TWI808118B - Apparatus for graphene-mediated production of metallized polymer articles - Google Patents

Abstract

Provided is an apparatus for manufacturing a surface-metalized polymer article, the apparatus comprising: (a) a graphene deposition chamber 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 surface of at least a polymer component for forming at least a graphene-coated polymer component; and (b) a metallization chamber that accommodates a plating solution for plating a layer of a desired metal on the at least a graphene-coated polymer component to obtain the surface-metalized polymer article.

Description

Equipment for graphene-mediated production of metallized polymer products

Cross References to Related Applications

This application claims priority to U.S. Patent Application No. 15/924,957, filed March 19, 2018, and U.S. Patent Application No. 15/924,971, filed March 19, 2018, which are hereby incorporated by reference for all purposes.

The present disclosure relates generally to the field of metallization of polymeric component surfaces, and more specifically, to graphene-mediated metallized polymeric articles and processes and equipment required for producing the same.

Metallized plastic is often used for decorative purposes. For example, metallizing the surface of plastics such as acrylonitrile-butadiene-styrene (ABS) and ABS-polycarbonate blends for use in bathroom fittings, automotive accessories, furniture, hardware, jewelry, and buttons/knobs. These articles of manufacture can be metallized to give the surface of the article an attractive appearance.

In addition, plastic, rubber, and polymer matrix composites such as fiber-reinforced or additive-filled thermoplastic, thermoset, and rubber-matrix composites can also be metallized for functional purposes. For example, metallization of plastic-based electronic components may be performed for electromagnetic interference (EMI) shielding. In addition, the surface properties of polymer parts can be changed in a controlled manner by metal coating.

Made of non-conductive polymers (e.g. plastic, rubber, polymer matrix composites, etc.) The products can be metallized by electroless metallization process. In a typical process, the article is first cleaned and etched, then treated with a noble metal such as palladium, and finally metallized in a metallization solution. The etching step typically involves the use of chromic acid or chromosulfuric acid. The etching step serves to render the surface of the article receptive to subsequent metallization by means of corresponding solutions in subsequent processing steps by means of improved surface wettability and to provide good adhesion of the finally deposited metal to the polymer surface.

In the etching step, the surface of the polymeric article is etched using chromium sulfuric acid to form surface microvoids into which the metal is deposited and adhered. After the etching step, the surface of the polymer part is activated by means of an activating reagent (or activator) typically comprising a noble metal, and then metallized using electroless plating. Subsequently, thicker metal layers can be deposited electrolytically.

Chromium sulfuric acid based etching solutions are toxic and should therefore be replaced where possible. For example, an etching solution based on chromium sulfuric acid may be replaced by an etching solution comprising permanganate. The use of permanganates in alkaline media for the metallization of circuit boards as carriers for electronic circuits has long been established. Since the hexavalent state (manganate) produced in oxidation is water soluble and sufficiently stable under alkaline conditions, similar to trivalent chromium, manganate can be electrolytically oxidized back to the original oxidant, in this case permanganate. For the metallization of ABS plastics, alkaline permanganate solutions have been found to be unsuitable, since in this way it is not possible to obtain sufficient adhesive strength between the metal layer and the plastic substrate. The adhesive strength is determined in the "peel test" and should have a value of at least 0.4 N/mm.

As an alternative to chromic sulfuric acid, WO 2009/023628 A2 proposes the use of strongly acidic solutions comprising alkali metal permanganates. The solution contains about 20 g/l of alkali metal permanganate in 40-85% by weight phosphoric acid. Such solutions form colloidal manganese(IV) species that are difficult to remove. In addition, colloids are also difficult to form good quality coatings. To solve this problem, WO 2009/023628 A2 proposes to use a source of manganese(VII) that does not contain any alkali metal or alkaline earth metal ions. However, the preparation of such sources of manganese(VII) is expensive and inconvenient.

Therefore, there is an urgent need for Industrial-scale metallization of polymer component surfaces.

Another major problem with prior art metallization processes is the notion that, after the etching step, the surface of the polymer component must be activated by means of an activating agent, typically comprising a noble metal such as palladium. Precious metals are known to be rare and expensive. In an alternative process [L. Naruskevicius et al. "Process for metallizing a plastic surface," US Pat. No. 6,712,948 (03/30/2004)], a chemically etched plastic surface is treated with a metal salt solution containing a cobalt, silver, tin, or lead salt. However, activated plastic surfaces must be further treated with sulfide solutions. The entire process is slow, cumbersome and expensive.

Therefore, there is another pressing need to carry out the industrial scale metallization of the surface of polymeric parts without using expensive noble metals in the activating reagents or even without an activation step if at all possible.

The present disclosure provides a surface metallized polymer article comprising: a polymer part having a surface, a first layer of a plurality of graphene sheets and a conductive filler coated on the surface of the polymer part, and a metallized second layer deposited on the first layer, wherein the plurality of graphene sheets comprise single or few-layer graphene sheets selected from a native graphene material having substantially 0% non-carbon elements or a non-native graphene material having 0.001% to 25% by weight non-carbon elements, wherein the non-native graphene sheets Graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodinated graphene, hydrogenated graphene, graphene nitride, doped graphene, chemically functionalized graphene, or combinations thereof, and wherein the plurality of graphene sheets and the conductive filler are bonded to the surface of the polymer part with or without a binder resin, and the first layer has a thickness from 0.34 nm to 30 μm.

The present disclosure also provides an apparatus that can be used to produce the surface metallized article. for The apparatus for making a surface metallized polymer article may comprise: (a) a graphene deposition chamber (e.g., a graphene dispersion bath) containing a graphene dispersion comprising a plurality of graphene sheets and optionally conductive fillers dispersed in a first liquid medium and an optional binder resin dissolved in the first liquid medium, wherein the graphene deposition chamber is operated to deposit the graphene sheets and optional conductive fillers onto the surface of at least one polymeric part to form at least one graphene-coated polymeric part; (b) a metallization chamber (e.g., a metal plating bath) in working relationship with the graphene deposition chamber, the metallization chamber containing a plating solution for plating a layer of the desired metal on the at least one graphene-coated polymer part to obtain a surface metallized polymer article; wherein the plurality of graphene sheets comprise single or few-layer graphene sheets selected from native graphene materials having substantially 0% non-carbon elements or non-native graphene materials having 0.001% to 25% by weight non-carbon elements, wherein the non-native graphene is selected from Graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodinated graphene, hydrogenated graphene, nitrided graphene, doped graphene, chemically functionalized graphene, or combinations thereof.

The apparatus may further comprise a removable carrier for carrying the at least one polymer part and contacting the at least one polymer part with the graphene dispersion (e.g., for dipping the at least one polymer part in the graphene dispersion bath and then withdrawing the at least one polymer part from the bath) to produce the at least one graphene-coated polymer part and/or for contacting the at least one graphene-coated polymer part with the plating solution (e.g., for dipping the at least one graphene-coated polymer part in the metal plating bath) bath, and then withdrawing the at least one graphene-coated polymer part from the bath) to obtain the desired surface metallized polymer article.

The apparatus may further comprise drying, heating or curing providing means (e.g., above the graphene dispersion bath) in working relationship with the graphene deposition chamber for partially or completely removing the first liquid medium from the at least one graphene-coated polymer part and/or for polymerizing or curing the An optional binder resin to produce the at least one graphene-coated polymer part comprising a plurality of graphene sheets bonded to the surface of the at least one polymer part.

In the apparatus, the plating solution may include an electroless plating solution, an electrochemical plating solution or an electrolytic solution. Preferably, the plating solution includes an electroless plating solution containing a metal salt dissolved in water or an organic solvent.

In certain embodiments, the conductive filler is selected from the group consisting of metal nanowires, carbon fibers, carbon nanofibers, carbon-coated fibers, conductive polymer fibers, _nanofibers or nanowires of SnO2 _{, ZnO2} , _In2O3 , or indium tin oxide (ITO), conductive polymers not in fiber form, or combinations thereof. The metal nanowires are preferably nanowires selected from silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), aluminum (Al), or combinations thereof. The conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothiadene (PITN), polyheteroarylidene vinylene (PArV) (wherein the heteroarylene group may be thiophene, furan or pyrrole), polyparaphenylene (PpP), polyphthalocyanine (PPhc) and the like, and derivatives thereof, and combinations thereof.

In some embodiments, the chemical functional group is selected from an alkyl or aryl silane, an alkyl or aralkyl group, a hydroxyl group, a carboxyl group, an amine group, a sulfonate group (—SO ₃ H), an aldehyde group, a quinoidal, a fluorocarbon, or a combination thereof.

及其組合。 Alternatively, the functional groups include derivatives of azido compounds selected from the group consisting of 2-azidoethanol, 3-azidopropan-1-amine, 4-(2-azidoethoxy)-4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropionate, chloroformate, azidocarbonate, dichlorocarbene, carbene, aryne, azone, (R-)-oxycarbonyl Nitrene, where R = any of the following groups:

and their combinations.

In certain embodiments, the functional group is selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde.在某些實施方式中，該官能化劑含有選自下組的官能基，該組由以下各項組成：SO ₃ H、COOH、NH ₂ 、OH、R'CHOH、CHO、CN、COCl、鹵根(halide)、COSH、SH、COOR'、SR'、SiR' ₃ 、Si(--OR'--) _y R' _3-y 、Si(--O--SiR' ₂ --)OR'、R”、Li、AlR' ₂ 、Hg--X、TlZ ₂和Mg--X；其中y係等於或小於3的整數，R'係氫、烷基、芳基、環烷基或芳烷基、環芳基或聚(烷基醚)，R”係氟代烷基、氟代芳基、氟代環烷基、氟代芳烷基或環芳基，X係鹵根，並且Z係羧酸根或三氟乙酸根、及其組合。

The functional groups may be selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), polyethylenepolyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated curing agents, non-amine curing agents, and combinations thereof.

In some embodiments, the functional group may be selected from: OY, NHY, O=C--OY, P=C--NR'Y, O=C--SY, O=C--Y, --CR'1--OY, N'Y or C'Y, and Y is a functional group of a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or transition state analog of an enzyme substrate or is selected from R'--OH, R'--NR'₂, R'SH, R'CHO, R'CN, R'X, R'N⁺(R')₃x^-, R'SiR'₃、R'Si(--OR'--)_{the y}R'_3-y, R'Si(--O--SiR'₂--)OR', R'--R", R'--N--CO, (C₂h₄O--)_wH, (--C₃h₆O--)_wH. (--C₂h₄O)_w--R', (C₃h₆O)_w--R', R', and w is an integer greater than 1 and less than 200.

The surface metallized polymeric article may be selected from faucets, shower heads, pipes, pipes, connectors, adapters, sinks (such as kitchen or bathroom sinks), bathtub covers, spouts, sink covers, bathroom accessories, or kitchen accessories.

In certain embodiments, the first layer contains a binder resin that chemically bonds the graphene sheets and the conductive filler to the surface of the polymer part. In certain alternative embodiments, the graphene sheet comprises a non-native graphene material having a content of non-carbon elements from 0.01% to 20% by weight, and the non-carbon elements include elements selected from the group consisting of oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron. These graphene sheets can be further chemically functionalized.

The polymer component may comprise plastic, rubber, thermoplastic elastomers, polymer matrix composites, rubber matrix composites, or combinations thereof. In certain embodiments, the polymeric component comprises thermoplastics, thermosetting resins, interpenetrating networks, rubber, thermoplastic elastomers, natural polymers, or combinations thereof. In certain preferred embodiments, the polymeric part comprises a plastic selected from the group consisting of: acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate, polyamide or nylon, polystyrene, high-impact polystyrene (HIPS), polyacrylate, polyethylene, polypropylene, polyacetal, polyester, polyether, polyetherpolyester, polyetheretherketone, polyphenylene oxide (PPO), polyvinyl chloride (PVC), poly Amides, polyamidoimides, polyurethanes, polyureas, or combinations thereof.

In surface metallized polymer articles, the metal to be plated is preferably selected from copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, alloys thereof, or combinations thereof. There is no restriction on the type of metal that can be plated.

