WO2019183044A1 - Métallisation des films polymères médiée par le graphène - Google Patents

Métallisation des films polymères médiée par le graphène Download PDF

Info

Publication number
WO2019183044A1
WO2019183044A1 PCT/US2019/022900 US2019022900W WO2019183044A1 WO 2019183044 A1 WO2019183044 A1 WO 2019183044A1 US 2019022900 W US2019022900 W US 2019022900W WO 2019183044 A1 WO2019183044 A1 WO 2019183044A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
polymer film
resin
acrylate
ether
Prior art date
Application number
PCT/US2019/022900
Other languages
English (en)
Inventor
Yi-Jun Lin
Shaio-Yen Lee
Yao-De Jhong
Aruna Zhamu
Bor Z. Jang
Original Assignee
Nanotek Instruments, Inc.
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
Priority claimed from US15/924,988 external-priority patent/US20190283379A1/en
Priority claimed from US15/924,991 external-priority patent/US20190284712A1/en
Priority claimed from US15/926,458 external-priority patent/US20190292675A1/en
Priority claimed from US15/943,081 external-priority patent/US20190292676A1/en
Application filed by Nanotek Instruments, Inc. filed Critical Nanotek Instruments, Inc.
Publication of WO2019183044A1 publication Critical patent/WO2019183044A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C3/00—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
    • B05C3/02—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material the work being immersed in the liquid or other fluent material
    • B05C3/12—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material the work being immersed in the liquid or other fluent material for treating work of indefinite length
    • B05C3/125—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material the work being immersed in the liquid or other fluent material for treating work of indefinite length the work being a web, band, strip or the like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/30—Purity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones

Definitions

  • the present disclosure relates generally to the field of metallization of polymer component surfaces and, more particularly, to a graphene-mediated metal-plated polymer thin film and a process and required apparatus for producing same.
  • Metallized plastics are commonly used for decorative purposes.
  • the surfaces of plastics such as acrylonitrile-butadiene- styrene (ABS) and ABS-polycarbonate blends, are metallized for use in sanitary fittings, automobile accessories, furniture, hardware, jewelries, and buttons/knobs. These articles of manufacture may be metallized to impart an attractive appearance to the article surfaces.
  • plastics, rubbers, and polymer matrix composites can also be metallized for functional purposes.
  • metallization of p!astics-based electronic components may be carried out for the purpose of shielding against electromagnetic interference (EMI).
  • EMI electromagnetic interference
  • the surface properties of polymeric components can be altered in a controlled manner through metallic coating.
  • Articles made from an electronically nonconductive polymer can be metallized by an electroless metallization process.
  • the article is first cleaned and etched, then treated with a noble metal (e.g palladium) and finally metallized in a metallizing solution.
  • the etching step typically involves the use of chromic acid or chromosulfuric acid.
  • the etching step serves to make the surface of the article receptive to the subsequent metallization through improved surface wettability by the respective solutions in the subsequent treatment steps and to make the ultimately deposited metal being well-adhered to the polymer surface.
  • the surface of a polymer article is etched using chromosulfuric acid to form surface micro-caverns in which metal is deposited and adhered.
  • the polymer component surface is activated by means of an activating agent (or activator), typically comprising a noble metal, and then metallized using electroless plating. Subsequently, a thicker metal layer can be deposited eiectrolytically
  • Chromosulfuric acid-based etching solutions are toxic and should therefore be replaced where possible.
  • the etching solutions based on chromosulfuric acid may be replaced with those comprising permanganate salts.
  • permanganates lit an alkaline medium for metallization of circuit boards as a carrier of electronic circuits has long been established. Since the hexavalent state (manganate) which arises in the oxidation is water-soluble and has sufficient stability under alkaline conditions, the manganate, similarly to trivalent chromium, can be oxidized eiectrolytically back to the original oxidizing agent, in this case the permanganate.
  • WO 2009/023628 A2 proposes the use of strongly acidic solutions comprising an alkali metal permanganate salt.
  • the solution contains about 20 g/1 alkali metal permanganate salt in 40-85% by weight phosphoric acid.
  • Such solutions form colloidal manganese(IV) species which are difficult to remove. Further, it is also difficult for colloids to form a coating of adequate quality.
  • WO 2009/023628 A2 proposes the use of manganese(VII) sources which do not contain any alkali metal or alkaline earth metal ions. However, the preparation of such manganese(VII) sources is costly and inconvenient.
  • the polymer component surface must be activated by means of an activating agent, which typically comprises a noble metal (e.g. palladium).
  • an activating agent typically comprises a noble metal (e.g. palladium).
  • the noble metals are known to be rare and expensive.
  • the chemically etched plastic surface is treated with a metal salt solution, containing cobalt salt, silver salt, tin salt, or lead salt.
  • the activated plastic surface must be further treated with a sulfide solution. The entire process is slow, tedious, and expensive.
  • the present disclosure provides a surface-metallized polymer film comprising:
  • a graphene layer having a thickness from 0.34 nm to 50 pm (preferably from 1 nm to 10 pm, and most preferably from 10 nm to 1 pm) and comprising multiple graphene sheets and an optional conductive filler coated on or bonded to at least one of the two primary surfaces with or without implementing an adhesive resin between graphene sheets and the primary surface of the polymer film; and
  • the multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof.
  • both primary surfaces are metallized.
  • each of the two primary surfaces is coated with or bonded to a graphene layer having a thickness from 0.34 nm to 50 pm and comprising multiple graphene sheets and an optional conductive filler.
  • a metal layer comprising a plated metal is deposited on the graphene layer of each of the two primary surfaces.
  • Also provided is process for producing a surface-metallized polymer film comprising: (a) preparing a graphene dispersion comprising multiple graphene sheets and an optional conductive filler dispersed in a first liquid medium, which is an adhesive monomer or contains a liquid adhesive monomer or oligomer dissolved in a solvent; (b) feeding a continuous polymer film from a feeder roller into a deposition zone, wherein the graphene dispersion is dispensed to deposit the graphene sheets to a surface of the polymer film; (c) moving the graphene-coated polymer film into a metallization chamber which accommodates a plating solution therein for plating a layer of a desired metal onto the graphene-coated polymer film to obtain a surface-metallized polymer film; and (d) operating a winding roller to collect the surface-metallized polymer film.
  • polymer films e.g. plastic, rubber, and polymer composite
  • polymer films can take on a luxurious chrome look and exhibit superior abrasion resistance, barrier properties (e.g. against permeation of water vapor, oxygen, etc.), heat radiation reflective properties, corrosion resistance, strength, and hardness.
  • barrier properties e.g. against permeation of water vapor, oxygen, etc.
  • heat radiation reflective properties e.g. against permeation of water vapor, oxygen, etc.
  • corrosion resistance e.g. against permeation of water vapor, oxygen, etc.
  • heat radiation reflective properties e.g. against permeation of water vapor, oxygen, etc.
  • corrosion resistance e.g. against permeation of water vapor, oxygen, etc.
  • heat radiation reflective properties e.g. against permeation of water vapor, oxygen, etc.
  • corrosion resistance e.g. against permeation of water vapor, oxygen, etc.
  • heat radiation reflective properties e.g. against permeation of water vapor, oxygen
  • metallized polymer components include push buttons and covers for hi-fi equipment, cell phones and coffee machines, LED lamp housing, EMI shielding coating layer for electronic equipment, metallized housings for telecommunications devices (e.g. smart phones, smart watches, wearable devices), laptop computers, tablet computers, telescope parts, susceptor for cooking in microwave ovens (e.g. a microwave popcorn bag).
  • the surface-metallized polymer article for use in bathroom or kitchen fittings may be selected from a faucet, a shower head, a tubing, a pipe, a connector, an adaptor, a sink (e.g.
  • a bathtub cover a spout, a sink cover, a bathroom accessory, or a kitchen accessory.
  • metallized polymer components include diffusion barrier coatings in the food packaging (e.g. candy wrapper), antistatic bag, protective clothing (high-energy radiation shield, heat shield from fuel fires, radiation heat reflector, etc.), aluminized blanket to keep patients warm, children's toys, product labels, mailers, sports cards, greeting cards, solar control window films, stamping foils, etc.
  • the present disclosure also provides an apparatus that can be used to produce the surface- metallized polymer film.
  • the apparatus for manufacturing a surface-metallized polymer film may comprise: (a) a polymer film feeder device (e.g. a feeder roller) that provides (pays out) a continuous polymer film; (b) a graphene deposition chamber (e.g.
  • a graphene dispersion bath that accommodates a graphene dispersion comprising multiple graphene sheets and an optional conductive filler dispersed in a first liquid medium and an optional adhesive resin dissolved in the first liquid medium, wherein the graphene deposition chamber is operated to deposit the graphene sheets and optional conductive filler to a primary surface or two primary surfaces of the continuous polymer film for forming a graphene-coated polymer film;
  • a metallization chamber e.g.
  • the multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non- pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof.
  • the apparatus may further comprise a series of guiding rollers or rods that control the movement directions of the polymer film so that the polymer film may be brought in contact with the graphene dispersion (e.g. for dipping the polymer film into the graphene dispersion bath and then retreating the polymer film from this bath) for producing a graphene-coated polymer and the graphene-coated polymer film be brought in contact with the plating solution (e.g. for dipping the graphene-coated polymer film into the plating solution in the metal plating bath and then retreating the metal-plated graphene-coated polymer film from this plating bath) to obtain the desired surface-metallized polymer film.
  • the plating solution e.g. for dipping the graphene-coated polymer film into the plating solution in the metal plating bath and then retreating the metal-plated graphene-coated polymer film from this plating bath
  • the apparatus may further comprise a drying, heating, or curing provision in a working relation with the graphene deposition chamber (e.g. above the graphene dispersion bath) for partially or completely removing the first liquid medium from the graphene-coated polymer film and/or for polymerizing or curing the optional adhesive resin for producing the graphene-coated polymer film containing multiple graphene sheets that are bonded to one or both primary surfaces of the polymer film.
  • a drying, heating, or curing provision in a working relation with the graphene deposition chamber (e.g. above the graphene dispersion bath) for partially or completely removing the first liquid medium from the graphene-coated polymer film and/or for polymerizing or curing the optional adhesive resin for producing the graphene-coated polymer film containing multiple graphene sheets that are bonded to one or both primary surfaces of the polymer film.
  • the plating solution may contain a chemical plating solution, an electrochemical plating solution, or an electrophoretic solution.
  • the plating solution contains a chemical plating solution comprising a metal salt dissolved in water or an organic solvent.
  • the metal salt e.g. CuS0 4 or NiN0 3
  • contains a metal ion e.g. Cu +2 or Ni +2 ) to be deposited onto polymer surfaces.
  • the conductive filler is selected from metal nanowires, carbon fibers, carbon nanofibers, carbon nanotubes, carbon-coated fibers, conductive polymer fibers, nanofibers or nanowires of Sn0 2 , Zn0 2 , ln 2 0 3 , or indium-tin oxide (ITO), a conductive polymer not in a fiber form, or a combination thereof.
  • the metal nanowires are preferably selected from nanowires of silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), aluminum (Al), or a combination thereof.
  • the conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), polyheteroarylenvinylene (PArV), in which the heteroarylene group can be the thiophene, furan or pyrrole, poly-p-phenylene (PpP), polyphthalocyanine (PPhc) and the like, and their derivatives, and combinations thereof.
  • the chemical functional groups attached to graphene sheets are preferably those that make the graphene exhibit a negative Zeta potential in an intended dispersion medium (e.g. water, salt-containing water, an organic solvent, etc.).
  • an intended dispersion medium e.g. water, salt-containing water, an organic solvent, etc.
  • the chemical functional group is selected from alkyl or aryl silane, alkyl or aralkyl group, hydroxyl group, carboxyl group, amine group, sulfonate group (— S0 3 H), aldehydic group, quinoidal, fluorocarbon, or a combination thereof.
  • the functional group is selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde.
  • the functionalizing agent contains a functional group selected from the group consisting of S0 3 H, COOH, NH 2 , OH, R'CHOH, CHO, CN, COC1, halide, COSH, SH, COOR', SR', SiR' 3 , Si(-OR'-) y R' 3 -y, Si(-0- SiR' 2 — )OR', R", Li, AlR' 2 , Hg— X, TlZ 2 and Mg— X; wherein y is an integer equal to or less than 3, R' is hydrogen, alkyl, aryl, cycloalkyl, or aralkyl, cycloaryl, or poly(alkylether), R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or
  • the functional group may be selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylene-tetramine (TETA), tetraethylene-pentamine (TEPA), polyethylene polyamine, polyamine epoxy adduct, phenolic hardener, non-brominated curing agent, non-amine curatives, and combinations thereof.
  • the first layer contains an adhesive resin that chemically bonds the graphene sheets and the conductive filler to a primary surface of the polymer film.
  • the graphene sheets contain a non-pristine graphene material having a content of non-carbon elements from 0.01% to 20% by weight and the non-carbon elements include an element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron. These graphene sheets may be further chemically functionalized to exhibit a negative Zeta potential.
  • the polymer film may contain a plastic, a rubber, a thermoplastic elastomer, a polymer matrix composite, a rubber matrix composite, or a combination thereof.
  • the polymer film contains a thermoplastic, a thermoset resin, an interpenetrating network, a rubber, a thermoplastic elastomer, a natural polymer, or a combination thereof.
  • the polymer film contains a plastic selected from acrylonitrile- butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate, polyamide or nylon, polystyrene, high-impact polystyrene (HIPS), polyacrylate, polyethylene, polypropylene, polyacetal, polyester, polyether, polyether sulfone, poly ether ether ketone, poly sulfone, polyphenylene oxide (PPO), polyvinyl chloride (PVC), polyimide, polyamide imide, polyurethane, polyurea, or a combination thereof.
  • ABS acrylonitrile- butadiene-styrene copolymer
  • SAN styrene-acrylonitrile copolymer
  • HIPS high-impact polystyrene
  • PPO polyphenylene oxide
  • PVC polyvinyl chloride
  • polyimide polyamide imide
  • the plated metal is preferably selected from copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, an alloy thereof, or a combination thereof. There is no limitation on the type of metals that can be plated.
  • the graphene sheets may be further decorated with nanoscaled particles or coating (having a diameter or thickness from 0.5 nm to 100 nm) of a catalytic metal selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof, and wherein the catalytic metal is different in chemical composition than the plated metal.
  • a catalytic metal selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof, and wherein the catalytic metal is different in chemical composition than the plated metal.
  • the polymer film surface prior to being deposited with the layer of graphene sheets and a conductive filler, contains only small openings or pores ha ving a diameter or a depth ⁇ 0.1 pm.
  • the multiple graphene sheets and the conductive filler are bonded to the polymer film surface with an adhesive resin having an adhesive-to-graphene weight ratio from 1/5000 to 1/10, preferably from 1/1000 to 1/100.
  • the disclosure also provides a process for producing a surface-metallized polymer film.
  • the process comprises:
  • the graphene deposition chamber accommodates a graphene dispersion comprising multiple graphene sheets and an optional conductive filler dispersed in a first liquid medium and an optional adhesive resin dissolved in this first liquid medium; (b) Operating the graphene deposition chamber to deposit the graphene sheets and optional conductive filler to at least a primary surface of the polymer film for forming a graphene- coated polymer film;
  • the multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof.
  • One or both primary surfaces of a polymer films may be metallized in this process.
  • the plating solution may contain a chemical plating solution, an electrochemical plating solution, or an electrophoretic solution.
