioned nonconductive substrate, activated metal seeds, an electroless metal deposited metal surface, and an electroplated metal surface, produced according to any one of the aspects and examples disclosed herein.
  • a method to metalize a chemically conditioned substrate is provided.
  • the substrate is hydrophilized using metal-absorbing functional groups.
  • the substrate may be selected from one or more long chained polymers containing double bonded carbon atoms.
  • the conditioning step may further include or comprise destressing a polymeric substrate.
  • the destress process may include a heat-treatment step.
  • the destressing step may include immersion in an organic solvent such as but not limited to acetic acid or acetone.
  • the conditioning step may comprise or include hydrophilizing the destressed substrate using a solution, the composition of which is selected based on the nature of the substrate.
  • the hydrophilizer may comprise one stable potassium permanganate salt, one acid and one phosphorous source containing phosphates or pyro phosphates.
  • the conditioning step may operate at temperatures between about 25 and about 45 degrees Celsius.
  • the conditioning step may include a manganese dioxide removal step using an oxalic and/or sulphuric acid solution by way of example.
  • the polymeric substrate is contacted for between about 1 and about 10 minutes using metal ions either by immersion or spraying the metal-containing solution comprising monovalent or divalent ions.
  • the catalyst ions may require an activation step.
  • the metal ion source is an aqueous silver nitrate solution.
  • the functional group(s) introduced during the conditioning step enable the absorption of metal ions. Without wanting to be bound by any particular theory, the hydrogen atoms on the conditioned polymeric surface are likely exchanged with the metal ions during this step. In a later step, the influence of external energy activates the metal ions and strengthens the bond between the polymeric surface and the metal ions. After a period of time, preferably between about 1 and about 10 minutes, the polymer chains reorient the hydroxyl groups and couple the metal seeds to the polymer surface.
  • the catalyst bath may include a surfactant.
  • a surfactant enables the uniform seeding of the polymer surface with the metal ions.
  • a one or two-step activation process may be employed to promote the reorientation of the metal seeded hydroxyl groups on the polymer surface.
  • the preferred example adopts a low velocity hot air flow.
  • An alternate activation step involves a two-step process, which comprises low velocity air drying followed by heat treatment in an oven.
  • the metallized polymer is post processed to increase the adhesion between metal coating and the polymer substrate by means of covalent bonds.
  • the post processing step comprises either heat treatment for a duration between about 1 to about 5 hours or aging in ambient conditions for between about 5 and about 10 days.
  • FIG 1 is a flow diagram of the method to metallise nonconductive surfaces
  • FIG 2 shows the results of ASTM D3359 cross hatch testing on various substrates.
  • FIG 3 shows the results of a peel test performed according to ASTM B533 on a metallic surface deposited according to aspects of the invention
  • FIG 4 shows the ASTM D3359 cross hatch testing on ABS treated with various activation enhancement treatments.
  • FIG 5 is an XPS analysis of an activated ABS surface showing the chemical bonding information between the polymer and the metal seed
  • FIG 6 is an SEM of conditioned ABS (left) and PPS (right) polymers according to aspects of the invention
  • FIG 7 is an SEM image of a traditionally etched polymer substrate
  • FIG 8 is an XPS analysis of an activate PPS surface.
  • FIG 9 is a surface and cross-section image of a PPS-CF substrate showing metallic adhesion developed through the disclosed process.
  • the term “about” or “approximately” usually means within 20%, more preferably within 10%, and most preferably still within 5% of a given value or range. Alternatively, the term “about” means within a log (i.e. , an order of magnitude) preferably within a factor of two of a given value.
  • Fig. 1 illustrates an example method for producing a metallic coating on a non- conductive polymer substrate.
  • the method conditions a polymer substrate.
  • the conditioning step prepares, for example but without limitation, a polymer substrate surface for bonding to a metal ion.
  • the conditioning step creates a hydrophilic surface on a polymer substrate and induces functional groups that easily absorb metal ions.
  • the polymeric substrate may be either a single polymer or co-polymer or be reinforced with glass fibres, carbon fibres or other reinforcing materials known in the art.
  • the preferred polymer chain contains easily oxidized functional groups, such as double bonded carbon as seen in hydrocarbons containing vinyl groups or benzyl rings and sulphides. Preferred structures are shown below. Polyesters and polymers that only contain C-C single bonds are less preferred.
  • the polymer substrate may be selected from Acrylonitrile Butadiene Styrene (ABS), polyamide (PA), Polyphenylene Sulphide (PPS), phenolic resin or blends of these polymers.
  • ABS Acrylonitrile Butadiene Styrene
  • PA polyamide
  • PPS Polyphenylene Sulphide
  • the polymeric substrate may be produced by injection moulding, 3D printing, or other such methods that create a desirable finish product shape.
  • the polymeric substrate may be solid or containing blind holes, open holes or channels or other features suitable for the final application.