The graphene sheet may be further decorated with nanoscale particles or coatings (having a diameter or thickness of from 0.5 nm to 100 nm) of a catalytic metal selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof, and wherein the catalytic metal is chemically different from the metal being plated.

In some embodiments, the surface of the polymer part is deposited with graphene sheets and conductive fillers The first layer before contains only small openings or pores with a diameter or depth of <0.1 μm.

In certain embodiments, the plurality of graphene sheets and conductive fillers are bonded to the surface of the polymeric part with a binder resin having a binder to graphene weight ratio of from 1/5000 to 1/10, preferably from 1/1000 to 1/100.

The present disclosure also provides a method of producing a surface metallized polymer article, the method comprising: (a) providing a graphene/conductive filler mixture dispersion comprising a plurality of graphene sheets and conductive filler dispersed in a liquid medium, contacting a surface of a polymer part with the dispersion and facilitating deposition of the graphene sheets and the conductive filler onto the surface of the surface-treated polymer part, wherein the graphene sheets and the conductive filler are bonded to the surface to form a bonded graphene sheet and conductive filler layer covering the surface of the polymer part (i.e., forming a graphene/conductive filler layer) a filler-coated polymer part surface); and (b) chemically, physically, electrochemically, or electrolytically depositing a metal layer on the covered polymer part surface to form the surface-metallized polymer article.

In certain embodiments, the method further comprises, prior to step (a), subjecting the surface of the polymeric part to a grinding treatment, an etching treatment, or a combination thereof. In some embodiments, step (a) includes the step of subjecting the surface of the polymeric part to an etching treatment using an etchant selected from an acid, an oxidizing agent, a metal salt, or a combination thereof.

Preferably, the method further comprises the step of subjecting the surface of the polymer part to an etching treatment without the use of chromic acid or chromic sulfuric acid prior to step (a). More preferably, the method further comprises, prior to step (a), the step of subjecting the surface of the polymeric part to an etching treatment using an etchant selected from an acid, an oxidizing agent, a metal salt, or a combination thereof under mild etching conditions, wherein the etching is performed at a temperature low enough for a short enough period of time so as not to produce microvoids having an average size greater than 0.1 μm.

The graphene sheets can be further decorated with nanoscale particles or coatings of catalytic metals selected from cobalt, nickel, copper, iron, manganese, tin, Zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof.

In certain embodiments, step (a) comprises soaking or immersing the polymeric part in a dispersion and then removing the polymeric part from the dispersion to effect deposition of the graphene sheets and conductive filler onto the surface of the surface-treated polymeric part, wherein the graphene sheets and the conductive filler are bonded to the surface to form a layer of bonded graphene sheets and conductive filler. Alternatively, the graphene/conductive filler mixture dispersion can simply be sprayed onto the polymer part surface, allowing the liquid components to evaporate, and allowing the binder (if present) to cure or set.

In the disclosed method, step (b) may comprise soaking the polymer part in a metallization bath. In a preferred procedure, step (b) comprises the step of immersing the polymer part comprising the layer of bonded graphene sheets/conductive filler in and then withdrawing from an electroless plating bath containing a metal salt dissolved in a liquid medium to effect metallization of the surface of the polymer part.

In certain embodiments, the graphene/conductive filler mixture dispersion further comprises a binder resin having a binder to graphene weight ratio of from 1/5000 to 1/10.

The graphene sheets may be further decorated with nanoscale particles or coatings of catalytic metals selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof, having a diameter or thickness of from 0.5 nm to 100 nm.

The liquid medium may comprise permanganic acid, phosphoric acid, nitric acid, or combinations thereof dissolved in the liquid medium. In certain embodiments, the liquid medium contains an acid, an oxidizing agent, a metal salt, or a combination thereof dissolved therein.

Step (b) may include immersing the polymeric part in a metallization bath to effectuate electroless or electroless plating. The high conductivity of the deposited graphene sheets and conductive fillers enables the plating of one or more metal layers on the graphene/conductive filler-coated polymer component surface. Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. may be chosen for the final metallization procedure.

The present disclosure also provides a graphene/conductive filler mixture dispersion comprising A plurality of graphene sheets and conductive fillers dispersed in a liquid medium, wherein the plurality of graphene sheets comprise single or few-layer graphene sheets selected from native graphene materials having substantially 0% non-carbon elements or non-native graphene materials having 0.001% to 25% by weight non-native graphene materials, wherein the non-native graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodinated graphene, hydrogenated graphene, nitrided graphene, doped graphene, chemical organo energized graphene, or a combination thereof, and wherein the dispersion further comprises one or more species selected from the group consisting of: (i) a binder resin dissolved or dispersed in the liquid medium, wherein the binder to graphene weight ratio is from 1/5000 to 1/10; (ii) an etchant selected from acids, oxidants, metal salts, or combinations thereof; (iii) nanoscale particles or coatings of catalytic metals selected from the group consisting of cobalt, nickel, copper, iron, Manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof; or (iv) combinations thereof.

The conductive filler may be selected from: metal nanowires, carbon fibers, carbon nanofibers, carbon coated fibers, conductive polymer fibers, _nanofibers or nanowires of SnO2 _{, ZnO2} , _In2O3 or indium tin oxide (ITO), conductive polymers not in fiber form, or combinations 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 combinations thereof. The conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothiadene (PITN), polyheteroarylidene vinylene (PArV) (wherein the heteroarylene group may be thiophene, furan or pyrrole), polyparaphenylene (PpP), polyphthalocyanine (PPhc) and the like, and derivatives thereof, and combinations thereof.

In the graphene-conductive filler dispersion, nanoparticles or coatings of catalytic metal may be deposited or modified on the surface of the plurality of graphene sheets. The acid may be selected from permanganate, phosphoric acid, nitric acid, chromic acid, chromic acid, carboxylic acid, acetic acid, and ascorbic acid, or combinations thereof.

Preferred first chemical functional group or preferred second chemical functional group Energy bases were discussed earlier in this section.

10: Faucet assembly

12: Graphene dispersion bath

14: Graphene dispersion

16, 26: Entrance

18, 28: Export

22: Metal plating bath

24: Plating solution

32: Device

Figure 1 shows a flowchart of the most commonly used process for producing graphene oxide sheets, which requires chemical oxidation/intercalation, washing and high temperature puffing procedures.

Figure 2. Schematic diagram of graphene-mediated metallization of polymer parts.

Figure 3. Schematic diagram of a system for graphene-mediated metallization of polymer articles.

The following include definitions of various terms and phrases used throughout this specification.

The term "graphene sheet" means a material comprising one or more planar sheets of bonded carbon atoms densely packed in a hexagonal lattice, wherein the carbon atoms are bonded together by strong in-plane covalent bonds, and also comprising mostly intact ring structures throughout the interior. Preferably, at least 80% of the internal aromatic linkages are intact. In the c-axis (thickness) direction, these graphene planes can be weakly bound together by van der Waals forces. Graphene sheets can contain non-carbon atoms such as OH and COOH functional groups on their edges or surfaces. The term graphene sheet includes pristine graphene, graphene oxide, reduced graphene oxide, halogenated graphene (including fluorinated graphene and chlorinated graphene), nitrided graphene, hydrogenated graphene, doped graphene, functionalized graphene, and combinations thereof. Typically, non-carbon elements comprise 0% to 25% by weight of the graphene sheet. Graphene oxide may contain up to 53% by weight oxygen. The term "doped graphene" covers graphene with less than 10% non-carbon elements. The non-carbon elements may include hydrogen, oxygen, nitrogen, magnesium, iron, sulfur, fluorine, bromine, iodine, boron, phosphorus, sodium, and combinations thereof. Graphene sheets may include single-layer graphene or few-layer graphene, where few-layer graphene is defined as a graphene platelet formed by fewer than 10 graphene planes. Graphene sheets may also include graphene nanoribbons. "Native graphene" covers stones with essentially 0% non-carbon elements Graphene sheet. "Nanographene platelets" (NGPs) refer to graphene sheets having a thickness from less than 0.34 nm (single layer) to 100 nm (multilayer).

The term "substantially" and variations thereof are defined as largely, but not necessarily entirely, what is specified (as understood by those skilled in the art), and in one non-limiting embodiment, generally refers to a range within 10%, within 5%, within 1%, or within 0.5% of the referenced range.

The term "substantially" and variations thereof are defined as largely, but not necessarily completely, what is specified (as understood by those skilled in the art), and in one non-limiting embodiment, generally means within 10%, within 5%, within 1%, or within 0.5% of the referenced range.

Other objects, features and advantages of the invention will become apparent from the following drawings, descriptions and examples. It should be understood, however, that the drawings, descriptions and examples, while indicating particular embodiments of the invention, are given by way of illustration only and are not meant to be limiting. In further embodiments, features from specific embodiments may be combined with features from other embodiments.

The present disclosure provides a surface metallized polymer article comprising: a polymer part having a surface, a first layer of a plurality of graphene sheets and a conductive filler coated on the surface of the polymer part, and a metallized second layer deposited on the first layer, wherein the plurality of graphene sheets comprise single or few-layer graphene sheets selected from a native graphene material having substantially 0% non-carbon elements or a non-native graphene material having 0.001% to 25% by weight non-carbon elements, wherein the non-native graphene sheets Graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodinated graphene, hydrogenated graphene, nitrided graphene, doped graphene, chemically functionalized graphene, or combinations thereof, and wherein the plurality of graphene sheets and the conductive filler are bonded to the surface of the polymer part with or without a binder resin, as shown in FIG. 2 . The first layer has a thickness typically from 0.34 nm to 30 μm (preferably from 1 nm to 1 μm, and further preferably from 1 nm to 100 nm). The second layer (covering metal layer) preferably has a thickness of from 0.5 nm to 1.0 mm, more preferably from 1 nm to 10 μm, and most preferably from 10 nm to 1 μm. use is also Such metallized polymer articles can be easily and easily produced by the surprisingly simple and efficient method described here. Functionalized graphene sheets are surprisingly capable of being bonded to many types of polymer part surfaces without the use of binder resins.

The present disclosure also provides an apparatus that can be used to produce the surface metallized polymer article.在某些實施方式中，如圖3中所示，該設備可以包括：(a)石墨烯沈積室(例如石墨烯分散體浴12 )，該石墨烯沈積室容納石墨烯分散體14 ，該石墨烯分散體包含分散在第一液體介質中的多個石墨烯片和視需要的導電填料以及溶解在該第一液體介質中的視需要的黏合劑樹脂，其中操作該石墨烯沈積室以將這些石墨烯片和視需要的導電填料沈積到至少一個聚合物部件的表面上，以形成至少一個石墨烯塗覆的聚合物部件(例如，水龍頭組件10 )；以及(b)與該石墨烯沈積室處於工作關係的金屬化室(例如金屬鍍浴22 )(例如，佈置在石墨烯分散體浴12附近)，該金屬化室容納鍍液24 ，該鍍液用於在該至少一個石墨烯塗覆的聚合物部件上鍍所需金屬的層以獲得該表面金屬化的聚合物製品。

Preferably, the graphene deposition chamber 12 has an inlet 16 and an outlet 18 , correspondingly, fresh graphene dispersion can be pumped into the graphene deposition chamber through the inlet, and waste graphene dispersion can be pumped out through the outlet. Further preferably, the metallization chamber 22 has an inlet 26 and an outlet 28 , correspondingly, fresh plating solution can be pumped into the metallization chamber through the inlet, and waste graphene dispersion can be pumped out through the outlet.

The apparatus may further comprise a removable carrier for carrying the at least one polymer part and contacting the at least one polymer part with the graphene dispersion (e.g., for dipping the at least one polymer part in the graphene dispersion bath and then withdrawing the at least one polymer part from the bath) to produce the at least one graphene-coated polymer part and/or for contacting the at least one graphene-coated polymer part with the plating solution (e.g., for dipping the at least one graphene-coated polymer part in the metal plating bath) bath, and then withdrawing the at least one graphene-coated polymer part from the bath) to obtain the desired polymeric surface metallization Items.