  • the process may further comprise operating a drying, heating, or curing means to partially or completely remove the first liquid medium from the graphene-coated polymer film and/or to polymerize or cure the optional adhesive resin for producing the graphene-coated polymer film containing the multiple graphene sheets that are bonded to the at least a primary surface or both primary surfaces of the polymer film.
  • the process further contains a step of chemically functionalizing the graphene sheets (pristine graphene, graphene oxide, reduced graphene oxide, fluorinated graphene, nitrogenated graphene, etc.) so that the graphene sheets exhibit a negative Zeta potential, preferably from -55 mV to -0.1 mV.
  • the graphene sheets pristine graphene, graphene oxide, reduced graphene oxide, fluorinated graphene, nitrogenated graphene, etc.
  • the process further comprises, prior to step (a), a step of subjecting the polymer film surface to a grinding treatment, an etching treatment, or a combination thereof.
  • step (a) includes a step of subjecting the polymer film surface to an etching treatment using an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof.
  • the process further comprises, prior to step (a), a step of subjecting the polymer fil surface to an etching treatment without using chromic acid or chromo ulfuric acid. More preferably, the process further comprises, prior to step (a), a step of subjecting the polymer film surface to an etching treatment using an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof under a mild etching condition wherein etching is conducted at a sufficiently low temperature for a sufficiently short period of time so as not to create micro- caverns having an average size greater than 0.1 pm.
  • an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof under a mild etching condition wherein etching is conducted at a sufficiently low temperature for a sufficiently short period of time so as not to create micro- caverns having an average size greater than 0.1 pm.
  • the graphene sheets may be further decorated with nanoscaled particles or coating of a catalytic metal, having a diameter or thickness from 0.5 nm to 100 nm, selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof.
  • a catalytic metal having a diameter or thickness from 0.5 nm to 100 nm, selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof.
  • step (a) and step (b) include immersing or dipping the polymer film in the dispersion and then removing the polymer film from the dispersion to effect deposition of graphene sheets and the conductive filler onto one or both primary surfaces of the surface-treated polymer film wherein the graphene sheets and the conductive filler (if present) are bonded to the surface to form a layer of bonded graphene sheets and conductive filler.
  • step (c) may contain immersing the polymer film in a metallizing bath.
  • step (c) includes a step of dipping the polymer film containing the layer of bonded graphene sheets/conductive filler into and then retreating from a chemical plating bath containing a metal salt dissolved in a liquid medium to effect metallization of the polymer film surface.
  • the graphene/conductive filler mixture dispersion further contains an adhesive resin having an adhesive-to-graphene weight ratio from 1/5000 to 1/10.
  • the graphene sheets may be further decorated with nanoscaled particles or coating of a catalytic metal, having a diameter or thickness from 0.5 nm to 100 nm, selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof.
  • the liquid medium may contain permanganic acid, phosphoric acid, nitric acid, or a combination thereof that is dissolved in said liquid medium.
  • the liquid medium contains an acid, an oxidizer, a metal salt, or a combination thereof dissolved therein.
  • Step (c) may contain immersing the polymer film in a metallizing bath to accomplish chemical plating or electroless plating.
  • the high electrical conductivity of deposited graphene sheets and conductive filler enables plating of metal layer(s) on graphene/conductive filler- coated polymer film surfaces.
  • the disclosure also provides a graphene/conductive filler mixture dispersion comprising multiple graphene sheets and an optional conductive filler dispersed in a liquid medium wherein the multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non- pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof, and wherein the dispersion further contains one or multiple species selected from (i) an adhesive resin dissolved or dispersed in the liquid medium, wherein an adhesive-to-graphene weight ratio is from 1/5000 to 1/10; (ii) an etchant selected from an
  • the chemically functionalized graphene is attached to a graphene sheet to make the graphene exhibit a negative Zeta potential in a desired liquid medium.
  • the conductive filler may be selected from metal nanowires, carbon fibers, carbon nanofibers, carbon nanotubes, carbon-coated fibers, conductive polymer fibers, nanofibers or nanowires of Sn0 2 , Zn0 2 , ln 2 0 3 , or indium-tin oxide (ITO), a conductive polymer not in a fiber form, or a combination thereof.
  • the metal nanowires may be selected from nanowires of silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), aluminum (Al), or a combination thereof.
  • the conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), poly
  • heteroarylenvinylene in which the heteroarylene group can be the thiophene, furan or pyrrole, poly-p-phenylene (PpP), polyphthalocyanine (PPhc) and the like, and their derivatives, and combinations thereof.
  • nano scaled particles or coating of a catalytic metal may be deposited or decorated on surfaces of said multiple graphene sheets.
  • the acid may be selected from permanganic acid, phosphoric acid, nitric acid, chromic acid, chromosulfuric acid, carboxylic acid, acetic acid, and ascorbic acid, or a combination thereof.
  • these functional groups are already discussed in the earlier part of this section.
  • these functional groups are attached to graphene sheets that make the graphene exhibit a negative Zeta potential, typically from -55 mV to -0.1 mV, in a desired dispersion medium.
  • the disclosure also provides a graphene dispersion for use in metallization of a polymer surface (e.g. polymer film primary surface).
  • the dispersion comprises multiple graphene sheets and an optional conductive filler dispersed in a liquid medium wherein the multiple graphene sheets contain single-layer or few-layer graphene sheets.
  • the graphene sheets in this liquid medium preferably contain a functional group attached to the graphene sheets to make the graphene sheets exhibit a negative Zeta potential from -55 mV to - 0.1 mV in the liquid medium.
  • the graphene sheets contain a carboxylic, acyl, aryl, aralkyl, halogen, alkyl, amino, halogen, or thiol group.
  • the graphene dispersion may further contain one or multiple species selected from (i) an adhesive resin dissolved or dispersed in said liquid medium, wherein an adhesive-to-graphene weight ratio is from 1/5000 to 1/10; (ii) an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof; (iii) nanoscaled particles or coating of a catalytic metal, having a diameter or thickness from 0.5 nm to 100 nm, selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof; or (iv) a combination thereof.
  • FIG. 1 A flow chart showing the most commonly used process for producing oxidized graphene sheets that entails chemical oxidation/intercalation, rinsing, and high-temperature exfoliation procedures.
  • FIG. 2 Schematic of a graphene-mediated metallized polymer film.
  • FIG. 3 Schematic of a system for graphene-mediated metallization of a continuous polymer film.
  • FIG. 4 Schematic of an alternative system for graphene-mediated metallization of a continuous polymer film.
  • graphene sheets means a material comprising one or more planar sheets of bonded carbon atoms that are densely packed in a hexagonal crystal lattice in which carbon atoms are bonded together through strong in-plane covalent bonds, and further containing an intact ring structure throughout a majority of the interior. Preferably at least 80% of the interior aromatic bonds are intact. In the c-axis (thickness) direction, these graphene planes may be weakly bonded together through van der Waals forces.
  • Graphene sheets may contain non-carbon atoms at their edges or surface, for example OH and COOH functionalities.
  • the term graphene sheets includes pristine graphene, graphene oxide, reduced graphene oxide, halogenated graphene including graphene fluoride and graphene chloride, nitrogenated graphene,
  • non-carbon elements comprise 0 to 25 weight % of graphene sheets.
  • Graphene oxide may comprise up to 53% oxygen by weight.
  • the term“doped graphene” encompasses graphene having less than 10% of a non-carbon element.
  • This non-carbon element can include hydrogen, oxygen, nitrogen, magnesium, iron, sulfur, fluorine, bromine, iodine, boron, phosphorus, sodium, and combinations thereof.
  • Graphene sheets may comprise single-layer graphene or few-layer graphene, wherein the few-layer graphene is defined as a graphene platelet formed of less than 10 graphene planes.
  • Graphene sheets may also comprise graphene nanoribbons.“Pristine graphene” encompasses graphene sheets having essentially zero % of non-carbon elements. “Nanographene platelet” (NGP) refers to a graphene sheet having a thickness from less than 0.34 nm (single layer) to 100 nm (multi-layer).
  • substantially and its variations are defined as being largely but not necessarily wholly what is specified as understood by one of ordinary skill in the art, and in one non-limiting embodiment substantially refers to ranges within 10%, within 5%, within 1%, or within 0.5% of a referenced range.
  • the present disclosure provides a surface-metallized polymer film comprising: (a) a polymer film having a thickness from 10 nm to 5 mm and two primary surfaces; (b) a graphene layer having a thickness from 0.34 nm to 50 pm (preferably from 1 nm to 10 pm, and most preferably from 10 nm to 1 pm) and comprising multiple graphene sheets and an optional conductive filler coated on or bonded to at least one of the two primary surfaces with or without implementing an adhesive resin between graphene sheets and the primary surface of the polymer film; and (c) a metal layer comprising a plated metal deposited on the graphene layer; wherein the multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non- pristine graphene is selected from graphene oxide, reduced graphene oxide, graph
  • the multiple graphene sheets and the conductive filler are bonded to the polymer film surface with or without an adhesive resin.
  • the first layer (the graphene layer) has a thickness typically from 0.34 nm to 30 pm (preferably from 1 nm to 1 pm and further preferably from 1 nm to 100 nm).
  • the second layer (covering metal layer) preferably has a thickness from 0.5 nm to 1.0 mm, more preferably from 1 nm to 10 pm, and most preferably from 10 nm to 1 pm.
  • This metal-plated polymer film can be easily and readily produced using surprisingly simple and effective methods that are also herein described. Functionalized graphene sheets are surprisingly capable of bonding to many types of polymer component surfaces without using an adhesive resin.
  • the surface-metallized polymer film is used in a wide variety of components; e.g. a vehicle component, an electronic appliance, an electronic device, a food packaging film or bag, a protective clothing, an antistatic film or bag, a susceptor in microwave cooking, a blanket, an anti-reflection accessary, a children's toy, a product label, a mailer, a sports card, a greeting card, a solar control window film, or a stamping foil.
  • the vehicle component may be selected from a radiator grill, a mirror cap, a door handle, or a trim.
  • the electronic appliance or electronic device may contain a push button or cover for hi-fi equipment, a cell phone, a coffee machine, a LED lamp housing, a wearable device, an electronic watch, a laptop computer, a tablet computer, or an EMI shielding coating layer for electronic equipment.
  • the apparatus may comprise a film feeder roller 32 that feeds a polymer film 33 (with or without a supporting substrate) into a graphene deposition chamber (e.g. a graphene dispersion bath 12) that accommodates a graphene dispersion 14 comprising multiple graphene sheets and an optional conductive filler dispersed in a first liquid medium and an optional adhesive resin dissolved in the first liquid medium.
  • a graphene deposition chamber e.g. a graphene dispersion bath 12
  • a graphene dispersion 14 comprising multiple graphene sheets and an optional conductive filler dispersed in a first liquid medium and an optional adhesive resin dissolved in the first liquid medium.
  • Guiding rollers or rods e.g. 34, 38, 36 are used to guide the movement of the polymer film 33.
  • the polymer film is moved to immerse into the graphene dispersion 14 contained in the graphene deposition bath 12.
  • the graphene deposition bath 12 is operated to deposit the graphene sheets and optional conductive filler to at least a primary surface of a polymer film for forming a graphene-coated polymer film (e.g. 35).
  • the graphene-coated, graphene-deposited or graphene-covered polymer film is then moved to enter a heating/drying/curing zone (e.g. underneath a heating/drying/curing device 41), allowing the graphene sheets and the optional conductive filler to get coated on or bonded to at least a primary surface of the polymer film, thereby forming a graphene-coated polymer film 37.
  • a heating/drying/curing zone e.g. underneath a heating/drying/curing device 41
  • the graphene-coated polymer film 37 is guided to move into a metallization chamber (e.g. a metal plating bath 22), disposed nearby the graphene dispersion bath 12, which accommodates a plating solution 24 for plating a layer of a desired metal on the at least one primary surface of a graphene-coated polymer film to obtain the surface-metallized polymer film 39.
  • the metallized polymer film is then wound on a winding roller 48 (take-up roller). It may be noted that both primary surfaces of a polymer film would be metallized if both surfaces of the polymer film are not covered by a sheet of paper or plastic. Only one primary surface is metallized if the other primary surface is covered, preventing the graphene solution from contacting this surface.
  • the graphene deposition bath 12 has an inlet 16 through which fresh graphene dispersion may be pumped into the graphene deposition chamber and an outlet 18 through which spent graphene dispersion may be pumped out, respectively.
  • the metallization chamber 22 has an inlet 26 through which fresh plating solution may be pumped into the metallization chamber and an outlet 28 through which spent plating solution may be pumped out, respectively.
  • the graphene dispersion bath and the metallization chamber provides for partially or completely removing the first liquid medium from the at least a graphene-coated polymer film and/or for polymerizing or curing the optional adhesive resin for producing the at least a graphene-coated polymer film containing multiple graphene sheets that are bonded to a primary surface of the polymer film.
  • the plating solution 24 may contain a chemical plating solution, an electrochemical plating solution, or an electrophoretic solution.
  • the plating solution contains a chemical plating solution comprising a metal salt dissolved in water or an organic solvent (e.g. CuS0 4 or N1NO3 dissolved in water for Cu plating or Ni plating).
  • a metal salt dissolved in water or an organic solvent (e.g. CuS0 4 or N1NO3 dissolved in water for Cu plating or Ni plating).
  • the various graphene sheets bonded on a polymer component surface are surprisingly capable of attracting metal ions to the graphene-covered or graphene-coated polymer component surface.
  • the adhesion of metal on this surface is surprisingly strong, scratch-resistant, and hard.
  • the deposited metal layer provides the desired gloss and metal appearance on the polymer component surface.
  • the apparatus may comprise a film feeder roller 32 that feeds a polymer film 33 (with or without a supporting substrate) into a graphene deposition zone, where a graphene dispersion dispensing device 50 dispenses and deposits graphene sheets and an optional conductive filler (e.g. CNT, carbon nanofibers, etc.) onto one or both primary surfaces of the polymer film.
  • the graphene dispersion contains multiple graphene sheets and an optional conducive filler dispersed in a first liquid medium, which is an adhesive monomer/oligomer in a liquid form or an adhesive resin
  • a dispensing device e.g. a liquid sprayer, coating device, painting device, casting device or printing device