  • the conditioning step may comprise or include destressing a substrate.
  • the destressing process is selected based on the polymeric substrate shape, its composition and processing conditions.
  • the destress process may include heat treatment between 60 and 75 degrees Celsius for 0 to 2 hours preferably.
  • the heat-treatment may be conducted in oven or in hot water.
  • the destress process may include immersion in an organic solvent between 15 and 30 degrees Celsius for 0.5 to 30 minutes.
  • An example of such organic solvent may be acetic acid.
  • an organic solvent may be 25% acetone.
  • the conditioning step may comprise hydrophilizing a polymeric substrate following destressing.
  • the hydrophilizer bath composition is selected based on the polymeric substrate chemistry, since the hydrophilizer selectively breaks the polymer chains and attaches active functional groups to the polymer chains. These active functional groups enhance the hydrophilicity of the polymeric substrate.
  • the hydrophilic groups possess an affinity for metal ions, such that metal ions are absorbed and bonded to the polymer chains.
  • Hydrophilic functional groups may be selected from polar groups such as hydroxyl, sulfonic and carbonyl groups among others known in the art.
  • the polymeric substrate is ABS and the conditioning step includes a hydrophilization step and the hydrophilizer solution comprises at least one permanganate salt, one acid and one source of phosphorous containing species selected from phosphate and pyrophosphate.
  • the permanganate salt may be selected from those well known in the art that dissolves in an aqueous solution, preferably potassium permanganate or sodium permanganate.
  • the concentration of the permanganate salt is between 10 g/L and 200 g/L or the maximum solubility of the particular permanganate salts.
  • the acid may be inorganic acid or organic acid.
  • the inorganic acid may be sulphuric acid, nitric acid or phosphoric acid.
  • the organic acid may be acetic acid.
  • the concentration of acid is between 3.8 and 10 mol/L for a monobasic acid.
  • the phosphorous containing species may be phosphate salt, hydrogen phosphate salt, dihydrogen phosphate salt or pyrophosphate salt.
  • the concentration of phosphorous containing species is between 0.05 and 1 mol/L.
  • the conditioning hydrophilizer may operate between 25 and 45 degrees Celsius and for 5 to 20 minutes.
  • Permanganate is a strong oxidizing agent, and its oxidizing power is further enhanced in an acidic environment or increases with decreasing pH of a solution. Compared with conventional chromic etch, permanganate is environmentally friendly and does not have health concerns, while maintaining sufficient oxidizing power. However, permanganate readily decomposes, especially in acidic solutions, to form divalent manganese ions and manganese dioxide. Divalent manganese ions further catalyse and therefore speed up the decomposition of permanganate. Complexing divalent manganese ions with stabilizing agents reduces their influence on permanganate anions, thus suppressing the decomposition of permanganate.
  • inorganic species are preferred over organic species, as organic species may be destroyed by permanganate.
  • phosphates and pyrophosphates are preferred complexing agents.
  • the lifetime of permanganate hydrophilizer could be extended.
  • the conditioning step includes a method to remove the residual manganese dioxide produced in the previous step.
  • the substrate is immersed in a solution that comprises oxalic acid between 5 and 20 g/L and sulphuric acid between 5 and 15 percent by volume.
  • the manganese dioxide removal step may be conducted by soaking or by sonication.
  • the manganese dioxide removal solution operates between 30 and 80 degrees Celsius, preferably between 50 and 60 degrees Celsius, for between 0.5 to 10 minutes, preferably between 2 and 5 minutes.
  • the removal step operates in sonication for 1 to 5 minutes, preferably 3 minutes.
  • the method comprises contacting the conditioned polymer surface with a solution containing metal ions.
  • the substrate is immersed in a bath to contact the solution, in an alternative example the solution is sprayed on the substrate.
  • the metal ions can be any monovalent or divalent metal ions suitable for catalysing electroless reduction of a coating metal, such metal ions include Ag + , Ni + , Ni 2+ , Cu + , Cu 2+ , Co + , Co 2+ amongst others.
  • Monovalent ions are preferred over divalent ions as hydrophilic hydroxyl groups introduced on the polymer surface can reduce a monovalent ion.
  • Divalent ions may require a further step of addition of a reduction chemical to complete the reduction. The reduction chemical will depend on the selected ion.
  • the preferred monovalent ion is silver.
  • the solution containing the metal ion source is aqueous and the Ag ion source may be selected from an Ag salt that is water soluble.
  • the Ag ion source is silver nitrate and the concentration in the bath is between 0.005 and 0.1 mol/L, preferably between 0.01 and 0.05 mol/L.
  • the preferred concentration of the silver ion source is determined by the plating rate of the following electroless deposition step.
  • the silver ion is complexed, and the complexing agent is ammonium ion, complexing the silver ion source helps prolong the life of the metal ion containing solution.
  • the silver ion is stabilized with Polyvinylpyrrolidone (PVP), to minimize the agglomeration of silver nanoparticles when activated.
  • PVP Polyvinylpyrrolidone
  • polar functional groups such as hydroxyl or carboxyl