The apparatus may further comprise drying, heating or curing providing means 32 in working relationship with the graphene deposition chamber (e.g., above and between the graphene dispersion bath and the metallization chamber) for partially or completely removing the first liquid medium from the at least one graphene-coated polymer part and/or for polymerizing or curing the optional binder resin to produce the at least one graphene-coated polymer part comprising a plurality of graphene sheets bonded to the surface of the at least one polymer part. As an example, as shown schematically in FIG. 3 , the faucet assembly 10 is shown having exited the graphene deposition bath 12 and being heated, dried or cured. After completing the drying/heating/curing procedure, the faucet is immersed in the metallization bath 22 .

In this apparatus, the plating solution 24 may comprise an electroless plating solution, an electrochemical plating solution, or an electrolytic solution. Preferably, the plating solution includes an electroless plating solution containing a metal salt dissolved in water or an organic solvent, such as CuSO ₄ or NiNO ₃ dissolved in water for copper or nickel plating. Various graphene sheets incorporated on the surface of polymer parts are surprisingly capable of attracting metal ions to the surface of graphene-covered or graphene-coated polymer parts. The adhesion of the metal to this surface is surprisingly strong, scratch-resistant and hard. The deposited metal layer provides the desired gloss and metallic appearance on the surface of the polymer part.

The operation of the above procedure can be carried out in a continuous or batch mode and can be fully automated.

In certain embodiments, the conductive filler is selected from the group consisting of metal nanowires, carbon fibers, carbon nanofibers, carbon-coated fibers, conductive polymer fibers, _nanofibers or nanowires of SnO2 _{, ZnO2} , _In2O3 , or indium tin oxide (ITO), conductive polymers not in fiber form, or combinations thereof. The metal nanowires are preferably nanowires selected from silver (Ag), gold (Au), copper (Cu), platinum (Pt), zinc (Zn), cadmium (Cd), cobalt (Co), molybdenum (Mo), aluminum (Al), or combinations thereof. The conductive polymer is preferably selected from the group consisting of polydiacetylene, polyacetylene (PAc), polypyrrole (PPy), polyaniline (PAni), polythiophene (PTh), polyisothiadene (PITN), polyheteroarylidene vinylene (PArV) (wherein the heteroarylene group may be thiophene, furan or pyrrole), polyparaphenylene (PpP), polyphthalocyanine (PPhc) and the like, and derivatives thereof, and combinations thereof.

及其組合。 In some embodiments, the chemically functionalized graphene sheet contains chemical functional groups selected from the group consisting of alkyl or aryl silanes, alkyl or aralkyl groups, hydroxyl groups, carboxyl groups, amine groups, sulfonic acid groups ( _--SO3H ), aldehyde groups, quinone groups, fluorocarbons, or combinations thereof. Alternatively, the functional groups include derivatives of azido compounds selected from the group consisting of 2-azidoethanol, 3-azidopropan-1-amine, 4-(2-azidoethoxy)-4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropionate, chloroformate, azidocarbonate, dichlorocarbene, carbene, aryne, azone, (R-)-oxycarbonyl Nitrene, where R = any of the following groups:

and their combinations.

In certain embodiments, the functional group is selected from the group consisting of hydroxyl, peroxide, ether, keto, and aldehyde.在某些實施方式中，該官能化劑含有選自下組的官能基，該組由以下各項組成：SO ₃ H、COOH、NH ₂ 、OH、R'CHOH、CHO、CN、COCl、鹵根(halide)、COSH、SH、COOR'、SR'、SiR' ₃ 、Si(--OR'--) _y R' _3-y 、Si(--O--SiR' ₂ --)OR'、R”、Li、AlR' ₂ 、Hg--X、TlZ ₂和Mg--X；其中y係等於或小於3的整數，R'係氫、烷基、芳基、環烷基或芳烷基、環芳基或聚(烷基醚)，R”係氟代烷基、氟代芳基、氟代環烷基、氟代芳烷基或環芳基，X係鹵根，並且Z係羧酸根或三氟乙酸根、及其組合。

The functional groups may be selected from the group consisting of amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines, anhydrides, ketimines, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), polyethylenepolyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated curing agents, non-amine curing agents, and combinations thereof.

In some embodiments, the functional group can be selected from: OY, NHY, O=C--OY, P=C--NR'Y, O=C--SY, O=C--Y, --CR'1--OY, N'Y or C'Y, and Y is a functional group of a protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme inhibitor or a transition state analog of an enzyme substrate or is selected from R'--OH, R'--NR'₂, R'SH, R'CHO, R'CN, R'X, R'N⁺(R')₃x^-, R'SiR'₃、R'Si(--OR'--)_{the y}R'_3-y, R'Si(--O--SiR'₂--)OR', R'--R", R'--N--CO, (C₂h₄O--)_wH, (--C₃h₆O--)_wH, (--C₂h₄O)_w--R', (C₃h₆O)_w--R', R', and w is an integer greater than 1 and less than 200.

The present disclosure also provides a method of metallizing a polymer surface (eg, a surface of a non-electronically conductive plastic). Within the scope of the method, according to an embodiment of the present disclosure, the plastic surface of a plastic article or the plastic surfaces of several plastic articles is metallized.

Coating polymer part surfaces with metals (also known as polymer plating or polymer metallization) is becoming increasingly important. With the polymer plating method, laminates are produced that combine the advantages of polymers and metals. The use of polymer components allows for significant weight savings compared to metal parts. Electroplating of polymer moldings is often performed for cosmetic purposes, EMI masking or modification of surface properties.

This section begins with a description of the most common prior art processes used to produce metallized plastic articles. It then focuses on describing the problems associated with this prior art process. This is followed by a discussion of the process and resulting product of the present disclosure which overcomes all of these problems.

In prior art processes for metallizing polymeric parts, these parts are typically held in a frame and exposed to a number of different process fluids in a specific process sequence. As a first step, the plastic is typically pretreated to remove impurities, such as grease, from the surface. Subsequently, an etching process is used to make the table Surface roughening ensures adequate adhesion of subsequent metal layers to the polymer surface. In etching operations, it is particularly important to form a uniform structure in the form of depressions, such as surface openings or microcavities, on the plastic surface. Subsequently, the roughened surface is treated with an activator to form a catalytic surface for subsequent electroless metallization or electroless plating. For this purpose, ion-generating activators or colloidal systems are used.

In the prior art procedure, the plastic surface intended for activation with an ion-generating system is first treated with tin(II) ions, after which treatment a firmly adhered tin oxide hydrate gel is produced and rinsed with water. During subsequent treatment with a palladium salt solution, palladium nuclei are formed on the surface by redox reactions with tin(II) species. These palladium nuclei are catalytic for chemical metallation. For activation with colloidal systems, colloidal palladium solutions are generally used, which are formed by reacting palladium chloride with tin(II) chloride in the presence of excess hydrochloric acid.

After activation, the plastic part is typically first chemically metallized using a metastable solution of a metallization bath. These baths generally contain the metal to be deposited as a salt in aqueous solution and a reducing agent for the metal salt. When the chemical metallization bath comes into contact with metal nuclei (eg, palladium seeds) on the plastic surface, a metal is formed by reduction, which deposits on the surface as a firmly adherent layer. The chemical metallization step is typically used to deposit copper, nickel or nickel alloys with phosphorous and/or boron.

The chemically metallized polymer surface can then be further electrolytically deposited with a metal layer. Electrolytic deposition of a copper layer or an additional nickel layer is typically performed prior to the electrochemical application of the desired decorative chromium layer.

There are several major problems associated with this prior art process for producing metallized polymer articles:

1) The process is tedious and involves many steps: pretreatment, chemical etching, activation, chemical metallization and electrolytic deposition of multiple metal layers (hence, multiple steps).

2) The most commonly used etchant is 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 during etching procedures, after handling and disposal. Due to chemical processes in the etching process (such as reduction of the chromium compounds used), the chromium-sulfuric acid etchant is used up and generally cannot be reused.

3) The key process step of plastic electroplating is to create micro-holes so that the metal can adhere to the plastic surface. These microvoids serve as starting points for the growth of metal nuclei in subsequent metallization steps. Typically, these microvoids have a size of about 0.1 μm to 10 μm. In particular, these microcavities exhibit a depth (ie, the degree from the plastic surface towards the interior) in the range from 0.1 μm to 10 μm. Unfortunately, surface microvoids can be stress concentration sites that can weaken plastic parts.

4) After etching or roughening of the plastic surface, the surface is first activated with colloidal palladium or ion-generating palladium. This activation is followed by removal of the protective tin colloid in the case of colloidal processes, or by reduction to elemental palladium in the case of ionogenic processes. Subsequently, copper or nickel is chemically deposited on the plastic surface as a conductive layer. After this, electroplating or metallization takes place. In practice, this direct metallization of plastic surfaces is only possible with certain plastics. If it is not possible to sufficiently roughen the plastic or form suitable microcavities by etching the plastic surface, a functionally firm adhesion of the metal layer to the plastic surface cannot be guaranteed. Therefore, in prior art processes, the amount of plastic that can be coated is very limited.

5) Precious metals such as palladium are very expensive.

The present disclosure provides a graphene-mediated method for producing metallized polymer articles. The disclosed method overcomes all these problems.

In certain embodiments, the method comprises: (a) optionally treating the surface of the polymeric part to produce a surface-treated polymeric part (this procedure is optional because the graphene dispersion itself is capable of pretreating the polymer surface); (b) providing a graphene dispersion (also referred to herein as a graphene/conductive filler mixture dispersion) comprising a plurality of graphene sheets (functionalized or unfunctionalized) and a conductive filler (in the form of nanofibers, nanoparticles, nanowires, etc.) dispersed in a liquid medium, such that the Surface-treated or untreated polymer parts are contacted with the graphene dispersion, and the graphite depositing olefin sheets and the conductive filler onto the surface of the surface-treated polymer part, wherein the graphene sheets and the conductive filler are bonded to the surface to form a layer of bonded graphene sheets/conductive filler covering (partially or completely) the surface of the polymer part; and (c) chemically, physically, electrochemically or electrolytically depositing a metal layer on the surface of the covered polymer part surface to form the surface metallized polymer article. Again, step (a) is optional in the disclosed methods.

二唑、聚苯並

唑、聚苯並二

唑、聚噻唑、聚苯並噻唑、聚苯並二噻唑、聚(對伸苯基伸乙烯基)、聚苯並咪唑、聚苯並二咪唑、其共聚物、其聚合物共混物、或其組合。 As an example, the polymeric component may be selected from polyethylene, polypropylene, polybutylene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene-styrene (ABS), polyester, polyvinyl alcohol, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene oxide (PPO), polymethyl methacrylate (PMMA), copolymers thereof, polymer blends thereof, or combinations thereof. The polymer can also be selected from phenolic resin, polyfurfuryl alcohol, polyacrylonitrile, polyimide, polyamide, poly

Oxadiazole, polybenzo

Azole, Polybenzobis

oxazole, polythiazole, polybenzothiazole, polybenzobithiazole, poly(p-phenylene vinylene), polybenzimidazole, polybenzodiimidazole, copolymers thereof, polymer blends thereof, or combinations thereof.

In certain embodiments, step (a) is omitted from the process because the liquid medium in the graphene dispersion is generally capable of removing grease and other undesirable species from the surface of the polymer part. Some liquid medium in the graphene dispersion can further provide an etching effect to produce small surface depressions with a depth of <0.1 μm (mild etching conditions). In these cases, the entire process requires only three simple steps.

In certain embodiments, step (a) may include the step of subjecting the surface of the polymeric part to an abrasive treatment, an etching treatment, or a combination thereof. In some embodiments, step (a) includes the step of subjecting the surface of the polymeric part to an etching treatment using an etchant selected from an acid, an oxidizing agent, a metal salt, or a combination thereof. Preferably, step (a) includes the step of subjecting the surface of the polymer part to an etching treatment without using chromic acid or chromic sulfuric acid. More preferably, step (a) comprises the step of subjecting the surface of the polymeric part to an etching treatment using an etchant selected from an acid, an oxidizing agent, a metal salt, or combinations thereof under mild etching conditions, wherein the etching is performed at a temperature sufficiently low for a sufficiently short period of time so that Microvoids with an average size greater than 0.1 μm were not produced.