  • the graphene-coated, graphene-deposited or graphene-covered polymer film is then moved to enter a heating/drying/curing zone (e.g.
  • the graphene-coated polymer film 37 is guided to move into a metallization chamber (e.g. a metal plating bath 22), which accommodates a plating solution 24 for plating a layer of a desired metal on the at least one primary surface of a graphene-coated polymer film to obtain the surface-metallized polymer film 39.
  • the metallized polymer film is then wound on a winding roller 48 (take-up roller). It may be noted that both primary surfaces of a polymer film would be metallized if both surfaces of the polymer film are not covered by a sheet of paper or plastic. Only one primary surface is metallized if the other primary surface is covered, preventing the graphene solution from contacting this surface.
  • the metallization chamber 22 has an inlet 26 through which fresh plating solution may be pumped into the metallization chamber and an outlet 28 through which spent plating solution may be pumped out, respectively.
  • the apparatus may further comprise a drying, heating, or curing provision 41 in a working relation with the graphene deposition zone (e.g. above and between the graphene deposition zone and the metallization chamber) for partially or completely removing the first liquid medium from the at least a graphene-coated polymer film and/or for polymerizing or curing the optional adhesive resin for producing the at least a graphene-coated polymer film containing multiple graphene sheets that are bonded to a primary surface of the polymer film.
  • a drying, heating, or curing provision 41 in a working relation with the graphene deposition zone (e.g. above and between the graphene deposition zone and the metallization chamber) for partially or completely removing the first liquid medium from the at least a graphene-coated polymer film and/or for polymerizing or curing the optional adhesive resin for producing the at least a graphene-coated polymer film containing multiple graphene sheets that are bonded to a primary surface of the polymer film.
  • the plating solution 24 may contain a chemical plating solution, an electrochemical plating solution, or an electrophoretic solution.
  • the plating solution contains a chemical plating solution comprising a metal salt dissolved in water or an organic solvent (e.g. CuS0 4 or N1NO3 dissolved in water for Cu plating or Ni plating).
  • a metal salt dissolved in water or an organic solvent (e.g. CuS0 4 or N1NO3 dissolved in water for Cu plating or Ni plating).
  • the various graphene sheets bonded on a polymer component surface are surprisingly capable of attracting metal ions to the graphene-covered or graphene-coated polymer component surface.
  • the adhesion of metal on this surface is surprisingly strong, scratch-resistant, and hard.
  • the deposited metal layer provides the desired gloss and metal appearance on the polymer component surface.
  • the operation of the aforementioned procedures may be conducted in a continuous or intermittent manner and can be fully automated.
  • the conductive filler is selected from metal nanowires, carbon fibers, carbon nanofibers, carbon nanotubes, carbon-coated fibers, conductive polymer fibers, nanofibers or nanowires of Sn0 2 , Zn0 2 , ln 2 0 3 , or indium-tin oxide (ITO), a conductive polymer not in a fiber form, or a combination thereof.
  • the metal nanowires are preferably selected from nanowires of silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), aluminum (Al), or a combination thereof.
  • the conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothionaphthene (PITN), polyheteroarylenvinylene (PArV), in which the heteroarylene group can be the thiophene, furan or pyrrole, poly-p-phenylene (PpP), polyphthalocyanine (PPhc) and the like, and their derivatives, and combinations thereof.
  • the chemically functionalized graphene sheets are preferably those exhibiting a negative Zeta potential in a given dispersion, typically in the range from -55 mV to -0.1 mV. These functionalized graphene sheets typically have a functional group that is attached to these sheets for imparting negative Zeta potential thereto.
  • Zeta potential is the potential difference between the dispersion medium and the stationary layer of fluid attached to the dispersed particles (e.g. graphene sheets) dispersed in this dispersion medium (e.g. water, organic solvent, electrolyte etc.).
  • Several commercially available instruments e.g. Zetasizer Nano from Malvern Panalytical and SZ-100 from Horiba Scientific can be used to measure the Zeta potential of different types of graphene sheets in different dispersion mediums.
  • a given type of graphene e.g. graphene oxide or reduced graphene oxide
  • the Zeta potential values provided are for the graphene sheets dispersed in an aqueous solution having a pH vale of 5.0-9.0 (mostly 7.0).
  • the chemically functionalized graphene sheets contain a chemical functional group selected from alkyl or aryl silane, alkyl or aralkyl group, hydroxyl group, carboxyl group, amine group, sulfonate group (— S0 3 H), aldehydic group, quinoidal, fluorocarbon, or a combination thereof.
  • the functional group is selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde.
  • the functionalizing agent contains a functional group selected from the group consisting of S0 3 H, COOH, NH 2 , OH, R'CHOH, CHO, CN, COC1, halide, COSH, SH, COOR', SR', SiR' 3 , Si(-OR'-) y R' 3 -y, Si(-0- SiR' 2 — )OR', R", Li, AlR' 2 , Hg— X, TlZ 2 and Mg— X; wherein y is an integer equal to or less than 3, R' is hydrogen, alkyl, aryl, cycloalkyl, or aralkyl, cycloaryl, or poly(alkylether), R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or
  • the functional group may be selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylene-tetramine (TETA), tetraethylene-pentamine (TEPA), polyethylene polyamine, polyamine epoxy adduct, phenolic hardener, non-brominated curing agent, non-amine curatives, and combinations thereof.
  • the present disclosure also provides a method of metallizing a polymer surface (e.g. surface of an electrically non-conductive plastic).
  • a polymer surface e.g. surface of an electrically non-conductive plastic.
  • the plastic surface of a plastic article or the plastic surfaces of several plastic articles are metallized.
  • polymer galvanizing also called polymer galvanizing or polymer metallization
  • metals also called polymer galvanizing or polymer metallization
  • polymer galvanizing methods laminates which combine advantages of polymers and metals are produced.
  • the use of polymer components can achieve a distinct reduction in weight in comparison to metal parts.
  • Galvanization of polymer moldings is often conducted for decorative purposes, for EMI shielding, or for surface property modifications.
  • the parts are usually secured in frames and contacted with a plurality of different treatment fluids in a particular process sequence.
  • the plastics are typically pretreated to remove impurities, such as greases, from the surface.
  • etching treatments are used to roughen the surface to ensure adequate adhesion of the subsequent metal layers to the polymer surface.
  • the formation of a homogeneous structure in the form of recesses (e.g. surface openings or micro-caverns) on the plastic surface is particularly crucial.
  • the roughened surface is treated with activators to form a catalytic surface for a subsequent chemical metallization or electroless plating.
  • either the ionogenic activators or colloidal systems are used.
  • plastic surfaces for activation with ionogenic systems are first treated with tin(II) ions, giving rise to firmly adhering gels of tin oxide hydrate after the treatment and rinsing with water.
  • palladium salt solution palladium nuclei are formed on the surface through redox reaction with the tin(II) species. These palladium nuclei are catalytic for the chemical metallization.
  • colloidal palladium solutions are used, formed by reaction of palladium chloride with tin(II) chloride in the presence of excess hydrochloric acid.
  • the plastic parts are typically first chemically metallized using a metastable solution of a metallization bath.
  • a metallization bath generally comprise the metal to be deposited in the form of salts in an aqueous solution and a reducing agent for the metal salt.
  • the chemical metallization baths come into contact with the metal nuclei on the plastic surface (e.g. the palladium seeds), metal is formed by reduction, which is deposited on the surface as a firmly adhering layer.
  • the chemical metallization step is commonly used to deposit copper, nickel or a nickel alloy with phosphorus and/or boron.
  • the chemically metallized polymer surface may then be electrolytically deposited further with metal layers.
  • an electrolytic deposition of copper layers or further nickel layers is conducted before the desired decorative chromium layer is applied electrochemically.
  • the most commonly used etchant is the chromium- sulfuric acid or chromo-sulfuric acid (chromium trioxide in sulfuric acid), especially for ABS (acrylonitrile-butadiene-styrene copolymer) or polycarbonate.
  • Chromium-sulfuric acid is very toxic and requires special precautions in the etching procedure, after treatment, and disposal. Because of chemical processes in the etching treatment (e.g. the reduction of the chromium compound used), the chromium-sulfuric acid etchant is used up and is generally not reusable.
  • a critical process step in plastic galvanizing is the creation of micro-cavems to enable the adhesion of the metal on the plastic surface.
  • These micro-caverns serve, in the later metallization steps, as the starting point for the growth of the metal nuclei.
  • These micro- caverns in general, have a size on the order of 0.1 to 10 pm.
  • these micro- cavems show a depth (i.e. an extent from the plastic surface toward the interior) in the range from 0.1 to 10 pm.
  • surface micro-cavems can be stress
  • the surface first is activated with colloidal palladium or ionogene palladium. This activation, in the case of the colloidal process, is followed by a removal of a protective tin colloid or, in the case of the ionogene process, a reduction to the elemental palladium. Subsequently, copper or nickel is chemically deposited on the plastic surface as a conducting layer. Following this, galvanizing or metallizing takes place. In practice, this direct metallizing of the plastic surface works only for certain plastics.
  • the method comprises: (a) optionally treating a surface of a polymer component to prepare a surface-treated polymer component (this procedure being optional since the graphene dispersion per se is capable of pre-treating the polymer surface); (b) providing a graphene dispersion (also herein referred to as graphene/conductive filler mixture dispersion) comprising multiple graphene sheets (functionalized or un-functionalized) and a conductive filler (in the form of nanofibers, nanoparticles, nanowires, etc.) dispersed in a liquid medium, bringing the surface-treated or un-treated polymer component into contact with the graphene dispersion, and enabling deposition of the graphene sheets and the conductive filler onto a surface of the surface-treated polymer component wherein the graphene sheets and the conductive filler are bonded to the surface to form a layer of bonded graphene sheets/conductive filler that covers (partially or fully) a polymer component surface; and (c) chemical
  • the polymer component may be selected from polyethylene, polypropylene, polybutylene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene- styrene (ABS), polyester, polyvinyl alcohol, poly vinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene oxide (PPO), poly methyl methacrylate (PMMA), a copolymer thereof, a polymer blend thereof, or a combination thereof.
  • ABS acrylonitrile-butadiene- styrene
  • polyester polyvinyl alcohol, poly vinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene oxide (PPO), poly methyl methacrylate (PMMA), a copolymer thereof, a polymer blend thereof, or a combination thereof.
  • PVDF poly vinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PPO polypheny
  • the polymer may also be selected from phenolic resin, poly furfuryl alcohol, polyacrylonitrile, polyimide, polyamide, polyoxadiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polybenzothiazole, polybenzobisthiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzobisimidazole, a copolymer thereof, a polymer blend thereof, or a combination thereof.
  • step (a) is omitted from the process since the liquid medium in the graphene dispersion is generally capable of removing grease and other undesirable species from polymer component surfaces.
  • Some liquid mediums in graphene dispersions can further provide etching effects to create small surface recesses having a depth ⁇ 0.1 pm (a mild etching condition). In these situations, the entire process requires only three simple steps.
  • step (a) can include a step of subjecting the polymer component surface to a grinding treatment, an etching treatment, or a combination thereof.
  • step (a) includes a step of subjecting the polymer component surface to an etching treatment using an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof.
  • step (a) includes a step of subjecting the polymer component surface to an etching treatment without using chromic acid or chromo sulfuric acid.
  • step (a) includes a step of subjecting the polymer component surface to an etching treatment using an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof under a mild etching condition wherein etching is conducted at a sufficiently low temperature for a sufficiently short period of time so as not to create micro - caverns having an average size greater than 0.1 pm.
  • an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof under a mild etching condition wherein etching is conducted at a sufficiently low temperature for a sufficiently short period of time so as not to create micro - caverns having an average size greater than 0.1 pm.
  • the mild etching referred to in the disclosure means that the“etching”, or the treatment of the plastic surface with a etching solution occurs at low temperatures and/or within a shorter time period at a low concentration of the etching solution. Mild etching conditions can be realized when one of the preceding three conditions is met.
  • the low temperature referred to in the disclosure means a maximum temperature of 40°C, preferably ⁇ 30°C, and most preferably from l5°C to 25 °C. With the low temperatures mentioned above, the pre-treatment with the etching solution takes place over a time period of 3 to 15 minutes, preferably 5 to 15 minutes and even more preferably 5 to 10 minutes. The treatment period is the shorter the higher the temperature.
  • the etching treatment takes place at temperatures of 40°C to 95°C, preferably 50°C to 70°C, for a treatment period of 15 seconds to 5 minutes, preferably 0.5 to 3 minutes.
  • the process temperature and/or process time is selected in accordance with the type of the etching solution employed.
  • Mild etching also means that, contrary to the prior art processes referred to above, roughening of the polymer surface, or the creation of micro-caverns in the polymer surface does not occur.
  • the micro-caverns created with etching according to the prior art process normally have a diameter or depth in the size range of 0.1 to 10 pm.
  • the etching conditions are adjusted so that only small openings or pores are created in the polymer surface which have a diameter and especially a depth of ⁇ 0.1 pm, with ⁇ 0.05 pm preferred.
  • depth means the extent of the openings/gateways from the polymer surface into the polymer interior.
  • the liquid medium in the graphene dispersion normally can create openings or pores having a size ⁇ 0.1 pm. Contrary to what the prior art teachings suggest, we have surprisingly observed that the presently disclosed graphene-mediated metallization approach does not require the creation of micro-caverns greater than 0.1 pm in size. The approach works even on highly smooth surface.
  • the etching treatment can be realized with a etching solution and/or by a plasma treatment or by plasma etching, ion bombardment, etc.
  • an etching solution used for etching contains at least one oxidizer.
  • Mild etching within the scope of the disclosure also means that an oxidizer is used in a low
  • etching is by an acid etching solution which contains at least one oxidizer.
  • the oxidizer and/or the acid or basic solution may be added into the graphene dispersion and, as such, step (a) and step (b) are essentially combined into one single step.