  • the metal ions When contacted with a solution containing monovalent metal ions, the metal ions are absorbed on the hydrophilic polymer surface.
  • hydrogen anions, from the functional groups exchange places with the monovalent metal ions, which are reduced.
  • monovalent metal ions At other places on the polymer surface monovalent metal ions are reduced but not being attached to the surface, do not contribute to the coating adhesion.
  • water molecules attached to the polymer chain or trapped in the polymer matrix are driven off, so that the bonding strength between metal atoms and polymer improves. Over time, the polymer chains reorientate the outwardly pointing hydroxyl groups to minimize the surface energy, which tightly couples the attached metal particles to polymer surface
  • the metal ion bath is at room temperature, alternatively the catalyst ion bath can be at any temperature between 10 degrees Celsius and 40 degrees Celsius.
  • the temperature being selected to maximize the lifetime of the metal ion solution and optimise the reaction between the metal ions and the hydrophilic groups on the substrate.
  • Sufficient time for the metal ions to be absorbed onto the hydrophilic groups is between 1 to 10 minutes, preferable 5 minutes. Excessive contact times between the substrate and metal ion solution absorbs too much metal ion on the surface which may cause an excessive reaction rate in the subsequent electroless deposition step.
  • the substrate is ABS and metal ion bath comprises 2 g/L silver nitrate and the contacting process operates at room temperature for 10 minutes.
  • the metal ion bath comprises 8 g/L silver nitrate and a liquid polymer/surfactant, such as, 40 g/L of Polyvinylpyrrolidone, to enable a more uniform seeding of the metal ions on the polymer surface.
  • a liquid polymer/surfactant such as, 40 g/L of Polyvinylpyrrolidone
  • the metal ion bath comprises 0.3 mol/L cuprous chloride with 5.2 mol/L hydrochloric acid to increase the solubility of cuprous chloride.
  • the catalyst metal bath comprises cupric ions between 0.1 and 0.2 mol/L.
  • the cupric ion maybe sourced from copper sulphate, copper acetate or any water-soluble cupric salts known in the art.
  • the method enhances the metal ion on the substrate.
  • the enhancement step reduces and fixes the metal ions to a polymer substrate. While reduction of the metal ion may occur naturally over time the process may be accelerated by external energy source, such as heat.
  • the enhancement process may comprise either one or two steps.
  • the enhancement step adopts a low velocity hot air flow at temperatures between 60 and 90 degrees Celsius for 2 to 10 minutes, preferable a flow rate of 15 m/s and temperature of 80 degrees Celsius and 3 minutes.
  • a two-step activation comprises drying in a low velocity compressed air flow at room temperature, followed by an oven heat treatment between 60 and 90 degrees Celsius for 5 to 10 minutes.
  • the activated substrate is stored for 1 hour before next step to further integrate the reduced Ag nanoparticles into the polymer substrate.
  • the method deposits a conductive surface on a polymer substrate from an electroless plating bath, that is compatible with metal catalysation seeds.
  • the electroless plating bath may be selected from commercial nickel or copper plating baths to produce a nickel or copper conductive layer.
  • the electroless plating bath comprises nickel sulphate hexahydrate 50g/L, sodium pyrophosphate 10Og/L and dimethylamine borane 3g/L and operates between 25 and 40 degrees Celsius and the polymer substrate is fully covered with a conductive layer in 30 minutes.
  • the method electroplates the substrate with one or more layers of surface metal selected according to the required component functionality.
  • the metal layer may comprise a single metal or metal alloy layer, or multiple metal or metal alloy layers.
  • the metal coating maybe selected from nickel with various finish of matt to full bright, copper, tin, cobalt, and nickel-zinc alloy among others.
  • the method post treats the metallised polymer surface to increase adhesion between the metal coating and the substrate. Post-treatments may comprise heat treatment between about 40 and about 70 degrees Celsius for about 1 to about 3 hours or aging at ambient conditions for about 1 week, or combination of these two steps. Post treatment further improve the coating adhesion by eliminating the moisture trapped in polymer substrate.
  • the adhesion between the polymer substrate and the metal surface is developed by covalent bonds between the metal atoms and the polymer surface. These covalent bonds are initially created by the hydroxyl or carboxyl groups introduced on the polymer surface by the conditioning step.
  • the conditioning step introduces the new functional groups by breaking the bonds on one or more surface polymers and attaching functional groups to the bone sites.
  • the metal ion is reduced by new functional groups as shown in the equation below.
  • the initial bonds of the catalyst atoms to the substrate may be improved by the rearrangement of the polymer chains to better integrate the metal nano particles.
  • This process is shown in the equation below. The process occurs naturally over time or may be accelerated by the application of heat.
  • the metal coated substrate is heat treated at a temperature between about 40 degrees Celsius and about 100 degrees Celsius, preferably about 60 degrees Celsius for a period between about 10 minutes and about 2 hours, preferably about 30 minutes.
  • the metallized polymer substrate is aged naturally for a period between about 12 hours and about 72 hours, preferably about 24 hours, at room temperature.