Mild etching as referred to in the present invention means that "etching" or treating the plastic surface with an etching solution occurs at low temperature and/or for a short period of time at a low concentration of the etching solution. Mild etching conditions can be achieved when one of the aforementioned three conditions is satisfied. Low temperature mentioned in this disclosure means a maximum temperature of 40°C, preferably <30°C, and most preferably from 15°C to 25°C. At the low temperature mentioned above, the pretreatment with the etching solution is carried out within a period of 3 minutes to 15 minutes, preferably 5 minutes to 15 minutes, and even more preferably 5 minutes to 10 minutes. The higher the temperature, the shorter the processing time. However, mild etch conditions can also be achieved at temperatures in excess of 40 °C if the selected processing time is suitably short. According to an embodiment of the present disclosure, the etching process is performed at a temperature of 40° C. to 95° C., preferably 50° C. to 70° C., for a processing time of 15 seconds to 5 minutes, preferably 0.5 minute to 3 minutes. Actually, the process temperature and/or process time are selected according to the type of etching solution used.

Gentle etching also means that, contrary to the above-mentioned prior art processes, no roughening of the polymer surface or generation of microvoids in the polymer surface takes place. Microcavities produced with etching according to prior art processes typically have a diameter or depth in the size range of 0.1 μm to 10 μm. In the present disclosure, the etching conditions are adjusted such that only small openings or pores are produced in the polymer surface, these small openings or pores having a diameter of <0.1 μm, preferably <0.05 μm and especially a depth. In this context, depth means the extent from the surface of the polymer to the openings/channels inside the polymer. Etching in the classical sense as in the case of prior art processes is therefore not performed here. In the process of the present disclosure, where step (a) is eliminated, the liquid medium in the graphene dispersion can typically produce openings or pores with a size <0.1 μm. Contrary to what was suggested by prior art teaching, we have surprisingly observed that the graphene-mediated metallization method of the present disclosure does not require the generation of microvoids with a size larger than 0.1 μm. The method works even on highly smooth surfaces.

In step (a), the etching treatment may be achieved with an etching solution and/or by plasma treatment or by plasma etching, ion bombardment, or the like.

Preferably, the etching solution used for etching contains at least one oxidizing agent. Mild etching within the scope of the present disclosure also means that the oxidizer is used in low concentrations. Permanganates and/or peroxodisulfates and/or periodates and/or peroxides can be used as oxidizing agents. According to one embodiment of the present disclosure, the etching is performed by an acid etching solution comprising at least one oxidizing agent. An oxidizing agent and/or an acid or basic solution (discussed below) may be added to the graphene dispersion instead of using a separate etching solution, and as such, step (a) and step (b) are essentially combined into a single step.

Preferably, an aqueous etching solution containing permanganate and phosphoric acid (H ₃ PO ₄ ) and/or sulfuric acid is used. Potassium permanganate can be used as permanganate. It is very preferred to use an acid etching solution which contains only phosphoric acid or mainly phosphoric acid and only small amounts of sulfuric acid.

According to another embodiment of the present disclosure, the etching treatment is performed by an alkaline aqueous solution containing permanganate. Here again, it is preferred to use potassium permanganate. The alkaline aqueous solution may contain lye. The type of etching solution used depends on the type of polymer being treated. A preferred concentration of the oxidizing agent in the etching solution is 0.05 mol/l to 0.6 mol/l. Preferably, the etching solution contains 0.05 mol/l to 0.6 mol/l of permanganate or persulfate. The etching solution may contain 0.1 mol/l to 0.5 mol/l of periodate or hydrogen peroxide. A preferred permanganate ratio is 1 g/l up to the solubility limit of permanganate, preferably potassium permanganate. The permanganate solution preferably contains 2 g/l to 15 g/l permanganate, more preferably 2 g/l to 15 g/l potassium permanganate. The permanganate solution may contain a wetting agent.

Mild etching can also be achieved by using dilute persulfate aqueous solution or periodide solution or dilute peroxide aqueous solution (used as a separate etching solution or as part of the graphene dispersion). It is preferable to perform the mild etching treatment with the etching solution while stirring the solution. After mild etching, the plastic surface is rinsed in water, eg, for 1 to 3 minutes. According to a preferred embodiment of the present disclosure, the treatment with the metal salt solution is carried out at a temperature <30°C, preferably between 15°C and 25°C (room temperature included). In practice, the treatment with the metal salt solution is carried out without stirring. The preferred treatment time is 30 seconds to 15 minutes, more preferably 3 minutes to 12 minutes. Preferably, the use of metal salts solution, the solution has a pH value between 7.5 and 12.5, preferably adjusted to between 8 and 12. Preferably, a metal salt solution containing ammonia and/or at least one amine is used. The above mentioned pH adjustment can be achieved with the aid of ammonia, and preferably with an alkali metal salt solution. Metal salt solutions containing one or more amines may also be used. For example, the metal salt solution may contain monoethanolamine and/or triethanolamine. Treatment with a metal salt solution means preferably immersing the surface of the polymer part in the metal salt solution.

In certain embodiments, step (b) comprises soaking or immersing the surface-treated or untreated polymeric part in a graphene dispersion, and then removing the polymeric part from the graphene dispersion to effect deposition of graphene sheets and conductive fillers onto the surface of the surface-treated polymeric part, wherein the graphene sheets and conductive fillers are bonded to the surface to form a bonded graphene sheet/conductive filler layer. Alternatively, the graphene dispersion can simply be sprayed onto the polymer part surface, the liquid component is allowed to evaporate, and the binder (if present) is allowed to cure or set.

If present, the adhesive resin layer may be formed of an adhesive resin composition containing an adhesive resin as a main component. The binder resin composition may contain a curing agent and a coupling agent as well as a binder resin. Examples of the binder resin may include ester resins, urethane resins, urethane ester resins, acrylic resins, and acrylic urethane resins, particularly ester resins containing neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid, and terephthalic acid. The curing agent may be present in an amount of 1 to 30 parts by weight based on 100 parts by weight of the binder resin. The coupling agent may include epoxysilane compounds.

Curing of the adhesive layer can be performed via heat, UV or ionizing radiation. This may involve heating the layer coated with the thermally curable composition to a temperature of at least 70°C, preferably 90°C to 150°C, for at least 1 minute (typically up to 2 hours, and more typically from 2 minutes to 30 minutes) to form a hard coating.

The surfaces of polymeric parts can be bonded to graphite using dipping, coating (e.g., doctor blade coating, rod coating, slot die coating, comma coating, reverse roll coating, etc.), roll-to-roll processing, inkjet printing, screen printing, microcontact, gravure coating, spray coating, ultrasonic spray coating, electrostatic spray coating, and flexographic printing. ene or CNT dispersions. The thickness of the hard coat layer or adhesive layer is usually about 1 nm to 10 μm, preferably 10 nm to 2 μm.

For thermally curable resins, the polyfunctional epoxy monomer may preferably be selected from diglyceryl tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether (such as pentaerythritol tetraglycidyl ether), or combinations thereof. The difunctional or trifunctional epoxy monomer may be selected from the group consisting of trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, triphenol triglycidyl ether, tetrahydroxyphenylethane triglycidyl ether, tetrahydroxyphenylethane triglycidyl ether, p-aminophenol triglycidyl ether, 1,2,6-hexane triglycidyl ether Alcohol Triglycidyl Ether, Glycerin Triglycidyl Ether, Diglycerol Triglycidyl Ether, Glycerin Ethoxylated Triglycidyl Ether, Castor Oil Triglycidyl Ether, Propoxylated Glycerol Triglycidyl Ether, Ethylene Glycol Diglycidyl Ether, 1,4-Butanediol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, Cyclohexanedimethanol Diglycidyl Ether, Dipropylene Glycol Diglycidyl Ether, Polypropylene Glycol Diglycidyl Ether, Dibromoneopentyl Glycidyl Diglycidyl Ether Hydrogenated glyceryl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl carboxylate and mixtures.

In certain embodiments, the thermally curable compositions of the present disclosure advantageously further contain a small amount, preferably from 0.05% to 0.20% by weight, of at least one surface active compound. Surfactants are important for good wetting of the substrate, resulting in a satisfactory final hardcoat.

UV radiation-curable resins and lacquers useful for the adhesive layer used in the present disclosure are those derived from photopolymerizable monomers and oligomers of polyfunctional compounds, such as acrylate and methacrylate oligomers (the term "(meth)acrylate" as used herein refers to acrylate and methacrylate), such as polyols with (meth)acrylate functionality and their derivatives, 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, 1,6-hexanediol di(meth)acrylate, or neopentyl glycol di(meth)acrylate and mixtures thereof, and acrylate and methacrylate oligomers derived from low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, epoxy acrylates, polybutadiene resins, and polythiol-polyene resins.

The UV polymerizable monomers and oligomers are applied (for example after exiting from dipping) and dried, and then exposed to UV radiation to form an optically clear crosslinked abrasion resistant layer. The preferred UV curing dose is between 50mJ/cm ² and 1000mJ/cm ² .

UV curable resins are typically also ionizing radiation curable. Ionizing radiation curable resins may contain relatively large amounts of reactive diluents. Reactive diluents useful herein include monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, vinyltoluene, and N-vinylpyrrolidone; and polyfunctional monomers such as 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 , 1,6-hexanediol di(meth)acrylate, or neopentyl glycol di(meth)acrylate.

In the disclosed method, step (c) may comprise soaking the graphene-bonded polymer part in a metallization bath. The high conductivity of the deposited graphene sheets readily enables the electroplating of one or more metal layers on the surface of graphene/conductive filler-coated polymer components.

Alternatively and advantageously, the final metallization step can be accomplished by using an electroless plating method that does not employ expensive precious metal solutions. This step may involve immersing (soaking) the graphene/conductive filler-coated polymer part in an _electroless plating bath containing a metal salt (a salt of a metal such as Cu, Ni, or Co expected) dissolved in a liquid medium (e.g., CuSO in water or _NiNO in water). Such an impregnation procedure typically requires a contact time of from 3 seconds to 30 minutes.

Copper metal plating baths (or nickel plating baths) may contain copper salts (or Ni salts) and additive depletion inhibitors compound. Additive depletion inhibiting compounds may include methylthione, methylthione, tetramethylenethione, mercaptoacetic acid, 2(5H)thiophenone, 1,4-dithiophene, trans-1,2-dithiophene, tetrahydrothiophen-3-one, 3-thiophenemethanol, 1,3,5-trithiophene, 3-thiopheneacetic acid, thiotetronic acid, crown thioether, tetrapyrid, dipropyltrisulfide, bis(3-trithiophene) Ethoxysilylpropyl tetrasulfide, dimethyl tetrasulfide, methyl methanethiosulfate, (2-sulfatoethyl)methane, p-tolyldisulfide, p-tolyldisulfide, bis(phenylsulfonyl)sulfide, 4-(chlorosulfonyl)benzoic acid, isopropylsulfonyl chloride, 1-propanesulfonyl chloride, lipoic acid, 4-hydroxybenzenesulfonic acid, phenylvinylsulfide, or mixtures thereof.

Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. may be chosen for the final metallization procedure.

The preparation of graphene sheets and graphene dispersions is described as follows: Carbon is known to have five unique crystal structures, including diamond, fullerene (0-D nanographite material), carbon nanotubes or carbon nanofibers (1-D nanographite material), graphene (2-D nanographite material), and graphite (3-D graphite material). Carbon nanotubes (CNTs) refer to tubular structures grown with single or multiple walls. Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have diameters of about several nanometers to several hundred nanometers. Its longitudinal, hollow structure endows the material with unique mechanical, electrical and chemical properties. CNT or CNF is one-dimensional nano-carbon or 1-D nano-graphite material.