  • an aqueous etching solution which contains permanganate and phosphoric acid (H 3 PO 4 ) and/or sulfuric acid.
  • Potassium permanganate may be used as the permanganate.
  • an acid etching solution which only contains phosphoric acid or principally phosphoric acid and only a small amount of sulfuric acid.
  • etching treatment is by a basic aqueous solution, containing permanganate.
  • potassium permanganate is preferably used.
  • the basic aqueous solution may contain lye.
  • the type of etching solution used depends on the type of polymer to be treated.
  • the preferred concentration of the oxidizer in the etching solution is 0.05 to 0.6 mol/l.
  • the etching solution contains 0.05 to 0.6 mol/l permanganate or persulfate.
  • the etching solution may contain 0.1 to 0.5 mol/l periodate or hydrogen peroxide.
  • the preferred permanganate proportion is 1 g/l up to the solubility limit of the permanganate, preferably potassium permanganate.
  • the permanganate solution preferably contains 2 to 15 g/l permanganate, more preferably 2 to 15 g/l potassium permanganate.
  • the permanganate solution may contain a wetting agent.
  • Mild etching can also be achieved by the use of a dilute aqueous persulfate solution or periodite solution or a dilute aqueous peroxide solution (used as a separate etching solution or as part of the graphene dispersion).
  • the mild etching treatment with an etching solution is carried out while agitating the solution.
  • the plastic surface is rinsed, for example, for 1 to 3 minutes in water.
  • the treatment with the metal salt solution is conducted at a temperature ⁇ 30°C, preferably between l5°C and 25 °C (including room temperature). In practice, the treatment with the metal salt solution is performed without agitation.
  • the preferred treatment time is 30 seconds to 15 minutes, preferably 3 to 12 minutes.
  • a metal salt solution is used which has a pH value of between 7.5 and 12.5, preferably adjusted to between 8 and 12.
  • a metal salt solution is used which contains ammonia and/or at least one amine.
  • the above-mentioned pH value adjustment can be effected with the help of ammonia, and an alkaline metal salt solution is preferably used.
  • a metal salt solution which contains one or more amines.
  • the metal salt solution may contain monoethanolamine and/or
  • Treatment with the metal salt solution means preferably the immersion of the polymer component surface into the metal salt solution.
  • step (b) includes immersing or dipping the surface-treated or un treated polymer component in the graphene dispersion and then removing the polymer component from the graphene dispersion to effect deposition of graphene sheets and the conductive filler onto a surface of the surface-treated polymer component wherein the graphene sheets and the conductive fillers are bonded to the surface to form a layer of bonded graphene sheets/conductive filler.
  • step (b) includes immersing or dipping the surface-treated or un treated polymer component in the graphene dispersion and then removing the polymer component from the graphene dispersion to effect deposition of graphene sheets and the conductive filler onto a surface of the surface-treated polymer component wherein the graphene sheets and the conductive fillers are bonded to the surface to form a layer of bonded graphene sheets/conductive filler.
  • the adhesive resin layer may be formed of an adhesive resin composition including an adhesive resin as a main ingredient.
  • the adhesive resin composition may include a curing agent and a coupling agent along with the adhesive resin. Examples of the
  • adhesive resin may include an ester resin, a urethane resin, a urethane ester resin, an
  • the curing agent may be present in an amount of 1 to 30 parts by weight based on 100 parts by weight of the adhesive resin.
  • the coupling agent may include epoxy silane compounds.
  • Curing of this adhesive layer may be conducted via heat, UV, or ionizing radiation. This can involve heating the layers coated with the heat-curable composition to a temperature of at least 70°C, preferably of 90°C to l50°C, for at least 1 minute (typically up to 2 hours and more typically from 2 minutes to 30 minutes), so as to form a hard coating layer.
  • the polymer component surfaces may be brought to be in contact with the graphene or CNT dispersion using dipping, coating (e.g. doctor-blade coating, bar coating, slot-die coating, comma coating, reversed-roll coating, etc.), roll-to-roll process, inkjet printing, screen printing, micro-contact, gravure coating, spray coating, ultrasonic spray coating, electrostatic
  • the thickness of the hard coat or adhesive layer is generally about 1 nm to 10 pm, preferably 10 nm to 2 pm.
  • the polyfunctional epoxy monomer may be selected preferably from diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether (e.g. pentaerythritol tetraglycidyl ether), or a combination thereof.
  • functional epoxy monomer can be selected from the group consisting of trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, trisphenol triglycidyl ether, tetraphenylol ethane triglycidyl ether, tetraglycidyl ether of tetraphenylol ethane, p-aminophenol triglycidyl ether, 1,2,6- hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxylate triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerine trig
  • polypropylene glycol diglycidyl ether dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-Epoxycyclohexane) methyl 3,4-epoxycylohexylcarboxylate and mixtures.
  • the heat-curable compositions of the present disclosure advantageously further contain small amounts, preferably from 0.05 to 0.20 % by weight, of at least one surface active compound.
  • the surface active agent is important for good wetting of the substrate resulting in satisfactory final hard-coating.
  • the UV radiation curable resins and lacquers usable for the adhesive layer useful in this disclosure are those derived from photo polymerizable monomers and oligomers, such as acrylate and methacrylate oligomers (the term“(meth) acrylate” used herein refers to acrylate and methacrylate), of polyfunctional compounds, such as polyhydric alcohols and their derivatives having (meth)acrylate functional groups such as ethoxylated trimethylolpropane
  • tri(meth)acrylate tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, l,6-hexanediol di(meth)acrylate, or neopentyl glycol di(meth)acrylate and mixtures thereof, and acrylate and methacrylate oligomers derived from low-molecular weight polyester resin, polyether resin, epoxy resin, polyurethane resin, alkyd resin, spiroacetal resin, epoxy acrylates, polybutadiene resin, and polythiol-polyene resin.
  • the UV polymerizable monomers and oligomers are coated (e.g. after retreating from dipping) and dried, and subsequently exposed to UV radiation to form an optically clear cross- linked abrasion resistant layer.
  • the preferred UV cure dosage is between 50 and 1000 mJ/cm .
  • UV-curable resins are typically ionizing radiation-curable as well.
  • the ionizing radiation- curable resins may contain a relatively large amount of a reactive diluent.
  • Reactive diluents usable herein include monofunctional monomers, such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, vinyltoluene, and N-vinylpyrrolidone, and polyfunctional monomers, for example, trimethylolpropane tri(meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, l,6-hexanediol di(meth)acrylate, or neopen
  • step (c) may contain immersing the graphene-bonded polymer component in a metallizing bath.
  • the high electrical conductivity of deposited graphene sheets readily enables electro-plating of metal layer(s) on graphene/conductive filler-coated polymer component surfaces.
  • the final metallization step may be accomplished by using a chemical plating method without using an expensive noble metal solution.
  • This step can include dipping (immersing) a graphene/conductive filler-coated polymer component in a chemical plating bath which contains a metal salt (salt of an intended metal, such as Cu, Ni, or Co) dissolved in a liquid medium (e.g. CuS0 4 in water or N1NO 3 in water).
  • a metal salt salt of an intended metal, such as Cu, Ni, or Co
  • a liquid medium e.g. CuS0 4 in water or N1NO 3 in water.
  • a copper metal plating bath may comprise a copper salt (or Ni salt) and an additive consumption-inhibiting compound.
  • the additive consumption-inhibiting compound may comprise methyl sulfoxide, methyl sulfone, tetramethylene sulfoxide, thioglycolic acid, 2 (5H) thiophenone, l,4-dithiane, trans-l,2-dithiane, tetrahydrothiophene-3- one, 3-thiophenemethanol, l,3,5-trithiane, 3-thiopheneacetic acid, thiotetronic acid, crown thioethers, tetrapyrids, dipropyltrisulfide, bis(3 -triethoxy silyl propyltetrasulfide, dimethyl tetrasulfide, methyl methanethiosulfate, (2-sulfonatoethyl) methane, p-tolyld
  • Carbon is known to have five unique crystalline structures, including diamond, fullerene (0-D nanographitic material), carbon nanotube or carbon nanofiber (l-D nanographitic material), graphene (2-D nanographitic material), and graphite (3-D graphitic material).
  • the carbon nanotube (CNT) refers to a tubular structure grown with a single wall or multi-wall.
  • Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have a diameter on the order of a few nanometers to a few hundred nanometers.
  • Their longitudinal, hollow structures impart unique mechanical, electrical and chemical properties to the material.
  • the CNT or CNF is a one dimensional nanocarbon or l-D nanographite material.
  • a single-layer graphene sheet is composed of carbon atoms occupying a two-dimensional hexagonal lattice.
  • Multi-layer graphene is a platelet composed of more than one graphene plane.
  • Individual single-layer graphene sheets and multi-layer graphene platelets are herein collectively called nanographene platelets (NGPs) or graphene materials.
  • NGPs include pristine graphene (essentially 99% of carbon atoms), slightly oxidized graphene ( ⁇ 5% by weight of oxygen), graphene oxide (> 5% by weight of oxygen), slightly fluorinated graphene ( ⁇ 5% by weight of fluorine), graphene fluoride ((> 5% by weight of fluorine), other halogenated graphene, and chemically functionalized graphene.
  • NGPs have been found to have a range of unusual physical, chemical, and mechanical properties. For instance, graphene was found to exhibit the highest intrinsic strength and highest thermal conductivity of all existing materials. Although practical electronic device applications for graphene (e.g., replacing Si as a backbone in a transistor) are not envisioned to occur within the next 5-10 years, its application as a nanofiller in a composite material and an electrode material in energy storage devices is imminent. The availability of processable graphene sheets in large quantities is essential to the success in exploiting composite, energy, and other applications for graphene.
  • NGPs and NGP nanocomposites were recently reviewed by us [Bor Z. Jang and A Zhamu,“Processing of Nano Graphene Platelets (NGPs) and NGP Nanocomposites: A Review,” J. Materials Sci. 43 (2008) 5092-5101].
  • FIG. 1 A highly useful approach (FIG. 1) entails treating natural graphite powder with an intercalant and an oxidant (e.g., concentrated sulfuric acid and nitric acid, respectively) to obtain a graphite intercalation compound (GIC) or, actually, graphite oxide (GO).
  • an intercalant e.g., concentrated sulfuric acid and nitric acid, respectively
  • GAC graphite intercalation compound
  • GO graphite oxide
  • the GIC or GO is exposed to a high temperature (typically 800°C-l,050°C) for a short period of time (typically 15 to 60 seconds) to exfoliate or expand the GIC or GO for the formation of exfoliated or further expanded graphite, which is typically in the form of a“graphite worm” composed of graphite flakes that are still
  • approach 1 basically entails three distinct procedures: first expansion (oxidation or intercalation), further expansion (or“exfoliation”), and separation.
  • first expansion oxidation or intercalation
  • further expansion or“exfoliation”
  • separation In the solution-based separation approach, the expanded or exfoliated GO powder is dispersed in water or aqueous alcohol solution, which is subjected to ultrasonication.
  • ultrasonification is used after intercalation and oxidation of graphite (i.e., after first expansion) and typically after thermal shock exposure of the resulting GIC or GO (after second expansion).
  • the GO powder dispersed in water is subjected to an ion exchange or lengthy purification procedure in such a manner that the repulsive forces between ions residing in the inter-planar spaces overcome the inter-graphene van der Waals forces, resulting in graphene layer separations.
  • the starting material for the preparation of graphene sheets or NGPs is a graphitic material that may be selected from the group consisting of natural graphite, artificial graphite, graphite oxide, graphite fluoride, graphite fiber, carbon fiber, carbon nanofiber, carbon nanotube, mesophase carbon microbead (MCMB) or carbonaceous microsphere (CMS), soft carbon, hard carbon, and combinations thereof.
  • MCMB mesophase carbon microbead
  • CMS carbonaceous microsphere
  • Graphite oxide may be prepared by dispersing or immersing a laminar graphite material (e.g., powder of natural flake graphite or synthetic graphite) in an oxidizing agent, typically a mixture of an intercalant (e.g., concentrated sulfuric acid) and an oxidant (e.g., nitric acid, hydrogen peroxide, sodium perchlorate, potassium permanganate) at a desired temperature (typically 0-70°C) for a sufficient length of time (typically 4 hours to 5 days).
  • an intercalant e.g., concentrated sulfuric acid
  • an oxidant e.g., nitric acid, hydrogen peroxide, sodium perchlorate, potassium permanganate
  • the resulting graphite oxide particles are then rinsed with water several times to adjust the pH values to typically 2-5.
  • the resulting suspension of graphite oxide particles dispersed in water is then subjected to ultrasonication to produce a dispersion of separate graphene oxide sheets dispersed in water.
  • a small amount of reducing agent e.g. Na ⁇ B
  • RDO reduced graphene oxide
  • GIC graphite intercalation compound
  • the GIC particles are then exposed to a thermal shock, preferably in a temperature range of 600°C-l,l00°C for typically 15 to 60 seconds to obtain exfoliated graphite or graphite worms, which are optionally (but preferably) subjected to mechanical shearing (e.g. using a mechanical shearing machine or an ultrasonicator) to break up the graphite flakes that constitute a graphite worm.
  • mechanical shearing e.g. using a mechanical shearing machine or an ultrasonicator
  • the pristine graphene material is preferably produced by one of the following three processes: (A) intercalating the graphitic material with a non-oxidizing agent, followed by a thermal or chemical exfoliation treatment in a non-oxidizing environment; (B) subjecting the graphitic material to a supercritical fluid environment for inter-graphene layer penetration and exfoliation; or (C) dispersing the graphitic material in a powder form to an aqueous solution containing a surfactant or dispersing agent to obtain a suspension and subjecting the suspension to direct ultrasonication to obtain a graphene dispersion.
  • a particularly preferred step comprises (i) intercalating the graphitic material with a non-oxidizing agent, selected from an alkali metal (e.g., potassium, sodium, lithium, or cesium), alkaline earth metal, or an alloy, mixture, or eutectic of an alkali or alkaline metal; and (ii) a chemical exfoliation treatment (e.g., by immersing potassium-intercalated graphite in ethanol solution).
  • a non-oxidizing agent selected from an alkali metal (e.g., potassium, sodium, lithium, or cesium), alkaline earth metal, or an alloy, mixture, or eutectic of an alkali or alkaline metal
  • a chemical exfoliation treatment e.g., by immersing potassium-intercalated graphite in ethanol solution.
  • a preferred step comprises immersing the graphitic material to a supercritical fluid, such as carbon dioxide (e.g., at temperature T > 3l°C and pressure P > 7.4 MPa) and water (e.g., at T > 374°C and P > 22.1 MPa), for a period of time sufficient for inter graphene layer penetration (tentative intercalation).
  • a supercritical fluid such as carbon dioxide (e.g., at temperature T > 3l°C and pressure P > 7.4 MPa) and water (e.g., at T > 374°C and P > 22.1 MPa)
  • a sudden de pressurization to exfoliate individual graphene layers.