  • Conditioning depends on the polymer substrate, the examples provided here discuss the conditioning according to aspects of the invention for a variety of commercially important substrates.
  • Conditioning disrupts the polymer chains on the surface of the substrate and introduces hydrophilic functional groups onto the surface of the substrate. While conditioning may also etch the surface, the development of a very rough surface is not required for coating adhesion.
  • the conditioning step comprise an optional destress step and a hydrophilization step.
  • a MnO 2 removal step may be required if hydrophilizer solution is permanganate based.
  • the effectiveness of a conditioning process can be measured by wettability test. A polymer surface is considered as sufficiently conditioned if its contact angle with water is less than 10°. Table 1 summarizes the conditions parameters for various polymer substrates.
  • conditioned ABS coupon was activated with Ag and plated with electroless Ni bath. ABS coupon is firstly conditioned in a solution comprising KMnC 20 g/L and H2SO4 20% by volume. The conditioning step was carried out at about 35°C for about 10 minutes. The residual MnOs produced from the conditioning step was then removed in a solution comprising 10 g/L oxalic acid and 10% sulphuric acid, operating at about 50°C for about 2 minutes.
  • ABS coupon was then rinsed with deionized water and immersed in a solution containing 10 g/L of silver nitrate for 10 minutes under room temperature. Following immersion, the ABS coupon was treated in a hot air stream at about 70°C till the surface dries, usually taking about 2 minutes, finally, the ABS coupon was immersed in an electroless Ni-B bath, comprising 50 g/L nickel sulphate hexahydrate, 100 g/L sodium pyrophosphate and 3 g/L of Dimethylamine Borane. Electroless Ni-B operates at about 30°C for about 30 minutes. The ABS coupon was fully plated with a conductive Ni layer and ready for subsequent electroplating with the metal of choice.
  • conditioned ABS was activated with Cu and plated with electroless Cu bath.
  • the ABS coupon was conditioned from the process detailed above.
  • the ABS coupon was then immersed in a solution containing cuprous chloride and chloric acid for about 10 minutes.
  • the ABS coupon was then enhanced in hot-air stream and plated with electroless Ni, as detailed above.
  • the PPS coupon was activated with Cu and plated with electroless Ni bath.
  • the PPS coupon was firstly conditioned in a solution comprising 20 g/L KMnC and 40% H2SO4. The conditioning operates at about 27°C for about 30min.
  • the residual MnC>2 produced from the conditioning step was then removed in a solution comprising 10 g/L oxalic acid and 10% sulphuric acid, operating at about 50°C with sonication for about 2 minutes. Following rinse with deionized water, the PPS coupon was then immersed in a solution containing cuprous ions.
  • the cuprous solution was prepared by mixing ascorbic acid solution with copper sulphate solution and contains 0.125 mol/L Cu and 0.002 mol/L ascorbic acid.
  • the PPS coupon was then rinsed with deionized water and plated with electroless Cu comprising 50 mmol/L EDTA, 50 mmol/L copper chloride, 0.1 mol/L boric acid and 0.1 mol/L of DM AB.
  • Table 2 summarizes the activation parameters using various metal ion sources. Table 2. Activation parameters for various metal ions
  • the objective of the disclosed methods was to create an adherent metallic coating on a polymer surface.
  • the two commonly adopted measurements for coating adhesion are quantitative peel testing and qualitative cross hatch testing. Peel testing was performed according to ASTM B533 with results continuously recorded as newtons/cm during the peel and presented as peak, average and standard deviation for the test.
  • Cross hatch testing was performed according to ASTM D3359 with qualitative results recorded as OB to 5B with 5B being the best adhesion with 0% coating removal.
  • ABS coupon was plated with electroless Ni according to the process detailed in Example 2 and then electroplated with bright Ni.
  • the bright Ni bath comprised 270 g/L nickel sulphate, 60 g/L nickel chloride, 40 g/L boric acid and commercially available additives.
  • Bright nickel was plated at about 4 A/dm 2 for about 20 minutes to create about 16 pm thick of nickel coating.
  • Cross hatch test following ASTM D3359 demonstrated excellent coating adhesion, was classified as 5B (Fig. 201 ).
  • ABS coupon was plated with electroless Ni according to the process detailed in Example 2 and then electroplated with bright Cu.
  • the bright Cu bath comprises 195 g/L copper sulphate, 75 g/L sulphuric acid and commercially available additives.
  • Bright Cu plating operates at about 4 A/dm 2 for about 100 minutes to create about 44 pm of copper coating.
  • the copper plated ABS coupon was conditioned at about 70°C for about 1 hour prior to peel strength test following ASTM B533 (Fig. 301). The average peel strength of 19.2 N/cm demonstrated excellent coating adhesion (Fig. 302).
  • the PPS coupon reinforced with glass fibre was firstly conditioned in a solution comprising KMnC 20g/L and H2SO440% by volume.
  • the conditioning operated at about 27°C for about 30 minutes.
  • the residual MnOs produced from the conditioning step was then removed in a solution comprising 10 g/L oxalic acid and 10% sulphuric acid, operating at about 50°C with sonication for about 2 minutes.
  • the PPS-GF coupon was then rinsed with deionized water and immersed in a solution containing 2 g/L of silver nitrate for about 10 minutes under room temperature.