As early as 2002, our research group pioneered the development of graphene materials and related production processes: (1) B.Z. Jang and W.C. Huang, "ano-scaled Graphene Plates [nano-scale graphene plates]", U.S. Patent No. 7,071,258 (07/04/2006), application filed on October 21, 2002; (2) B.Z. Jang et al. "Process for Producing Nano-scaled Graphene Plates," U.S. Patent Application No. 10/858,814 (06/03/2004) (U.S. Patent Publication No. 2005/0271574); and (3) B.Z. Jang, A. Zhamu, and J. Guo, "Process for Producing Nano-scaled Platelets and Nano composites [Processes for the production of nanoscale platelets and nanocomposites]", U.S. Patent Application No. 11/509,424 (08/25/2006) (U.S. Patent Publication No. 2008-0048152).

5重量%的氧)、微氟化石墨烯(<5重量%的氟)、氟化石墨烯(

5重量%的氟)、其他鹵化石墨烯、以及化學官能化石墨烯。 Single-layer graphene sheets are made of carbon atoms occupying a two-dimensional hexagonal lattice. Multilayer graphene is a lamella composed of more than one plane of graphene. Individual single-layer graphene sheets and multi-layer graphene platelets are collectively referred to herein as nanographene platelets (NGPs) or graphene materials. NGPs include pristine graphene (essentially 99% carbon atoms), micrographene oxide (<5% by weight oxygen), graphene oxide (

5% by weight of oxygen), microfluorinated graphene (<5% by weight of fluorine), fluorinated graphene (

5% by weight of fluorine), other halogenated graphene, and chemically functionalized graphene.

NGPs have been found to possess a range of unusual physical, chemical and mechanical properties. For example, graphene was found to exhibit the highest intrinsic strength and highest thermal conductivity of all existing materials. Although practical electronic device applications of graphene (e.g., replacing Si as the backbone in transistors) are not envisioned to occur within the next 5–10 years, its applications as nanofillers in composite materials and as electrode materials in energy storage devices are imminent. The availability of large quantities of processable graphene sheets is critical to the successful development of graphene for composites, energy, and other applications.

Recently, we reviewed the processes for producing NGP and NGP nanocomposites [Bor Z. Jang and A Zhamu, "Processing of Nano Graphene Platelets (NGPs) and NGP Nanocomposites: A Review," J. Materials Sci. 43 (2008) 5092-510 1].

A very useful method (Fig. 1) entails treating natural graphite powder with an intercalation agent and an oxidizing agent (e.g., concentrated sulfuric acid and nitric acid, respectively) to obtain graphite intercalation compounds (GICs) or indeed graphite oxide (GO). [William S.Hummers, Jr. et al., Preparation of Graphitic Oxide[Graphite Oxide Preparation], Journal of the American Chemical Society[American Chemical Society Journal], 1958, p. 1339. ] Prior to intercalation or oxidation, graphite has a graphene interplanar spacing of approximately 0.335 nm ( L _d =½ d ₀₀₂ =0.335 nm). In the case of intercalation and oxidation treatments, the intergraphene spacing increases to values typically greater than 0.6 nm. This is the first expansion stage that graphite materials undergo during this chemical route. The resulting GiC or GO is then subjected to further expansion (often referred to as exfoliation ) using thermal shock exposure or solution-based ultrasonic treatment-assisted exfoliation of the graphene layer.

In the thermal shock exposure method, GiC or GO is exposed to high temperature (typically 800°C-1,050°C) for a short period of time (typically 15 to 60 seconds) to puff or expand the GIC or GO to form puffed or further expanded graphite, typically in the form of "graphite worms" composed of graphite flakes that are still interconnected to each other. This thermal shock procedure can produce some detached graphite flakes or graphene sheets, but usually most of the graphite flakes remain interconnected. Typically, the extruded graphite or graphite worms are then subjected to flake separation using air milling, mechanical shearing, or ultrasonic treatment in water. Thus, Method 1 essentially requires three distinct procedures: first expansion (oxidation or intercalation), further expansion (or "expansion"), and separation.

In the solution-based separation method, swollen or puffed GO powders were dispersed in water or alcoholic aqueous solutions and subjected to sonication. It is important to note that in these processes, ultrasonic treatment is used after the intercalation and oxidation of graphite (ie, after the first expansion) and typically after the thermal shock exposure of the resulting GIC or GO (after the second expansion). Alternatively, GO powders dispersed in water were subjected to ion exchange or lengthy purification procedures in such a way that the repulsive forces between ions present in the interplanar space outweighed the van der Waals forces between the graphenes, resulting in graphene layer separation.

In the above example, the starting material for preparing graphene sheets or NGPs is a graphite material, which can be selected from the group consisting of natural graphite, artificial graphite, graphite oxide, fluorinated graphite, graphite fiber, carbon fiber, carbon nanofiber, carbon nanotube, mesocarbon microbeads (MCMB) or carbonaceous microspheres (CMS), soft carbon, hard carbon, and combinations thereof.

Graphite oxide can be prepared by dispersing or soaking a layered graphite material (e.g., powder of natural flake graphite or synthetic graphite) in an oxidizing agent, typically a mixture of an intercalating agent (e.g., concentrated sulfuric acid) and an oxidizing agent (e.g., nitric acid, hydrogen peroxide, sodium perchlorate, potassium permanganate) at a desired temperature (typically 0°C to 70°C) or soaking for a sufficient period of time (typically 4 hours to 5 days). The resulting graphite oxide particles are then washed several times with water to adjust the pH to typically 2-5. The resulting suspension of graphite oxide particles dispersed in water was then subjected to ultrasonic treatment to produce a dispersion of isolated graphene oxide sheets dispersed in water. A small amount of reducing agent such as _Na4B can be added to obtain reduced graphene oxide (RDO) sheets.

To reduce the time required to generate the precursor solution or suspension, one may choose to oxidize the graphite to some extent for a shorter period of time (eg, 30 minutes to 4 hours) to obtain a graphite intercalation compound (GIC). The GIC particles are then exposed to thermal shock, preferably in the temperature range of 600°C to 1,100°C typically for 15 seconds to 60 seconds, to obtain expanded graphite or graphite worms, which are optionally (but preferably) subjected to mechanical shear (e.g. using a mechanical shear or ultrasonic wave generator) to break up the graphite flakes that make up the graphite worms. The graphene sheets that have been separated (after mechanical shearing) or unbroken graphite worms or individual graphite flakes are then redispersed in water, acid or organic solvents and ultrasonicated to obtain graphene dispersions.

The native graphene material is preferably produced by one of the following three processes: (A) intercalation of the graphite material with a non-oxidizing agent followed by thermal or chemical expansion in a non-oxidizing environment; (B) subjecting the graphite material to a supercritical fluid environment for infiltration and expansion between graphene layers; or (C) dispersing the graphite material in powder form into an aqueous solution containing a surfactant or dispersant to obtain a suspension and subjecting the suspension to direct ultrasonic treatment to obtain a graphene dispersion.

In procedure (A), a particularly preferred step comprises (i) intercalating the graphite material with a non-oxidizing agent selected from an alkali metal (e.g., potassium, sodium, lithium, or cesium), an alkaline earth metal, or an alloy, mixture, or eutectic of an alkali metal or an alkaline earth metal; and (ii) chemical expansion treatment (e.g., by soaking the potassium intercalated graphite in an ethanol solution).

In procedure (B), a preferred step involves immersing the graphite material in a supercritical fluid such as carbon dioxide (e.g., at a temperature T>31° C. and a pressure P>7.4 MPa) and water (e.g., at a temperature T>374° C. and a pressure P>22.1 MPa) for a period of time sufficient to allow graphene interlayer infiltration (temporary intercalation). This step is then followed by a sudden decompression to expand the individual graphene layers. Other suitable supercritical fluids include methane, ethane, ethylene, hydrogen peroxide, ozone, water oxides (water with high concentrations of dissolved oxygen), or a mixture thereof.

In procedure (C), the preferred steps include (a) dispersing particles of graphitic material in a liquid medium containing a surfactant or dispersant therein to obtain a suspension or slurry; and (b) exposing the suspension or slurry to ultrasonic waves of a certain energy level (a process commonly referred to as sonication) for a time sufficient to produce a graphene dispersion of isolated graphene sheets (non-oxidized NGP) dispersed in a liquid medium such as water, alcohol or an organic solvent.

NGPs can be produced with an oxygen content of not more than 25% by weight, preferably less than 20% by weight, more preferably less than 5%. Typically, the oxygen content is between 5% and 20% by weight. Oxygen content can be determined using chemical elemental analysis and/or X-ray photoelectron spectroscopy (XPS).

The layered graphite material used in the prior art processes for the production of GIC, graphite oxide and subsequently fabricated exfoliated graphite, flexible graphite flakes and graphene platelets is in most cases natural graphite. However, the present disclosure is not limited to 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 fibers, carbon fibers, carbon nanofibers, carbon nanotubes, mesocarbon microbeads (MCMB) or carbonaceous microspheres (CMS), soft carbon, hard carbon, and combinations thereof. All of these materials contain graphitic crystallites consisting of planar layers of graphene stacked or bonded together via van der Waals forces. In natural graphite, multiple planar stacks of graphene (where the orientation of the graphene planes vary from stack to stack) are clustered together. In carbon fibers, graphene planes are usually oriented in a preferred direction. In general, soft carbons are carbonaceous materials obtained by carbonization of liquid aromatic molecules. Their aromatic rings or graphene structures are substantially parallel to each other, enabling further graphitization. Hard carbons are carbonaceous materials obtained from aromatic solid materials such as polymers such as phenolic resins and polyfurfuryl alcohol. Their graphene structures are relatively randomly oriented, and thus further graphitization is difficult to achieve even at temperatures above 2,500°C. However, graphene sheets do exist in these carbons.

Fluorinated graphene or graphene fluoride is used herein as an example of the group of halogenated graphene materials. There are two different approaches, which have been followed to produce fluorinated graphene: (1) fluorination of pre-synthesized graphene: this method requires treatment of graphene prepared by mechanical expansion or by CVD growth with a fluorinating agent such as _XeF2 or F-based plasma; (2) expansion of multilayer fluorinated graphite: both mechanical expansion and liquid phase expansion of fluorinated graphite can be easily achieved [F. Karlicky et al. " Halagenated Graphenes: Rapidly Growing Families ly of Graphene Derivatives "[Halographene: a rapidly growing family of graphene derivatives] ACS Nano [ACS Nano], 2013, 7(8), pp. 6434-6464].

x

24)。在(CF) _n 中碳原子係sp3雜化的並且因此氟碳化合物層係波紋狀的，由反式連接的環己烷椅組成。在(C₂F) _n 中，只有一半的C原子被氟化，並且每對相鄰的碳片藉由共價C-C鍵連接在一起。對氟化反應的系統研究表明，所得到的F/C比率在很大程度上取決於氟化溫度、氟化氣體中氟的分壓和石墨先質的物理特性，包括石墨化度、粒度和比表面積。除了氟(F₂)之外，可以使用其他氟化劑，儘管大多數現有文獻涉及用F₂氣體進行氟化(有時在氟化物的存在下)。 The interaction of F ₂ with graphite at high temperature leads to covalent fluorinated graphite (CF) _n or (C ₂ F) _n , while at low temperature a graphite intercalation compound (GIC) C _x F(2

x

twenty four). The carbon atoms in (CF) _n are sp3 hybridized and thus the fluorocarbon layer is corrugated, consisting of trans-linked cyclohexane chairs. In (C ₂ F) _n , only half of the C atoms are fluorinated, and each pair of adjacent carbon sheets is linked together by covalent CC bonds. Systematic studies of fluorination reactions have shown that the resulting F/C ratios are highly dependent on the fluorination temperature, the partial pressure of fluorine in the fluorination gas, and the physical properties of the graphitic precursors, including degree of graphitization, particle size, and specific surface area. In addition to fluorine ( _F2 ), other fluorinating agents can be used, although most of the existing literature refers to fluorination with _F2 gas (sometimes in the presence of fluoride).