  • suitable supercritical fluids include methane, ethane, ethylene, hydrogen peroxide, ozone, water oxidation (water containing a high concentration of dissolved oxygen), or a mixture thereof.
  • a preferred step comprises (a) dispersing particles of a graphitic material in a liquid medium containing therein a surfactant or dispersing agent to obtain a suspension or slurry; and (b) exposing the suspension or slurry to ultrasonic waves (a process commonly referred to as ultrasonication) at an energy level for a sufficient length of time to produce a graphene dispersion of separated graphene sheets (non-oxidized NGPs) dispersed in a liquid medium (e.g. water, alcohol, or organic solvent).
  • a liquid medium e.g. water, alcohol, or organic solvent
  • NGPs can be produced with an oxygen content no greater than 25% by weight, preferably below 20% by weight, further preferably below 5%. Typically, the oxygen content is between 5% and 20% by weight.
  • the oxygen content can be determined using chemical elemental analysis and/or X-ray photoelectron spectroscopy (XPS).
  • the laminar graphite materials used in the prior art processes for the production of the GIC, graphite oxide, and subsequently made exfoliated graphite, flexible graphite sheets, and graphene platelets were, in most cases, natural graphite.
  • the starting material may be selected from the group consisting of natural graphite, artificial graphite (e.g., highly oriented pyrolytic graphite, HOPG), graphite oxide, graphite fluoride, graphite fiber, carbon fiber, carbon nanofiber, carbon nanotube, mesophase carbon microbead (MCMB) or carbonaceous microsphere (CMS), soft carbon, hard carbon, and combinations thereof.
  • All of these materials contain graphite crystallites that are composed of layers of graphene planes stacked or bonded together via van der Waals forces.
  • graphite multiple stacks of graphene planes, with the graphene plane orientation varying from stack to stack, are clustered together.
  • carbon fibers the graphene planes are usually oriented along a preferred direction.
  • soft carbons are carbonaceous materials obtained from carbonization of liquid-state, aromatic molecules. Their aromatic ring or graphene structures are more or less parallel to one another, enabling further graphitization.
  • Hard carbons are carbonaceous materials obtained from aromatic solid materials (e.g., polymers, such as phenolic resin and polyfurfuryl alcohol). Their graphene structures are relatively randomly oriented and, hence, further graphitization is difficult to achieve even at a temperature higher than 2,500°C. But, graphene sheets do exist in these carbons.
  • Fluorinated graphene or graphene fluoride is herein used as an example of the halogenated graphene material group.
  • fluorination of pre- synthesized graphene This approach entails treating graphene prepared by mechanical exfoliation or by CVD growth with fluorinating agent such as XeF 2 , or F-based plasmas;
  • Exfoliation of multilayered graphite fluorides Both mechanical exfoliation and liquid phase exfoliation of graphite fluoride can be readily accomplished [F. Karlicky, et al.“ Halogenated Graphenes: Rapidly Growing Family of Graphene Derivatives” ACS Nano, 2013, 7 (8), pp. 6434-6464].
  • the process of liquid phase exfoliation includes ultra-sonic treatment of a graphite fluoride in a liquid medium to produce graphene fluoride sheets dispersed in the liquid medium. The resulting dispersion can be directly used in the graphene deposition of polymer component surfaces.
  • the nitrogenation of graphene can be conducted by exposing a graphene material, such as graphene oxide, to ammonia at high temperatures (200°C-400°C). Nitrogenated graphene could also be formed at lower temperatures by a hydrothermal method; e.g. by sealing GO and ammonia in an autoclave and then increased the temperature to l50°C-250°C. Other methods to synthesize nitrogen doped graphene include nitrogen plasma treatment on graphene, arc- discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions, and hydrothermal treatment of graphene oxide and urea at different temperatures.
  • a graphene material such as graphene oxide
  • Nitrogenated graphene could also be formed at lower temperatures by a hydrothermal method; e.g. by sealing GO and ammonia in an autoclave and then increased the temperature to l50°C-250°C.
  • Other methods to synthesize nitrogen doped graphene
  • NGPs or graphene materials include discrete sheets/platelets of single-layer and multi-layer (typically less than 10 layers, the few-layer graphene) pristine graphene, graphene oxide, reduced graphene oxide (RGO), graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, chemically functionalized graphene, doped graphene (e.g. doped by B or N).
  • Pristine graphene has essentially 0% oxygen.
  • RGO typically has an oxygen content of 0.00l%-5% by weight.
  • Graphene oxide (including RGO) can have 0.00l%-50% by weight of oxygen.
  • all the graphene materials have 0.00l%-50% by weight of non-carbon elements (e.g. O, H, N, B, F, Cl, Br, I, etc.). These materials are herein referred to as non-pristine graphene materials.
  • non-pristine graphene materials e.g. O, H, N, B, F, Cl, Br, I, etc.
  • the presently disclosed graphene can contain pristine or non-pristine graphene and the disclosed method allows for this flexibility. These graphene sheets all can be chemically functionalized.
  • Graphene sheets have a significant proportion of edges that correspond to the edge planes of graphite crystals.
  • the carbon atoms at the edge planes are reactive and must contain some heteroatom or group to satisfy carbon valency.
  • functional groups e.g. hydroxyl and carboxylic
  • Many chemical function groups e.g. - NH 2 , etc. can be readily imparted to graphene edges and/or surfaces using methods that are well-known in the art.
  • the resulting functionalized graphene sheets may broadly have the following formula(e): [NGP]— R m , wherein m is the number of different functional group types (typically between 1 and 5), R is selected from S0 3 H, COOH, NH 2 , OH, R'CHOH, CHO, CN, COC1, halide, COSH, SH, COOR', SR', SiR' 3 , Si(-OR'-) y R' 3 -y, Si(-0- SiR' 2 — )OR', R", Li, AlR' 2 , Hg— X, TlZ 2 and Mg— X; wherein y is an integer equal to or less than 3, R' is hydrogen, alkyl, aryl, cycloalkyl, or aralkyl, cycloaryl, or poly(alkylether), R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroara
  • DETA diethylenetriamine
  • one of the three -NH 2 groups may be bonded to the edge or surface of a graphene sheet and the remaining two un-reacted -NH 2 groups will be available for reacting with epoxy resin later.
  • Such an arrangement provides a good interfacial bonding between the NGP (graphene sheets) and the matrix resin of a composite material.
  • Other useful chemical functional groups or reactive molecules may be selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylene-tetramine (TETA), tetraethylene-pentamine (TEPA), hexamethylenetetramine, polyethylene polyamine, polyamine epoxy adduct, phenolic hardener, non-brominated curing agent, non-amine curatives, and combinations thereof.
  • These functional groups are multi functional, with the capability of reacting with at least two chemical species from at least two ends. Most importantly, they are capable of bonding to the edge or surface of graphene using one of their ends and, during subsequent epoxy curing stage, are able to react with epoxide or epoxy resin at one or two other ends.
  • the above-described [NGP]— R m may be further functionalized.
  • the NGPs and conductive additives may also be functionalized to produce compositions having the formula: [NGP]— [R'— A] m , where m, R' and A are as defined above.
  • the compositions of the disclosure also include NGPs upon which certain cyclic compounds are adsorbed. These include compositions of matter of the formula: [NGP]— [X—
  • RJ m where a is zero or a number less than 10
  • X is a polynuclear aromatic, polyheteronuclear aromatic or metallopolyheteronuclear aromatic moiety and R is as defined above.
  • Preferred cyclic compounds are planar. More preferred cyclic compounds for adsorption are porphyrins and phthalocyanines. The adsorbed cyclic compounds may be functionalized. Such compositions include compounds of the formula, [NGP]— [X— A a ] m, where m, a, X and A are as defined above.
  • the functionalized NGPs of the instant disclosure can be directly prepared by
  • the graphene platelets can be processed prior to being contacted with a functionalizing agent. Such processing may include dispersing the graphene platelets in a solvent. In some instances, the platelets or may then be filtered and dried prior to contact.
  • a functionalizing agent such processing may include dispersing the graphene platelets in a solvent. In some instances, the platelets or may then be filtered and dried prior to contact.
  • One particularly useful type of functional group is the carboxylic acid moieties, which naturally exist on the surfaces of NGPs if they are prepared from the acid intercalation route discussed earlier. If carboxylic acid functionalization is needed, the NGPs may be subjected to chlorate, nitric acid, or ammonium persulfate oxidation.
  • Carboxylic acid functionalized graphene sheets or platelets are particularly useful because they can serve as the starting point for preparing other types of functionalized NGPs.
  • alcohols or amides can be easily linked to the acid to give stable esters or amides. If the alcohol or amine is part of a di- or poly-functional molecule, then linkage through the O- or NH- leaves the other functionalities as pendant groups.
  • These reactions can be carried out using any of the methods developed for esterifying or aminating carboxylic acids with alcohols or amines as known in the art. Examples of these methods can be found in G. W. Anderson, et ah, J. Amer. Chem. Soc. 86, 1839 (1964), which is hereby incorporated by reference in its entirety.
  • Amino groups can be introduced directly onto graphitic platelets by treating the platelets with nitric acid and sulfuric acid to obtain nitrated platelets, then chemically reducing the nitrated form with a reducing agent, such as sodium dithionite, to obtain amino-functionalized platelets.
  • a reducing agent such as sodium dithionite
  • the graphene dispersions produced may be further added with an acid, a metal salt, an oxidizer, or a combination thereof to prepare a more reactive dispersion for use in the graphene coating of a polymer component.
  • An optional adhesive resin may also be added.
  • the surface cleaning, etching, and graphene coating can be accomplished in one step.
  • One may simply dip a polymer component into the graphene solution for several seconds to several minutes (preferably 5 seconds to 15 minutes) and then retreat the polymer component from the graphene-liquid dispersion. Upon removal of the liquid (e.g. via natural or forced vaporization), graphene sheets are naturally coated on and bonded to polymer component surfaces.
  • functionalized graphene sheets and/or conductive filler may be pre-coated or decorated with nanoscaled particles of a catalytic metal, which can catalyze the subsequent chemical metallization process.
  • This catalytic metal is preferably in the form of discrete nanoscaled particles or coating having a diameter or thickness from 0.5 nm to 100 nm and is preferably selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof.
  • the catalytic metal may alternatively be initially in a precursor form (e.g. as a metal salt) which is later converted into nanoscaled metal deposited on graphene surfaces.
  • the disclosure also provides a graphene dispersion (or graphene/conductive filler dispersion) for use in metallization of a polymer surface.
  • the graphene dispersion comprises comprising multiple graphene sheets and a conductive filler dispersed in a liquid medium wherein the multiple graphene sheets contain single-layer or few-layer graphene sheets selected from a pristine graphene material having essentially zero % of non-carbon elements, or a non- pristine graphene material having 0.001% to 25% by weight of non-carbon elements wherein said non-pristine graphene is selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof, and wherein the dispersion further contains one or multiple species selected from (i) an adhesive resin dissolved or dispersed in the liquid medium, wherein
  • step (c) in the disclosed method may contain immersing the graphene/conductive filler-bonded polymer component in a metallizing bath for electroless plating of metals (chemical metallization). It is highly surprising that graphene surfaces per se (even without transition metal or noble metal) are capable of promoting conversion of some metal salts to metal deposited on graphene surfaces. This would obviate the need to use expensive noble metals (e.g. palladium or platinum) as nuclei for subsequent chemical growth of metal crystals, as required of the prior art process.
  • noble metals e.g. palladium or platinum
  • the high electrical conductivity and high specific surface areas of the deposited graphene sheets enable electro-plating of metal layer(s) on graphene-coated polymer component surfaces.
  • Graphene sheets, deposited on polymer component surfaces are also found to significantly enhance the strength, hardness, durability, and scratch resistance of the deposited metal layer.
  • the disclosed method produces a surface-metallized polymer article comprising a polymer component having a surface, a first layer of multiple graphene sheets and a conductive filler coated on the polymer component surface, and a second layer of a plated metal deposited on the first layer, wherein the multiple graphene sheets (functionalized or un-functionalized) contain single-layer graphene sheets or few-layer graphene sheets (2-10 graphene planes) wherein the multiple graphene sheets are bonded to the polymer component surface with or without an adhesive resin.
  • the first layer typically has a thickness from 0.34 nm to 30 pm (preferably from 1 nm to 1 pm and further preferably from 1 nm to 100 nm).
  • the second layer preferably has a thickness from 0.5 nm to 1.0 mm, and more preferably from 1 nm to 10 pm.
  • the doped graphene preferably contains N-doped, boron-doped, phosphorus-doped graphene, or a combination thereof.
  • the graphene sheets contain a pristine graphene and the first layer contains an adhesive resin that chemically bonds the graphene sheets to the polymer component surface.
  • the graphene sheets contain a non-pristine graphene material having a content of non-carbon elements from 0.01% to 20% by weight and the non-carbon elements include an element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.
  • the surface-metallized polymer article may be selected from a faucet, a shower head, a tubing, a pipe, a connector, an adaptor, a sink (e.g. kitchen or bathroom sink), a bathtub cover, a spout, a sink cover, a bathroom accessory, or a kitchen accessory.
  • a sink e.g. kitchen or bathroom sink
  • a bathtub cover e.g. a spout, a sink cover, a bathroom accessory, or a kitchen accessory.
  • the polymer component may contain a plastic, a rubber, a thermoplastic elastomer, a polymer matrix composite, a rubber matrix composite, or a combination thereof.
  • the polymer component contains a thermoplastic, a thermoset resin, an
  • interpenetrating network a rubber, a thermoplastic elastomer, a natural polymer, or a
  • the polymer component contains a plastic selected from acrylonitrile-butadiene- styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate, polyamide or nylon, polystyrene, polyacrylate, polyethylene, polypropylene, polyacetal, polyester, polyether, polyether sulfone, poly ether ether ketone (PEEK), poly sulfone, polyphenylene oxide (PPO), polyvinyl chloride (PVC), polyimide, polyamide imide, polyurethane, polyurea, or a combination thereof.
  • ABS acrylonitrile-butadiene- styrene copolymer
  • SAN styrene-acrylonitrile copolymer
  • PES polycarbonate
  • polyamide or nylon polystyrene
  • polyacrylate polyamide or nylon
  • polystyrene polyacrylate
  • polyethylene polyethylene
  • the plated metal is preferably selected from copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, an alloy thereof, or a combination thereof.
  • the graphene sheets may be further decorated with nanoscaled particles or coating (having a diameter or thickness from 0.5 nm to 100 nm) of a catalytic metal selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, an alloy thereof, or a combination thereof, and wherein the catalytic metal is different in chemical composition than the plated metal.
  • the catalytic metal particles or coating are covered by at least a layer of plated metal