  • the PPS-GF coupon was treated in a hot air stream at about 70°C till the surface dried. Finally, the PPS-GF coupon was plated with electroless Ni and electrolytic Ni of about 10 pm.
  • the PETG coupon is firstly conditioned in a solution comprising KMnO4 20 g/L and H2SO440% by volume.
  • the conditioning operates at about 27°C for about 1 hour.
  • the residual MnO2 produced from the conditioning step was then removed in a solution comprising 10 g/L oxalic acid and 10% sulphuric acid, operating at about 50°C for about 2 minutes.
  • the PETG coupon was then rinsed with deionized water and immersed in a solution containing 2 g/L of silver nitrate for about 10 minutes under room temperature. Following immersion, the PETG coupon was treated in a hot air stream at about 70°C till the surface dried.
  • the PPS coupon was plated with electroless Ni.
  • the Ni coating pass cross hatch test following ASTM D3359, was classified as 5B (Fig. 203).
  • the PA6 coupon was firstly conditioned in a solution comprising 20% sulphuric acid, at about 20 degrees Celsius for about 20 seconds. Following rinsing with deionized water, the conditioned PA6 coupon was then immersed in a solution containing 2 g/L of silver nitrate for about 10 minutes at room temperature. The PA6 coupon was then activated in a hot air stream at about 70 degrees Celsius till the surface dried. Finally, the PA6 coupon was plated with electroless and electrolytic Ni of about 10 pm. The Ni coating adhesion was classified as 5B, following ASTM D3359.
  • the paper reinforced phenolic resin coupon was firstly conditioned in a solution comprising 20 g/L potassium permanganate and 20% sulphuric acid at about 35 degrees Celsius for about 15 minutes. The residual Mn ⁇ 2 were removed in a solution comprising 10 g/L oxalic acid and 10% sulphuric acid, at about 50 degrees Celsius for about 2 minutes. Following rinsing in deionized water, the conditioned paper reinforced phenolic resin was immersed in a solution containing 2 g/L silver nitrate for about 5min, at room temperature. The paper reinforced phenolic resin was then treated in hot air stream at about 70 degrees Celsius for about 2 minutes. The activated paper reinforced phenolic resin was finally plated with electroless and electrolytic Ni of about 10 pm. The Ni coating adhesion was classified as 5B, following ASTM D3359. Table 3 summarizes the coating adhesion results of the various polymeric substrates.
  • a method to activate a polymeric surface for electroless plating by an external heat source is described herein.
  • the following examples demonstrate how the heat treatment develops coating adhesion.
  • ABS coupons in this example were conditioned as detailed in Table 3 and immersed in a solution containing 10 g/L silver nitrate, at room temperature for about 10 minutes.
  • the ABS coupon was then left at ambient conditions until dry and then plated with electroless and electrolytic Ni.
  • Cross hatch testing following ASTM reveals coating adhesion, classified as 1 B (Fig. 401).
  • the ABS coupon was activated in a hot air stream at about 70C and left for about 1 hour prior to electroless and electrolytic Ni plating.
  • the coating had excellent adhesion, classified as 5B (Fig. 402).
  • excess Ag solution was blown off the ABS coupon using cold air, and the coupon was heat treated in an oven at about 60°C for about 5min prior to electroless and electrolytic Ni plating.
  • the coating had excellent adhesion, classified as 5B (Fig. 403).
  • excess Ag solution was blown off the ABS coupon using cold air, and the coupon was heat treated in an oven at about 40°C for about 5min prior to electroless and electrolytic Ni plating.
  • the coating exhibited good adhesion, classified as 4B (Fig. 404).
  • PPS is traditionally a very difficult substrate on which to develop adherent metallic coatings and frequently mechanical etching provides the only viable approach.
  • hydrophilization in the permanganate, sulphuric acidbased solution effectively developed sulphonic functional groups to which silver was covalently bonded after heat activation.
  • Fig. 8, 801 shows the aromatic polymer signature corresponding to the benzyl ring (803) of the hydrophilized substrate.
  • Fig. 8, 802 shows that the metal seeds are bound to the PPS polymeric surface by covalent bonds between Ag and (-C6H4S-) functional group (804).
  • Fig. 8, 805 provides concentration data of the metal seeds on the polymeric surface and at a depth of 15 nm from the surface.
  • the increased concentration of metal seeds at the sub-surface demonstrates that the enhancement process described in the invention, i.e., reorientation of polar groups and associated movement of metal seeds into the polymeric sub-surface.
  • PPS-CF carbon fiber substrates are inherently difficult surfaces on which to develop adherent metallic coatings.
  • hydrophilization in permanganate, sulphuric-acid based solution effectively developed sulphonic functional groups to which silver was covalently bonded after heat activation.
  • adherent plating on such an activated surface was demonstrated.
  • the activated PPS-CF coupon was then immersed in an electroless Ni plating bath.
  • the resultant coating (FIG. 9) was about 9
  • the image, 901 demonstrates that the Ni coating is adherent not only to the PPS matrix but also to the carbon fiber fillers in the composite.
  • the present disclosure in a preferred form provides the advantages of greater adhesion, more energy efficiency with shorter processing times; and provides an inherently safer process due to lower processing temperatures and elimination of toxic chemicals than are often associated with methods in the prior art.