In order to puff layered precursor materials into individual graphene-layer or few-layer states, it is necessary to overcome the attractive forces between adjacent layers and further stabilize these layers. This can be achieved by covalently modifying the graphene surface with functional groups or by non-covalent modification using specific solvents, surfactants, polymers, or donor-acceptor aromatic molecules. The process of liquid phase expansion involves ultrasonic treatment of fluorinated graphite in a liquid medium to produce fluorinated graphene sheets dispersed in the liquid medium. The resulting dispersion can be used directly for graphene deposition on the surface of polymer parts.

Nitriding of graphene can be performed by exposing graphene material (eg graphene oxide) to ammonia at high temperature (200ºC-400ºC). Graphene nitride can also be formed at lower temperatures by a hydrothermal method; for example by sealing GO and ammonia in an autoclave and then raising the temperature to 150ºC-250ºC. Other methods of synthesizing nitrogen-doped graphene include nitrogen plasma treatment on graphene, graphene in the presence of ammonia, Arc discharge between electrodes, ammonolysis of graphene oxide under CVD conditions, and hydrothermal treatment of graphene oxide and urea at different temperatures.

For purposes of defining the scope of the present application, NGP or graphene materials include single and multilayer (typically less than 10 layers, few-layer graphene) discrete platelets/platelets of native graphene, graphene oxide, reduced graphene oxide (RGO), fluorinated graphene, chlorinated graphene, brominated graphene, iodinated graphene, hydrogenated graphene, nitrided graphene, chemically functionalized graphene, doped graphene (e.g., doped with B or N). Native graphene has essentially 0% oxygen. RGO typically has an oxygen content of 0.001% to 5% by weight. Graphene oxide (including RGO) may have 0.001 wt% to 50 wt% oxygen. Except native graphene, all graphene materials have 0.001 wt% to 50 wt% of non-carbon elements (eg, O, H, N, B, F, Cl, Br, I, etc.). These materials are referred to herein as non-native graphene materials. The graphenes of the present disclosure can contain native or non-native graphene, and the disclosed methods allow for this flexibility. These graphene sheets can all be chemically functionalized.

Graphene sheets have a substantial proportion of edges corresponding to the edge planes of graphite crystals. The carbon atoms on the edge planes are reactive and must contain some kind of heteroatom or group to satisfy the carbon valence. In addition, there are many types of functional groups, such as hydroxyl and carboxyl groups, which naturally occur on the edges or surfaces of graphene sheets produced by chemical or electrochemical methods. Many chemical functional groups (eg _-NH2 , etc.) can be readily imparted to graphene edges and/or surfaces using methods well known in the art.

In a preferred embodiment, the resulting functionalized graphene sheet (NGP) can broadly have the following formula (e): [NGP]--R_m, where m is the number of different functional group types (typically between 1 and 5), and R is selected from SO₃H, COOH, NH₂, OH, R'CHOH, CHO, CN, COCl, Halide, COSH, SH, COOR', SR', SiR'₃、Si(--OR'--)_{the y}R'_3-y, Si(--O--SiR'₂-)OR', R", Li, AlR'₂, Hg--X, TlZ₂and Mg—X; wherein y is an integer equal to or less than 3, R' is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly(alkyl ether), R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate.

In order for NGPs to be effective reinforcing fillers in epoxy resins, the functional group _-NH2 is of particular interest. For example, a common curing agent for epoxy resins is diethylenetriamine (DETA), which has three _-NH2 groups. If DETA is included in the impact chamber, one of the three _-NH2 groups can bond to the edge or surface of the graphene sheet, and the remaining two unreacted _-NH2 groups will be available for subsequent reaction with epoxy resin. This arrangement provides good interfacial bonding between the NGPs (graphene sheets) of the composite and the matrix resin.

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), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), hexamethylenetetramine, polyethylenepolyamines, polyamine epoxy adducts, phenolic hardeners, non-brominated curing agents , non-amine curing agents, and combinations thereof. These functional groups are polyfunctional, having the ability to react with at least two chemical species from at least two ends. Most importantly, they can use one of their ends to bond to the edge or surface of the graphene, and one or both of the other ends can be reacted with epoxy or epoxy resin during the subsequent epoxy curing stage.

The [NGP]-- _Rm described above can be further functionalized.所得石墨烯片包括具有下式的組成物：[NGP]--A _m ，其中A選自OY、NHY、O=C--OY、P=C--NR'Y、O=C--SY、O=C--Y、--CR'1--OY、N'Y或C'Y，並且Y係蛋白質、肽、胺基酸、酶、抗體、核苷酸、寡核苷酸、抗原、或酶底物、酶抑制劑或酶底物的過渡態類似物的適當官能基或者選自R'--OH、R'--NR' ₂ 、R'SH、R'CHO、R'CN、R'X、R'N ⁺ (R') ₃ X ^- 、R'SiR' ₃ 、R'Si(--OR'--) _y R' _3-y 、R'Si(--O--SiR' ₂ --)OR'、R'--R”、R'--N--CO、(C ₂ H ₄ O--) _w H、(--C ₃ H ₆ O--) _w H、(--C ₂ H ₄ O) _w --R'、(C ₃ H ₆ O) _w --R'、R'，並且w係大於1且小於200的整數。CNT可以類似地官能化。

NGPs and conductive additives (such as carbon nanofibers) can also be functionalized to produce compositions with the formula: [NGP]—[R′—A] _m , where m, R′ and A are as defined above. The compositions of the present disclosure also include NGPs on which certain cyclic compounds are adsorbed. These include compositions of matter having the following formula: [NGP]—[X—R _a ] _m , where a is zero or a number less than 10, X is a polynuclear aromatic moiety, a polyheteronuclear aromatic moiety or a metal polyheteronuclear aromatic moiety, and R is as defined above. Preferred cyclic compounds are planar. More preferred cyclic compounds for adsorption are porphyrins and phthalocyanines. Adsorbed cyclic compounds can be functionalized. Such compositions include compounds having the formula [NGP]--[X--A _a ] _m , wherein m, a , X and A are as defined above.

The functionalized NGPs of the present disclosure can be directly prepared by sulfonation, electrophilic addition to the surface of deoxygraphene platelets, or metallization. Graphene platelets can be processed prior to exposure to functionalizing agents. Such processing may include dispersing the graphene platelets in a solvent. In some examples, the platelets can then be filtered and dried prior to contacting. One particularly useful type of functional group is the carboxylic acid moiety, which occurs naturally on the surface of the NGP if the NGP is prepared from the acid intercalation route discussed above. If carboxylic acid functionalization is desired, NGPs can be subjected to chlorate, nitric acid, or ammonium persulfate oxidation.

Carboxylic acid-functionalized graphene sheets or platelet systems are particularly useful, as they can serve as starting points for the preparation of other types of functionalized NGPs. For example, alcohols or amides can be readily attached to the acid to give stable esters or amides. If the alcohol or amine is part of a di- or poly-functional molecule, the linkage via O- or NH- leaves other functional groups as side groups. These reactions can be performed using any method developed for esterification with alcohols or amination of carboxylic acids with amines as known in the art. Examples of these methods can be found in G. W. Anderson et al., J. Amer. Chem. Soc. 86, 1839 (1964), which is hereby incorporated by reference in its entirety. Amino groups can be introduced directly onto graphite platelets by treating the platelets with nitric and sulfuric acid to obtain nitrated platelets, followed by chemical reduction of the nitrated form with a reducing agent such as sodium dithionite to obtain amine-functionalized platelets.

The resulting graphene dispersion can be further added with acid, metal salt, oxidizing agent, or a combination thereof to prepare a more reactive dispersion for graphene coating of polymer parts. A binder resin may also be added as needed. In these cases, surface cleaning, etching, and graphene coating can Done in one step. The polymer part can simply be dipped into the graphene solution for a few seconds to minutes (preferably 5 seconds to 15 minutes), and then the polymer part is withdrawn from the graphene-liquid dispersion. After removal of the liquid (eg, via natural or forced evaporation), the graphene sheets are naturally coated and bonded to the surface of the polymer part.

In certain embodiments, functionalized graphene sheets and/or conductive fillers can be pre-coated or decorated with nanoparticles of catalytic metals that can catalyze the subsequent chemical metallization process. The catalytic metal is preferably in the form of discrete nanoscale particles or coatings having a diameter or thickness of 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, alloys thereof, or combinations thereof. Alternatively, the catalytic metal may initially be in the form of a precursor (eg, as a metal salt) that is subsequently converted to a nanoscale metal deposited on the graphene surface.

Accordingly, the present disclosure also provides metallized graphene dispersions (or graphene/conductive filler dispersions) for use on polymer surfaces. The graphene dispersion comprises a plurality of graphene sheets and conductive fillers dispersed in a liquid medium, wherein the plurality of graphene sheets comprise single or few-layer graphene sheets selected from native graphene materials having substantially 0% non-carbon elements or non-native graphene materials having 0.001 wt. Graphene, chemically functionalized graphene, or a combination thereof, and wherein the dispersion further comprises one or more species selected from: (i) a binder resin dissolved or dispersed in the liquid medium, wherein the binder to graphene weight ratio is from 1/5000 to 1/10; (ii) an etchant selected from acids, oxidants, metal salts, or combinations thereof; (iii) nanoscale particles or coatings of catalytic metals selected from cobalt, nickel, having a diameter or thickness of from 0.5 nm to 100 nm , copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof; or (iv) combinations thereof.

Once the graphene sheets are bonded to the surface of the polymer part, step (c) of the disclosed method may include immersing the graphene/conductive filler bonded polymer part in a metallization bath for metallization. Electroless plating (chemical metallization). Quite unexpectedly, the graphene surface itself (even in the absence of transition metals or noble metals) is able to facilitate the conversion of some metal salts to metals deposited on the graphene surface. This would eliminate the need to use expensive noble metals such as palladium or platinum as nuclei for subsequent chemical growth of metal crystals, as required by prior art processes.

The high conductivity and high specific surface area of the deposited graphene sheets (capable of covering a wide surface area of a polymer part) enables the electroplating of one or more metal layers on the surface of a graphene-coated polymer part. It was also found that the graphene sheets deposited on the surface of the polymer part significantly enhanced the strength, hardness, durability and scratch resistance of the deposited metal layer.

Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. may be chosen for the final metallization procedure.

Thus, the disclosed method produces a surface metallized polymeric article comprising: a polymeric part having a surface, a first layer of a plurality of graphene sheets and conductive fillers coated on the surface of the polymeric part, and a metallized second layer deposited on the first layer, wherein the plurality of graphene sheets (functionalized or non-functionalized) includes single-layer graphene sheets or few-layer graphene sheets (2-10 graphene planes), wherein the plurality of graphene sheets are bonded to the surface with or without a binder resin. Polymer part surfaces.

The first layer typically has a thickness of from 0.34 nm to 30 μm (preferably from 1 nm to 1 μm, and further preferably from 1 nm to 100 nm). The second layer preferably has a thickness of from 0.5 nm to 1.0 mm, and more preferably from 1 nm to 10 μm. The doped graphene preferably comprises N-doped, boron-doped, phosphorus-doped graphene, or a combination thereof. The graphene sheets contain native graphene, and the first layer contains a binder resin that chemically bonds the graphene sheets to the surface of the polymer part. In certain alternative embodiments, the graphene sheet comprises a non-native graphene material having a content of non-carbon elements from 0.01% to 20% by weight, and the non-carbon elements include elements selected from the group consisting of oxygen, fluorine, chlorine, bromine, iodine, nitrogen, hydrogen, or boron.

As some examples, the surface metallized polymeric article may be selected from faucets, shower heads, pipes, pipes, connectors, adapters, sinks (such as kitchen or bathroom sinks), bathtub covers, spouts, sink covers, bathroom accessories, or kitchen accessories.

The polymer component may comprise plastic, rubber, thermoplastic elastomers, polymer matrix composites, rubber matrix composites, or combinations thereof. In certain embodiments, the polymeric component comprises thermoplastics, thermosetting resins, interpenetrating networks, rubber, thermoplastic elastomers, natural polymers, or combinations thereof. In certain preferred embodiments, the polymeric part comprises a plastic selected from the group consisting of acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate, polyamide or nylon, polystyrene, polyacrylate, polyethylene, polypropylene, polyacetal, polyester, polyether, polyetheretherketone (PEEK), polyphenylene oxide (PPO), polyvinyl chloride (PVC), polyimide, Polyamideimide, polyurethane, polyurea, or combinations thereof.