  • the polymer component surface, prior to being deposited with the first layer of graphene sheets contains only small openings or pores having a diameter or a depth ⁇ 0.1 pm.
  • the multiple graphene sheets are bonded to the polymer film surface with an adhesive resin having an adhesive-to-graphene weight ratio from 1/5000 to 1/10, preferably from 1/1000 to 1/100.
  • the presently disclosed surface-metallized polymer film may be used for or in a product such as a vehicle component, an electronic appliance, an electronic device, a food packaging film or bag, a protective clothing, an antistatic film or bag, a susceptor in microwave cooking, a blanket, an anti-reflection accessary, an EMI-shielding film, a children's toy, a product label, a mailer, a sports card, a greeting card, a solar control window film, or a stamping.
  • the electronic appliance or electronic device contains a push button or cover for hi-fi equipment, a cell phone, a coffee machine, a LED lamp housing, a wearable device, an electronic watch, a laptop computer, or a tablet computer.
  • MCMB meocarbon microbeads
  • This material has a density of about 2.24 g/cm with a median particle size of about 16 pm.
  • MCMBs (10 grams) were intercalated with an acid solution (sulfuric acid, nitric acid, and potassium permanganate at a ratio of 4:1:0.05) for 48 hours. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The intercalated MCMBs were repeatedly washed in a 5% solution of HC1 to remove most of the sulfate ions. The sample was then washed repeatedly with deionized water until the pH of the filtrate was neutral.
  • the slurry was dried and stored in a vacuum oven at 60°C for 24 hours.
  • the dried powder sample was placed in a quartz tube and inserted into a horizontal tube furnace pre-set at a desired temperature, 800°C-l,l00°C for 30-90 seconds to obtain graphene sheets.
  • a quantity of graphene sheets was mixed with water and ultrasonicated at 60-W power for 10 minutes to obtain a graphene dispersion.
  • the oxygen content of the graphene powders (GO or RGO) produced was from 0.1% to approximately 25%, depending upon the exfoliation temperature and time.
  • Graphite oxide was prepared by oxidation of graphite flakes with sulfuric acid, sodium nitrate, and potassium permanganate at a ratio of 4:1:0.05 at 30°C for 48 hours, according to the method of Hummers [US Pat. No.2, 798, 878, July 9, 1957].
  • the mixture was poured into deionized water and filtered.
  • the sample was then washed with 5% HC1 solution to remove most of the sulfate ions and residual salt and then repeatedly rinsed with deionized water until the pH of the filtrate was approximately 4.
  • the intent was to remove all sulfuric and nitric acid residue out of graphite interstices.
  • the slurry was dried and stored in a vacuum oven at 60°C for 24 hours.
  • the dried, intercalated (oxidized) compound was exfoliated by placing the sample in a quartz tube that was inserted into a horizontal tube furnace pre-set at l,050°C to obtain highly exfoliated graphite.
  • the exfoliated graphite was dispersed in water along with a 1% surfactant at 45°C in a flat-bottomed flask and the resulting suspension was subjected to ultrasonication for a period of 15 minutes to obtain dispersion of graphene oxide (GO) sheets.
  • Pristine graphene sheets were produced by using the direct ultrasonication or liquid-phase exfoliation process. In a typical procedure, five grams of graphite flakes, ground to
  • HEG highly exfoliated graphite
  • FHEG fluorinated highly exfoliated graphite
  • a pre-cooled Teflon reactor was filled with 20-30 mL of liquid pre-cooled ClF 3 , and then the reactor was closed and cooled to liquid nitrogen temperature. Subsequently, no more than 1 g of HEG was put in a container with holes for C1F 3 gas to access the reactor. After 7-10 days, a gray-beige product with approximate formula C 2 F was formed. GF sheets were then dispersed in halogenated solvents to form suspensions.
  • Graphene oxide (GO), synthesized in Example 2 was finely ground with different proportions of urea and the pelletized mixture heated in a microwave reactor (900 W) for 30 s. The product was washed several times with deionized water and vacuum dried. In this method graphene oxide gets simultaneously reduced and doped with nitrogen.
  • the products obtained with graphene/urea mass ratios of 1/0.5, 1/1 and 1/2 are designated as N-l, N-2 and N-3 respectively and the nitrogen contents of these samples were 14.7, 18.2 and 17.5 wt.% respectively as determined by elemental analysis. These nitrogenated graphene sheets remain dispersible in water.
  • a first set of several rectangular bars of ABS plastic each having a surface of 50 cm" were immersed for 3 minutes at 70°C in an etching solution consisting of 4 M H2SO4 and 3.5 M Cr0 3 .
  • the bars were rinsed with water.
  • a second set of several bars of identical dimensions were used without etching.
  • the two sets of specimens were immersed for a time period of 30 seconds at 40°C in a RGO-water solution prepared in Example 1 and then removed from the solution and dried in air. Subsequently, the RGO-bonded ABS bars were copper-plated in a sulfuric acid-containing copper electrolyte.
  • the bonded metal layers mediated by graphene sheets perform equally well in terms of surface hardness, scratch resistance, and durability against heating/cooling cycles.
  • a first set of several rectangular bars of ABS plastic each having a surface of 50 cm 2 were immersed for 3 minutes at 70°C in an etching solution consisting of 4 M H 2 S0 4 and 3.5 M Cr(3 ⁇ 4. The bars were rinsed with water. On a separate basis, a second set of several bars of identical dimensions were used without etching.
  • the two sets of specimens were immersed for a time period of 5 minutes at 40°C in a Pd/Sn colloid-containing solution which contains 250 mg/L palladium, 10 g/L tint II) and 1 10 g/L HC1. Subsequently, the specimens were rinsed in water and copper-plated in a sulfuric acid- containing copper electrolyte.
  • a Pd/Sn colloid-containing solution which contains 250 mg/L palladium, 10 g/L tint II) and 1 10 g/L HC1.
  • the specimens were rinsed in water and copper-plated in a sulfuric acid- containing copper electrolyte.
  • ABS plastic surfaces could not be properly (evenly) metallized even when some significant amount of expensive rare metal (e.g. Pd) was implemented on etched surfaces.
  • a first set of several rectangular bars of HIPS plastic each ha ving a surface of 50 car were immersed for 3 minutes at 70°C in an etching solution consisting of 4 M H 2 SO 4 and 3.5 M Crt3 ⁇ 4. The bars were rinsed with water. On a separate basis, a second set of several bars of identical dimensions were used without etching.
  • the plastic articles were spray-coated with a pristine graphene-adhesive solution containing 5% by weight graphene sheets and 0.01 % by weight epoxy resin. Upon removal of the liquid medium (acetone) and cured at 150°C for 15 minutes, graphene sheets were well bonded to plastic surfaces.
  • the graphene-bonded plastic articles were subjected to electro chemical nickel plating.
  • the articles were treated for 15 minutes in a Watts electrolyte, containing 1.2 M NiS0 4 .7H 2 0, 0.2 M NiCl 2. 6H 2 0 and 0.5 M H3BO3.
  • the initial current was 0.3 A/dm 2 , and the nickel plating was carried out at 40°C.
  • COMPARATIVE EXAMPLE 7a Sulfide- Activated High-Impact Polystyrene (HIPS) A first set of several rectangular bars of HIPS plastic each having a surface of 50 cm were immersed for 3 minutes at 70°C in an etching solution consisting of 4 M H 2 S0 4 and 3.5 M CrQ . The bars were rinsed with water. On a separate basis, a second set of several bars of identical dimensions were used without etching.
  • HIPS Sulfide- Activated High-Impact Polystyrene
  • the plastic articles were treated for 30 seconds in an ammonia solution with 0.5 M CuS0 4 .5 H 2 0 having a pH value of 9.5 and a temperature of 20°C.
  • the plastic articles then were submerged for 20 seconds in distilled water and, subsequently, for 30 seconds treated with a sulfide solution, containing 0.1 M Na 2 S 2 at 20°C.
  • the plastic articles were again washed in cold water. This was followed by electro-chemical nickel plating. For this, the articles were treated for 15 minutes in a Watts electrolyte, containing 1.2 M
  • the initial current was 0.3 A/dm 2 , and the nickel plating was carried out at 40°C.
  • HIPS plastic surfaces could not be evenly metallized using the sulfide seeding approach.
  • the instant graphene -mediation approach enables successful plating of practically ail kinds of metals on not just HIPS surfaces but any other types of polymer surfaces.
  • EXAMPLE 8 Graphene-Enabled Polyurethane-Based Thermoplastic Elastomer (TPE)
  • TPE bars were immersed in an aqueous alkaline solution containing 5 g/L sodium hydroxide and 0.5 g/L of GO for 15 minutes. The bars were then removed from the solution (actually a graphene dispersion), enabling graphene oxide sheets to get coated onto TPE surfaces while water was removed. Residual NaOH was rinsed away by water.
  • the GO-coated bars were subjected to electroless plating of nickel in an ammonia- containing nickel electrolyte at 30°C for 10 minutes.
  • Ni layer was directly deposited electrochemically onto GO-coated TPE surfaces. Both approaches were found to provide Ni layers that have high hardness, scratch resistance, and glossiness. This elegantly simple 2-step process is surprisingly effective in providing a wide variety of metallized polymer articles.
  • the TPE parts could not be uniformly metallized with the assistance of Pd/Sn catalyst seeds if without using strong chromo sulfuric acid as an etchant to produce large-sized micro-caverns (surface cavities) deeper than 0.3 pm.
  • This Pd/Sn catalyst was deposited onto large surface cavities of TPE after immersing etched TPE specimens in a Pd/Sn colloid- containing solution which contains 80 mg/L palladium, 10 g/L tin(II) and 110 g/L HC1 at 30°C for 10 minutes.
  • Catalytic metal can be deposited onto graphene surfaces using a variety of processes: physical vapor deposition, sputtering, chemical vapor deposition, chemical reduction/oxidation, electrochemical reduction/oxidation, etc.
  • Co is used as a representative catalytic metal and chemical oxidation/reduction from solution is used for deposition of nanoparticles on graphene surfaces.
  • a cobalt salt solution was used as the metal salt solution.
  • the aqueous cobalt (II) salt solution contains 1 to 10 g/L C0SO4.7H2O and one oxidizer, hydrogen peroxide.
  • Graphene oxide sheets were dispersed in the solution to form a dispersion. Heating of such a dispersion enabled at least part of the cobalt (II) to be oxidized by H 2 0 2 into cobalt (III), which was deposited on graphene surfaces upon further heating.
  • the electrolytic direct metallization of the composite surface was then allowed to proceed.
  • the composite surface was plated in a nickel bath, wherein an initial current density of 0.3 A/dm was used for electro -chemical nickel plating which later was increased to 3 A/dm .
  • Electro-chemical nickel plating was conducted in a Watts electrolyte at 30°C to 40°C for a treatment time of 10 to 15 minutes.
  • the Watts electrolyte contains 1.2 M NiS0 4 .7H 2 0, 0.2 M NiCl 2 .6H 2 0 and 0.5 M H3BO3.
  • EXAMPLE 10 Functionalized Graphene- and CNT-Bonded Poly Ether Ether Ketone (PEEK) and Other Polymer Components
  • a first set of several rectangular bars of PEEK plastic each having a surface of 50 cm" were immersed for 3 minutes at 70°C in an etching solution consisting of 4 M H 2 S0 4 and 3.5 M Cr0 3 .
  • the bars were rinsed with water.
  • a second set of several bars of identical dimensions were used without etching.
  • the plastic articles were dipped into a functionalized graphene/CNT- adhesive dispersion containing 5% by weight of graphene sheets or carbon nanotubes (CNT) and 0.01% by weight of epoxy resin or polyurethane.
  • Chemical functional groups involved in this study include an azide compound (2-azidoethanol), alkyl silane, hydroxyl group, carboxyl group, amine group, sulfonate group (— S0 3 H), and diethylenetriamine (DETA).
  • These functionalized graphene sheets and CNTs are supplied from Taiwan Graphene Co., Taipei, Taiwan. Upon removal of the liquid medium (acetone) and cured at 150°C for 15 minutes, graphene sheets and CNTs were well bonded to plastic surfaces.
  • the graphene ⁇ and CNT-bonded plastic articles were subjected to chemical nickel plating or chemical copper plating.
  • nickel plating the functionalized graphene- and CNT-bonded articles were treated for 15 minutes in a chemical plating solution containing 1.2 M NiS0 4 -7H 2 0 at 40°C.
  • Cu plating the functionalized graphene- and CNT- bonded plastic parts were dipped in an ammonia solution with 0.5 M CuS0 4 .5 3 ⁇ 40 having a pH value of 9.5 and a temperature of 20°C for 30 seconds.
  • the polymer components can be well-metallized using the presently disclosed functionalized graphene mediation approach evert without an etching treatment.
  • metal was well-bonded to polymer component surfaces having excellent matte appearance and outstanding scratching resistance.
  • the metallized surfaces are generally smoother if functionalized graphene sheets are included alone or in combinations with functionalized CNTs as compared to the use of functionalized CNTs alone in the dipping dispersion.
  • EXAMPLE 11 Graphene/Conductive Additive-Bonded Poly Ether Sulfone (PES) and Other Polymer Films
  • a first set of several rectangular films of PES plastic each having a surface of 50 cnf were immersed for 3 minutes at 70°C in an etching solution consisting of 4 M H 2 S0 4 and 3.5 M Cr0 3 .
  • the bars were rinsed with water.
  • a second set of several bars of identical dimensions were used without etching.
  • the plastic films were dipped into a graphene/conductive filler/adhesive dispersion containing 5% by weight of graphene sheets, 0.5% by weight vapor-grown carbon nanofibers, and 0.01% by weight of epoxy resin or polyurethane, Cu nanowires and Ni-coated polyacrylonitrile nanofibers (obtained by eiectrospinning) were also used as a conductive filler in tins example.
  • Chemical functional groups involved in this study include alkyl silane, hydroxyl group, carboxyl group, amine group, and diethylenetriamine (DETA). These functionalized graphene sheets are supplied from Taiwan Graphene Co., Taipei, Taiwan. Upon removal of the liquid medium (acetone) and cured at 150°C for 15 minutes, graphene sheets were well bonded to plastic film surfaces.
  • the graphene/conductive filler-bonded plastic films were subjected to chemical nickel plating or chemical copper plating.
  • nickel plating the bonded or covered polymer components were treated for 15 minutes in a chemical plating solution containing 1.2 M NiS0 4 -7H 2 0 at 40°C.
  • Cu plating the bonded or covered plastic parts were dipped in an ammonia solution with 0.5 M CuS0 4 .5 I3 ⁇ 40 having a pH value of 9.5 and a temperature of 20°C for 30 seconds.
  • the polymer films can be well-metallized using the presently disclosed functionalized graphene mediation approach even without an etching treatment.
  • metal was well-bonded to polymer film surfaces having excellent gloss and metal reflectivity and outstanding scratching resistance.
  • the metallized surfaces are generally smoother if graphene sheets are included alone or in combinations with a conductive filler as compared to the use of the conductive filler alone in the dipping dispersion.
  • a wide variety of chemical functional groups can be attached to the edges or surfaces of mediating graphene sheets and optional conductive filler (e.g. carbon nanotubes, metal nanowires, etc.) that enable rapid metallization of polymer films.
  • conductive filler e.g. carbon nanotubes, metal nanowires, etc.
  • the graphene sheets that exhibit a negative Zeta potential value in an intended liquid medium are particularly effective in promoting metallization of polymer films.
  • the disclosed process can be conducted under very mild conditions requiring only a short period of time. Optimal results are also achievable without the repetition of the process steps commonly required of prior art processes.
  • the process can be controlled in a functionally secure and simple manner which ultimately affects the quality of the metal layers.
  • polymer film surface with a graphene dispersion e.g. a spraying step, a coating step, a painting step, a casting step, a printing, or a dipping step
  • a graphene dispersion e.g. a spraying step, a coating step, a painting step, a casting step, a printing, or a dipping step