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé destiné à fournir une surface conductrice sur une surface non conductrice, en particulier une surface polymère. Le procédé concerne en particulier la fixation d'ions d'argent sur une surface polymère pour faciliter l'adhérence d'une couche métallique à la surface polymère.
PCT/NZ2023/050092 2022-09-07 2023-09-07 Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice Ceased WO2024054122A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2025514281A JP2025529349A (ja) 2022-09-07 2023-09-07 非導電性ポリマー表面上に導電性表面を提供する方法
CN202380063717.8A CN119836490A (zh) 2022-09-07 2023-09-07 用于在非导电聚合物表面上提供导电表面的方法
CA3265932A CA3265932A1 (fr) 2022-09-07 2023-09-07 Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice
EP23863570.0A EP4584421A1 (fr) 2022-09-07 2023-09-07 Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice
KR1020257006845A KR20250067125A (ko) 2022-09-07 2023-09-07 비전도성 중합체 표면에 전도성 표면을 제공하는 방법
AU2023338599A AU2023338599A1 (en) 2022-09-07 2023-09-07 Method for providing a conductive surface on a non-conductive polymeric surface

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263404524P 2022-09-07 2022-09-07
US63/404,524 2022-09-07

Publications (1)

Publication Number Publication Date
WO2024054122A1 true WO2024054122A1 (fr) 2024-03-14