In surface metallized polymer articles, the metal to be plated is preferably selected from copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, alloys thereof, or combinations thereof.

The graphene sheet may be further decorated with nanoscale particles or coatings (having a diameter or thickness of from 0.5 nm to 100 nm) of a catalytic metal selected from the group consisting of cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof, and wherein the catalytic metal is chemically different from the metal being plated. The catalytic metal particles or coating are covered by at least one layer of metallization.

In certain embodiments, the surface of the polymeric part contains only small openings or pores having a diameter or depth of <0.1 μm prior to deposition of the first layer of graphene sheets.

In certain embodiments, the plurality of graphene sheets are bonded to the surface of the polymer part with a binder resin, having a binder to graphene weight ratio of from 1/5000 to 1/10, preferably from 1/1000 to 1/100.

The following examples are used to illustrate some specific details regarding the best mode of practicing the disclosure and should not be construed as limiting the scope of the invention.

Example 1 : Sulfuric acid intercalation and expanded graphene oxide from MCMB

MCMB (Mesocarbon Microbeads) were supplied by China Steel Chemical Co. This material has a density of about 2.24 g/cm ³ and a median particle size of about 16 μm. MCMB (10 g) was intercalated with an acid solution (4:1:0.05 ratio of sulfuric acid, nitric acid, and potassium permanganate) for 48 h. After the reaction was complete, the mixture was poured into deionized water and filtered. The intercalated MCMB was repeatedly washed in 5% HCl to remove most of the sulfate ions. The samples were 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 preset at a desired temperature of 800°C-1,100°C for 30 seconds to 90 seconds to obtain graphene sheets. A certain amount of graphene flakes was mixed with water and treated with 60W power ultrasonic wave for 10 minutes to obtain graphene dispersion.

A small amount was sampled, dried and studied with TEM, showing that the majority of NGPs were between 1 and 10 layers. The oxygen content of the resulting graphene powder (GO or RGO) is from 0.1% to about 25%, depending on the puffing temperature and time.

Several graphene dispersions were separately added with various acids, metal salts and oxidizing species for metallization of the polymers.

Example 2 : Oxidation and expansion of natural graphite

According to the method of Hummers [US Pat. No. 2,798,878, Jul. 9, 1957], graphite oxide was prepared by oxidizing graphite flakes with sulfuric acid, sodium nitrate, and potassium permanganate in a 4:1:0.05 ratio at 30° C. for 48 hours. After the reaction was complete, the mixture was poured into deionized water and filtered. The samples were then washed with 5% HCl solution to remove most of the sulfate ions and residual salts, and then rinsed repeatedly with deionized water until the pH of the filtrate was about 4. The intent is to remove all sulfuric and nitric acid residues from the graphite interstitials. The slurry was dried and stored in a vacuum oven at 60°C for 24 hours.

The dried, intercalated (oxidized) compound was expanded by placing the sample in a quartz tube inserted into a horizontal tube furnace preset at 1.050° C. to obtain highly expanded graphite. exfoliated graphite Disperse with 1% surfactant in water in a flat-bottomed flask at 45°C, and subject the resulting suspension to ultrasonic treatment for a period of 15 minutes to obtain a dispersion of graphene oxide (GO) sheets.

Example 3 : the preparation of native graphene

Native graphene sheets are produced by using direct ultrasonic treatment or liquid phase expansion processes. In a typical procedure, 5 grams of graphite flakes ground to a size of about 20 μm were dispersed in 1,000 mL of deionized water (containing 0.1 wt % dispersant, ^Zonyl® FSO from DuPont) to obtain a suspension. An ultrasonic energy level of 85 W (Branson S450 ultrasonic generator) was used for the expansion, separation and size reduction of the graphene sheets for a period of 15 minutes to 2 hours. The resulting graphene sheets are never oxidized and are oxygen-free and relatively defect-free pristine graphene.

Example 4 : the preparation of fluorinated graphene

We have used several processes to produce GF, but this article describes only one process as an example. In a typical procedure, highly expanded graphite (HEG) is composed of intercalation compounds C ₂ F. x ClF ₃ preparation. HEG is further fluorinated by chlorine trifluoride vapor to produce fluorinated highly expanded graphite (FHEG). A pre-cooled Teflon reactor was filled with 20 mL-30 mL of pre-cooled liquid _ClF3 , and the reactor was then closed and cooled to liquid nitrogen temperature. Subsequently, no more than 1 g of HEG was placed in a container with a hole for the _ClF gas to enter the reactor. After 7-10 days, a gray beige product of approximate formula _C2F was formed. The GF flakes were then dispersed in a halogenated solvent to form a suspension.

Example 5 : the preparation of graphene nitride

The graphene oxide (GO) synthesized in Example 2 was finely ground with different proportions of urea, and the granulated mixture was heated (900W) in a microwave reactor for 30s. The product was washed several times with deionized water and dried under vacuum. In this method, graphene oxide is simultaneously reduced and doped with nitrogen. The products obtained with graphene/urea mass ratios of 1/0.5, 1/1, and 1/2 were named N-1, N-2, and N-3, respectively, and the nitrogen contents of these samples, as determined by elemental analysis, were 14.7 wt.%, 18.2 wt.%, and 17.5 wt.%, respectively. These graphene nitride sheets remained dispersible in water.

Example 6: Graphene-bound/activated ABS

A first set of several _rectangular strips of ABS plastic each with a surface of 50 ^cm2 was soaked in an etching solution consisting of 4M _H2SO4 and 3.5M _CrO3 at 70 °C for 3 min. Rinse the strips with water. On a separate basis, use a second set of several strips of the same size, but do not etch.

Both sets of samples were soaked in the RGO-water solution prepared in Example 1 at 40°C for a period of 30 seconds, and then removed from the solution and dried in air. Subsequently, the RGO-bonded ABS strips were copper-plated in a sulfuric acid-containing copper electrolyte. We have surprisingly observed that the method of the present disclosure can successfully metallize ABS and various plastics without etching. Bonded metal layers mediated by graphene sheets performed equally well in terms of surface hardness, scratch resistance, and durability to heating/cooling cycles.

Comparative Example 6a: Pd/Sn activated ABS

A first set of several rectangular strips of ABS plastic each with a _surface of 50 ^cm2 was soaked in an etching solution consisting of 4M _H2SO4 and 3.5M _CrO3 at 70 °C for 3 min. Rinse the strips with water. On a separate basis, use a second set of several strips of the same size, but do not etch.

Two sets of samples were soaked at 40° C. for a period of 5 minutes in a solution containing Pd/Sn colloid containing 250 mg/L palladium, 10 g/L tin(II) and 110 g/L HCl. Subsequently, these samples were rinsed in water and copper-plated in a copper electrolyte containing sulfuric acid. We observed that ABS plastic surfaces could not be properly (uniformly) metallized without heavy etching, even when some large amount of expensive rare metals (such as Pd) were implemented on the etched surface.

Example 7: Graphene-incorporated/activated high-impact polystyrene (HIPS)

A first set of several rectangular strips of HIPS plastic, each with a surface _of ⁵⁰ cm, was soaked in an etching solution consisting of 4M _H2SO4 and 3.5M _CrO3 at 70 °C for 3 min. Rinse the strips with water. On a separate basis, use a second set of several strips of the same size, but do not etch.

Thereafter, the plastic was sprayed with a virgin graphene-adhesive solution containing 5% by weight of graphene sheets and 0.01% by weight of epoxy resin. After removing the liquid medium (acetone) and curing at 150°C for 15 minutes Afterwards, the graphene sheets were well bonded to the plastic surface.

After this treatment, the graphene-bonded plastic was subjected to electrochemical nickel plating. For this, the articles were treated for 15 minutes in a Watts electrolyte containing 1.2M NiSO ₄ .7H ₂ O, 0.2M NiCl ₂ .6H ₂ O and 0.5M H ₃ BO ₃ . The initial current was 0.3 A/dm ² , and nickel plating was performed at 40°C.

Comparative Example 7a: Sulfide Activated High Impact Polystyrene (HIPS)

A first set of several rectangular strips of HIPS plastic, each with a surface _of ⁵⁰ cm, was soaked in an etching solution consisting of 4M _H2SO4 and 3.5M _CrO3 at 70 °C for 3 min. Rinse the strips with water. On a separate basis, use a second set of several strips of the same size, but do not etch.

Thereafter, the plastic article was treated for 30 seconds in an ammonia solution containing 0.5M CuSO _{4.5H 2} O, the solution having a pH value of 9.5 and a temperature of 20°C. The plastic articles were then immersed in distilled water for 20 seconds and subsequently treated with _a sulfide solution containing 0.1M _Na2S2 for 30 seconds at 20°C. After this treatment, wash the plastic again in cold water. This is followed by electrochemical nickel plating. For this, the articles were treated for 15 minutes in a Watts electrolyte containing 1.2M NiSO ₄ .7H ₂ O, 0.2M NiCl ₂ .6H ₂ O and 0.5M H ₃ BO ₃ . The initial current was 0.3 A/dm ² , and nickel plating was performed at 40°C. We observed that the HIPS plastic surface could not be uniformly metallized using the sulfide seeding method without heavy etching. In contrast, the graphene-mediated method of the present invention enables the successful plating of almost all kinds of metals on not only HIPS surfaces but also on any other type of polymer surface.

Example 8: Graphene-Enabled Polyurethane-Based Thermoplastic Elastomers (TPE)

Soak the TPE strips in an alkaline aqueous solution containing 5 g/L NaOH and 0.5 g/L GO for 15 min. The strips were then removed from the solution (actually the graphene dispersion), allowing the graphene oxide sheets to be coated onto the TPE surface while the water was being removed. Rinse off residual NaOH with water.

The GO-coated strips were subjected to electroless nickel plating in an ammoniacal nickel electrolyte at 30 °C for 10 min. On a separate basis, a Ni layer was directly electrochemically deposited onto the GO-coated TPE surface. Both methods were found to provide Ni layers with high hardness, scratch resistance and gloss. This simple and simple two-step process improves It is surprisingly effective in providing a wide variety of metallized polymer articles.

In contrast, TPE parts cannot be uniformly metallized under the instruction of Pd/Sn catalyst seeds without the use of strong chromium-sulfuric acid as etchant to generate large-sized microcavities (surface voids) with a depth greater than 0.3 μm. After immersing the etched TPE samples in a solution containing 80 mg/L palladium, 10 g/L tin(II), and 110 g/L HCl containing Pd/Sn colloids at 30 °C for 10 min, this Pd/Sn catalyst was deposited onto the large surface cavities of the TPE.

Example 9: Graphene-Incorporated Glass Fiber Reinforced Polyester Composites

Catalytic metals 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. In this example, Co was used as a representative catalytic metal, and chemical oxidation/reduction from solution was used to deposit nanoparticles on the graphene surface.

A cobalt salt solution was used as the metal salt solution. The cobalt(II) brine solution contains 1g/L to 10g/L CoSO ₄ .7H ₂ O and an oxidizing agent, namely hydrogen peroxide. The graphene oxide sheets are dispersed in the solution to form a dispersion. Heating this dispersion causes at least part of the cobalt(II) to be oxidized by _H2O2 to _cobalt (III), which deposits on the graphene surface upon further heating. Electrolytic direct metallization of the composite surface is then allowed to proceed. The composite surface was electroplated in a nickel bath, where an initial current density of 0.3 A/dm ² was used for electrochemical nickel plating, which was later increased to 3 A/dm ² . Electrochemical nickel plating is carried out in Watts electrolyte at 30°C to 40°C for a treatment time of 10 minutes to 15 minutes. The Watts electrolyte contained 1.2M NiSO ₄ .7H ₂ O, 0.2M NiCl ₂ .6H ₂ O and 0.5M H ₃ BO ₃ .