Abstract

L'invention concerne un film polymère métallisé en surface (et son procédé de production) comprenant : (a) un film polymère ayant une épaisseur de 10 nm à 5 mm et deux surfaces primaires ; (b) une couche de graphène ayant une épaisseur de 0,34 nm à 50 µm et comprenant de multiples feuillets de graphène et une charge conductrice facultative appliquée sur ou liée à au moins l'une des deux surfaces primaires avec ou sans utilisation de résine adhésive ; et (c) une couche métallique comprenant un métal plaqué déposé sur la couche de graphène ; où les feuillets de graphène contiennent des feuillets de graphène monocouche ou à faible nombre de couches choisis parmi le graphène de pristine, l'oxyde de graphène, l'oxyde de graphène réduit, le fluorure de graphène, le chlorure de graphène, le bromure de graphène, l'iodure de graphène, le graphène hydrogéné, le graphène azoté, le graphène dopé, le graphène chimiquement fonctionnalisé, ou une combinaison de ceux-ci. Le film obtenu présente une résistance aux rayures, résistance mécanique, dureté, conductivité électrique, conductivité thermique, réflectivité de la lumière élevées, un fort brillant, etc.
PCT/US2019/022900 2018-03-19 2019-03-19 Métallisation des films polymères médiée par le graphène WO2019183044A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US15/924,988 2018-03-19
US15/924,991 2018-03-19
US15/924,988 US20190283379A1 (en) 2018-03-19 2018-03-19 Graphene-mediated metallization of polymer films
US15/924,991 US20190284712A1 (en) 2018-03-19 2018-03-19 Apparatus for graphene-mediated metallization of polymer films
US15/926,458 US20190292675A1 (en) 2018-03-20 2018-03-20 Process for graphene-mediated metallization of polymer films
US15/926,458 2018-03-20
US15/943,081 2018-04-02
US15/943,081 US20190292676A1 (en) 2018-03-20 2018-04-02 Process for graphene-mediated metallization of polymer films

Publications (1)

Publication Number Publication Date
WO2019183044A1 true WO2019183044A1 (fr) 2019-09-26

Family

ID=67986341

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2019/022900 WO2019183044A1 (fr) 2018-03-19 2019-03-19 Métallisation des films polymères médiée par le graphène

Country Status (1)

Country Link
WO (1) WO2019183044A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114714684A (zh) * 2021-10-15 2022-07-08 常州威斯双联科技有限公司 一种高导热石墨烯磁性复合材料及制备方法
CN115682810A (zh) * 2022-10-27 2023-02-03 常州富烯科技股份有限公司 石墨烯金属复合散热翅片、散热器、制备方法
WO2024054122A1 (fr) * 2022-09-07 2024-03-14 Cirrus Materials Science Limited Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110017955A1 (en) * 2009-07-23 2011-01-27 Aruna Zhamu Nano graphene-modified curing agents for thermoset resins
US20120196074A1 (en) * 2009-08-31 2012-08-02 Kyushu University Graphene sheet and method for producing the same
US20150021554A1 (en) * 2011-10-19 2015-01-22 Sunedison Semiconductor Limited (Uen201334164H) Direct formation of graphene on semiconductor substrates
US20170162291A1 (en) * 2015-12-03 2017-06-08 Aruna Zhamu Highly conducting and oriented graphene film and production process
US20170166722A1 (en) * 2015-12-10 2017-06-15 Aruna Zhamu Chemical-free production of graphene-reinforced polymer matrix composites
US20190145007A1 (en) * 2017-11-15 2019-05-16 Nanotek Instruments, Inc. Functionalized Graphene-Mediated Metallization of Polymer Article

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110017955A1 (en) * 2009-07-23 2011-01-27 Aruna Zhamu Nano graphene-modified curing agents for thermoset resins
US20120196074A1 (en) * 2009-08-31 2012-08-02 Kyushu University Graphene sheet and method for producing the same
US20150021554A1 (en) * 2011-10-19 2015-01-22 Sunedison Semiconductor Limited (Uen201334164H) Direct formation of graphene on semiconductor substrates
US20170162291A1 (en) * 2015-12-03 2017-06-08 Aruna Zhamu Highly conducting and oriented graphene film and production process
US20170166722A1 (en) * 2015-12-10 2017-06-15 Aruna Zhamu Chemical-free production of graphene-reinforced polymer matrix composites
US20190145007A1 (en) * 2017-11-15 2019-05-16 Nanotek Instruments, Inc. Functionalized Graphene-Mediated Metallization of Polymer Article

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114714684A (zh) * 2021-10-15 2022-07-08 常州威斯双联科技有限公司 一种高导热石墨烯磁性复合材料及制备方法
CN114714684B (zh) * 2021-10-15 2023-09-12 常州威斯双联科技有限公司 一种高导热石墨烯磁性复合材料及制备方法
WO2024054122A1 (fr) * 2022-09-07 2024-03-14 Cirrus Materials Science Limited Procédé destiné à fournir une surface conductrice sur une surface polymère non conductrice
CN115682810A (zh) * 2022-10-27 2023-02-03 常州富烯科技股份有限公司 石墨烯金属复合散热翅片、散热器、制备方法

Similar Documents

Publication Publication Date Title
US20190292675A1 (en) Process for graphene-mediated metallization of polymer films
US20190292722A1 (en) Process for graphene-mediated metallization of fibers, yarns, and fabrics
US20190292721A1 (en) Process for graphene-mediated metallization of fibers, yarns, and fabrics
US20190143656A1 (en) Products containing graphene-mediated metallized polymer component
US20190283379A1 (en) Graphene-mediated metallization of polymer films
US20190143369A1 (en) Process for graphene-mediated metallization of polymer article
US20190283377A1 (en) Conductive graphene mixture-mediated metallization of polymer article
TWI784124B (zh) 包括石墨烯介導的金屬化聚合物部件之產品
US20190292720A1 (en) Graphene-Mediated Metallization of Fibers, Yarns, and Fabrics
US20190283378A1 (en) Apparatus for graphene-mediated production of metallized polymer articles
WO2019183205A1 (fr) Métallisation de fibres, de fils et de tissus médiée par le graphène
US20190292676A1 (en) Process for graphene-mediated metallization of polymer films
US20190292671A1 (en) Metal matrix nanocomposite containing oriented graphene sheets and production process
US10730070B2 (en) Continuous process for manufacturing graphene-mediated metal-plated polymer article
US11332830B2 (en) Functionalized graphene-mediated metallization of polymer article
US11629420B2 (en) Production process for metal matrix nanocomposite containing oriented graphene sheets
TWI720365B (zh) 石墨烯介導的鍍金屬的聚合物製品及生產方法
Tien et al. Using self-assembly to prepare a graphene-silver nanowire hybrid film that is transparent and electrically conductive
WO2019183044A1 (fr) Métallisation des films polymères médiée par le graphène
KR101537638B1 (ko) 그라펜 박막을 이용한 수지의 도금 방법
US20190144621A1 (en) Graphene-Mediated Metal-Plated Polymer Article and Production Method
CN101474898A (zh) 基于石墨烯的导电碳膜及制备方法和应用
WO2019191014A1 (fr) Nanocomposite à matrice métallique contenant des feuilles de graphène orientées et procédé de production
Wang et al. A facile process to manufacture high performance copper layer on ceramic material via biomimetic modification and electroless plating
US20190284712A1 (en) Apparatus for graphene-mediated metallization of polymer films

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: 19771740

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19771740

Country of ref document: EP

Kind code of ref document: A1