Family

ID=90191618

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NZ2023/050092 Ceased WO2024054122A1 (fr) 2022-09-07 2023-09-07 Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice

Country Status (8)

Country Link
EP (1) EP4584421A1 (fr)
JP (1) JP2025529349A (fr)
KR (1) KR20250067125A (fr)
CN (1) CN119836490A (fr)
AU (1) AU2023338599A1 (fr)
CA (1) CA3265932A1 (fr)
TW (1) TW202424265A (fr)
WO (1) WO2024054122A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090075089A1 (en) * 2006-03-23 2009-03-19 Tetsuji Ohta Material for Forming Electroless Plate and Method for Forming Electroless Plate Using the Same
US20170096515A1 (en) * 2014-03-18 2017-04-06 Nippon Shokubai Co., Ltd. Resin particles, conductive microparticles, and anisotropic conductive material using same
WO2019183044A1 (fr) * 2018-03-19 2019-09-26 Nanotek Instruments, Inc. Métallisation des films polymères médiée par le graphène
US20200255947A1 (en) * 2017-09-28 2020-08-13 Srg Global Liria S.L. Surface activated polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090075089A1 (en) * 2006-03-23 2009-03-19 Tetsuji Ohta Material for Forming Electroless Plate and Method for Forming Electroless Plate Using the Same
US20170096515A1 (en) * 2014-03-18 2017-04-06 Nippon Shokubai Co., Ltd. Resin particles, conductive microparticles, and anisotropic conductive material using same
US20200255947A1 (en) * 2017-09-28 2020-08-13 Srg Global Liria S.L. Surface activated polymers
WO2019183044A1 (fr) * 2018-03-19 2019-09-26 Nanotek Instruments, Inc. Métallisation des films polymères médiée par le graphène

Also Published As

Publication number Publication date
KR20250067125A (ko) 2025-05-14
AU2023338599A1 (en) 2025-03-20
EP4584421A1 (fr) 2025-07-16
CN119836490A (zh) 2025-04-15
TW202424265A (zh) 2024-06-16
CA3265932A1 (fr) 2024-03-14
JP2025529349A (ja) 2025-09-04

Similar Documents

Publication Publication Date Title
EP0913498B1 (fr) Procédé de plaquage autocatalytique
CA1191745A (fr) Conditionnement d'un substrat pour le plaquage direct non electrolytique de ses trous et surfaces
JP4044286B2 (ja) 金属を用いた基板の被覆方法
WO2005094394A2 (fr) Metallisation non chromique de matieres plastiques
JP6482049B1 (ja) 無電解めっきの前処理用組成物、無電解めっきの前処理方法、無電解めっき方法
WO2007122869A1 (fr) Composition PERMETTANT UN traitement d'attaque chimique d'un article MOULÉ en RÉSINE
CN1333843A (zh) 塑料表面敷镀金属的方法
EP2725118B1 (fr) Procédé de dépôt autocatalytique et solution utilisée pour celui-ci
CN105274504A (zh) 一种在膨胀石墨表面化学镀铜的方法
KR20010086023A (ko) 플라스틱 표면을 금속 처리하는 방법
JPWO2007116493A1 (ja) プラスチック用の表面改質液およびそれを利用したプラスチック表面の金属化方法
CN106868479B (zh) 用于印刷电路板和通孔的无电极金属化的环保稳定催化剂
WO2024054122A1 (fr) Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice
CN106868560A (zh) 用于印刷电路板和通孔的无电极金属化的环保稳定催化剂
JP4646376B2 (ja) ダイレクトプレーティング用アクセレレータ浴液およびダイレクトプレーティング方法
JP5339023B2 (ja) スミア除去用組成物
CN101245481A (zh) 无铬污染的abs工程塑料零部件表面微蚀方法
JP5083005B2 (ja) 表層に貴金属を固定させた樹脂基板、その製造方法、回路基板、及びその製造方法
JP3560764B2 (ja) ポリアミド樹脂用のエッチング液
JP2586466B2 (ja) 金属被覆炭素材料の製造法
CN114829672B (zh) 避免在用于电沉积的支架涂层上的不需要的镀覆
JP2023060704A (ja) 無電解めっき方法
CN106554515B (zh) 氧化铜包覆硅藻土复合材料和包含其的塑料组合物与塑料制品以及它们的制备方法
PL189155B1 (pl) Sposób bezpośredniej metalizacji dielektryków, zwłaszcza ścianek otworów obwodów drukowanych
JP2019203168A (ja) 無電解めっきの前処理用組成物、無電解めっきの前処理方法、無電解めっき方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23863570

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202380063717.8

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 819256

Country of ref document: NZ

Ref document number: AU2023338599

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2025514281

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025514281

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 2023338599

Country of ref document: AU

Date of ref document: 20230907

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 819256

Country of ref document: NZ

WWE Wipo information: entry into national phase

Ref document number: 2023863570

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2023863570

Country of ref document: EP

Effective date: 20250407

WWP Wipo information: published in national office

Ref document number: 202380063717.8

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2023863570

Country of ref document: EP