Example 10: Functionalizing Graphene- and CNT-Combined Polyetheretherketone (PEEK) and Other Polymer Components

A first set of several rectangular strips of PEEK plastic, each with a 50 ^cm surface, was soaked in _an etching solution consisting of 4M _H2SO4 and 3.5M _CrO3 at 70 °C for 3 min. Rinse the strips with water. Separately, a second set of several strips of the same size was used, but not etched.

Subsequently, the plastic article was dipped into a functionalized graphene/CNT-binder dispersion containing 5% by weight of graphene sheets or carbon nanotubes (CNTs) and 0.01% by weight of epoxy resin or polyurethane. The chemical functional groups involved in this study include azides (2-azidoethanol), alkylsilanes, hydroxyl groups, carboxyl groups, amine groups, sulfonic acid groups ( _--SO3H ), and diethylenetriamine (DETA). These functionalized graphene sheets and CNTs were supplied by Taiwan Graphene Co., Taipei, Taiwan. After removing the liquid medium (acetone) and curing at 150 °C for 15 min, the graphene sheets and CNTs were well bonded to the plastic surface.

After this treatment, the graphene- and CNT-bonded plastics were subjected to electroless nickel or copper plating. For nickel plating, the functionalized graphene- and CNT-bound articles were treated in an electroless plating solution containing 1.2M NiSO ₄ .7H ₂ O at 40 °C for 15 min. For Cu plating, the functionalized graphene- and CNT-bonded plastic parts were immersed for 30 seconds in an ammonia solution containing 0.5M CuSO _{4.5H 2} O with a pH of 9.5 and a temperature of 20°C.

A similar procedure was performed for the metallization of other polymer parts, including carbon black-filled natural rubber, silicone rubber, chlorinated rubber, polycarbonate, ABS, polyethylene terephthalate (PET), and chopped Kevlar fiber-filled phenolic resins.

We have observed that, in general, polymeric parts can be well metallized using the functionalized graphene-mediated methods of the present disclosure even without an etching process. In all instances, the metal bonded well to the polymer part surfaces, which had an excellent matte appearance and outstanding scratch resistance. If functionalized graphene sheets were included alone or in combination with functionalized CNTs, the metallized surface was generally smoother compared to functionalized CNTs alone in the impregnation dispersion.

Example 11: Graphene/conductive additive combined polyethersulfone (PES) and other polymer parts

A first set of several _rectangular strips of PES plastic each with a surface of 50 ^cm2 was soaked in an etching solution consisting of 4M _H2SO4 and 3.5M _CrO3 at 70 °C for 3 min. Rinse the strips with water. Separately, a second set of several strips of the same size was used, but not etched.

Subsequently, the plastic article was dipped into a graphene/conductive filler/binder dispersion containing 5 wt% graphene sheets, 0.5 wt% vapor-grown carbon nanofibers, and 0.01 wt% epoxy or polyurethane. In this example, Cu nanowires and Ni-coated polyacrylonitrile nanofibers (obtained by electrospinning) were also used as conductive fillers. The chemical functional groups involved in this study include alkylsilanes, hydroxyl groups, carboxyl groups, amine groups, and diethylenetriamine (DETA). These functionalized graphene sheets were supplied by Taiwan Graphene Corporation, Taipei, Taiwan. After removing the liquid medium (acetone) and curing at 150 °C for 15 minutes, the graphene sheets were well bonded to the plastic surface.

After this treatment, the graphene/conductive filler combined plastic was subjected to electroless nickel or electroless copper plating. For nickel plating, the bonded or covered polymer parts were treated in an electroless bath containing 1.2M NiSO ₄ .7H ₂ O at 40°C for 15 minutes. For Cu plating, the bonded or covered plastic parts were dipped for 30 seconds in an ammonia solution containing 0.5M CuSO _{4.5H 2} O having a pH of 9.5 and a temperature of 20°C.

A similar procedure was performed for the metallization of other polymer parts, including carbon black-filled SBR rubber, silicone rubber, polycarbonate, ABS, polyethylene terephthalate (PET), and chopped glass-fiber-filled phenolic resin.

We have observed that, in general, polymeric parts can be well metallized using the functionalized graphene-mediated methods of the present disclosure even without an etching process. In all instances, the metal bonded well to the polymer part surfaces, which had an excellent matte appearance and outstanding scratch resistance. If graphene sheets are included alone or in combination with conductive fillers, metallized surfaces are generally smoother than when conductive fillers are used alone in the impregnation dispersion.

The present disclosure has the following unexpected advantages:

1. Even without the use of chromic acid or chromic sulfuric acid, strong adhesion between deposited metal layers and lightly etched polymer surfaces can be achieved via functionalized graphene sheet-mediated and/or functionalized CNT-mediated. These well-bonded metal layers exhibit resistance to high temperature cycling and withstand all usual temperatures Loop shock.

2. A wide variety of chemical functional groups can be attached to the edges or surfaces of mediating graphene sheets or carbon nanotubes enabling rapid metallization of polymer parts.

3. The disclosed process can be performed under very mild conditions requiring only a short period of time. Optimal results are also achieved without duplication of process steps typically required by prior art processes.

4. High-quality metal layers can be deposited on the surface of polymer parts without huge capital investment and large material consumption. Furthermore, the process can be controlled in a functionally safe and simple manner which ultimately affects the quality of the metal layer.

5. A surprisingly wide variety of polymers (including not only plastics but also rubbers and composites) can be effectively metallized. In contrast, only a limited number of plastics can be satisfactorily metallized with prior art processes.

6. Since there is no need to etch the plastic surface at high temperature, energy saving can be achieved. Since mild etch conditions are required only when necessary and in rare cases (eg, highly smooth UHMWPE surfaces), a wider range of mild etch solutions can be used; avoiding the need to use environmentally restricted chemicals.

7. The process or method of the present disclosure may involve only two steps: contacting the polymer part surface with the graphene dispersion (e.g., a dipping step), and contacting the graphene/conductive filler-bonded polymer part surface with an electroless or electrochemical plating solution (e.g., another quick dipping step). In contrast, prior art processes require many steps: pretreatment, chemical etching, activation, chemical metallization, and electrolytic deposition of multiple metal layers (hence, additional multiple steps).

Claims (19)

A surface metallized polymeric article comprising: a polymeric part having a surface, a first layer consisting of a plurality of graphene sheets and a conductive filler coated on the surface of the polymeric part, and a metallized second layer deposited on the first layer, wherein the plurality of graphene sheets comprise single or few-layer graphene sheets selected from a native graphene material having substantially 0% non-carbon elements or a non-native graphene material having 0.001% to 25% by weight non-carbon elements, wherein the non-native graphene is selected from graphene oxide Graphene, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated graphene, graphene nitride, doped graphene, chemically functionalized graphene, or combinations thereof, and wherein the plurality of graphene sheets and the conductive filler are bonded to the surface of the polymer part with or without a binder resin, and the first layer has a thickness from 0.34 nm to 30 μm, wherein the conductive filler is selected from the group consisting of: carbon nanofibers; carbon-coated fibers; SnO₂.ZnO₂、In₂o₃or nanofibers or nanowires of indium tin oxide (ITO); and combinations thereof. The surface metallized polymer article as described in claim 1 , wherein the second layer has a thickness from 0.5 nm to 1.0 mm. The surface metallized polymer product as described in claim 1 , wherein the surface metallized polymer part is selected from faucets, shower heads, pipes, tubes, connectors, adapters, kitchen sinks or bathroom sinks, bathtub covers, spouts, sink covers, bathroom accessories, or kitchen accessories. The surface metallized polymer article as described in claim 1 , wherein the first layer includes an adhesive resin that chemically bonds the graphene sheet and the conductive filler to the surface of the polymer component. The surface metallized polymer product as described in item 4 of the scope of the patent application, wherein the binder resin includes ester resin, neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid, terephthalic acid, urethane resin, urethane ester resin, acrylic resin, acrylic urethane resin, or a combination thereof. The surface metallized polymer article as described in item 4 of the patent claims, wherein the binder resin contains 1 to 30 parts by weight of curing agent and/or coupling agent based on 100 parts by weight of the binder resin. The surface metallized polymer product as described in item 4 of the scope of the patent application, wherein the binder resin comprises a heat-curable resin, and the heat-curable resin comprises a polyfunctional epoxy monomer selected from the group consisting of diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, or a combination thereof. If the scope of patent application4The surface metallized polymer article of claim 1, wherein the binder resin comprises a thermally curable resin comprising a difunctional or trifunctional epoxy monomer selected from the group consisting of trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, triphenol triglycidyl ether, tetraphenylolethane triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether Ether, p-aminophenol triglycidyl ether, 1,2,6-hexanetriol triglycidyl ether, glycerin triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxy triglycidyl ether, castor oil triglycidyl ether, propoxylated glycerol triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dipropylene glycol diglycidyl ether Glyceryl ether, polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl carboxylate, and mixtures thereof. If the scope of patent application4The surface metallized polymer article of claim 1, wherein the binder resin comprises a UV radiation curable resin or lacquer selected from the group consisting of acrylate and methacrylate oligomers, (meth)acrylates (acrylates and methacrylates), polyols with (meth)acrylate functionality and derivatives thereof, including ethoxylated trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate, quaternary Pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate esters, or neopentyl glycol di(meth)acrylates and mixtures thereof, and acrylate and methacrylate oligomers derived from low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, epoxy acrylates, polybutadiene resins, and polythiol-polyene resins. The surface metallized polymer product as described in item 1 of the scope of the patent application, wherein the metal to be plated is selected from copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, alloys thereof, or combinations thereof. The surface metallized polymer product as described in item 1 of the scope of the patent application, wherein the graphene sheet is further modified with nano-scale particles or coatings having a diameter or thickness from 0.5nm to 100nm of a catalytic metal, the catalytic metal is selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof, and wherein the catalytic metal is chemically different from the metal to be plated. A method of producing a surface metallized polymer article as described in claim 1, the method comprising: a) providing a graphene-conductive filler mixture dispersion comprising a plurality of graphene sheets and conductive fillers dispersed in a liquid medium, contacting the surface of a polymer part with the dispersion and promoting deposition of the plurality of graphene sheets and the conductive filler onto the surface of the polymer part to form a first layer, wherein the plurality of graphene sheets and the conductive filler are bonded to the surface to form a layer of bonded graphene sheets and conductive fillers covering the surface of the polymer part, wherein The plurality of graphene sheets comprises single or few-layer graphene sheets selected from native graphene materials having substantially 0% non-carbon elements or non-native graphene materials having 0.001% to 25% by weight non-carbon elements, wherein the non-native graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated graphene, nitrided graphene, doped graphene, chemically functionalized graphene, or combinations thereof, and wherein the plurality of graphene sheets and the conductive A filler is bonded to the surface of the polymer part with or without a binder resin, and the first layer has a thickness from 0.34 nm to 30 μm, wherein the conductive filler is selected from the group consisting of: carbon nanofibers; carbon Coated fibers; SnO₂.ZnO₂、In₂o₃or nanofibers or nanowires of indium tin oxide (ITO); and combinations thereof; and b) chemically, physically, electrochemically or electrolytically depositing a second layer of metal on said first layer of the surface of said covered polymer component to form said surface metallized polymer article. The method as described in claim 12 , further comprising a step of subjecting the surface of the polymer component to grinding treatment, etching treatment, or a combination thereof prior to step (a). The method of claim 12 , wherein said step (b) comprises the step of dipping said covered polymeric part into and then withdrawing from an electroless plating bath comprising a metal salt dissolved in a liquid medium to effect metallization of the surface of said polymeric part. The method described in claim 12 , wherein the liquid medium comprises permanganic acid, phosphoric acid, nitric acid, or a combination thereof dissolved in the liquid medium. An apparatus for making a surface metallized polymer article, the apparatus comprising: (a) a graphene deposition chamber containing a graphene dispersion comprising a plurality of graphene sheets dispersed in a first liquid medium, wherein the graphene deposition chamber is operative to deposit the graphene sheets onto the surface of at least one polymer part to form at least one graphene-coated polymer part; A graphene-coated polymer part coated with a layer of the desired metal to obtain said surface metallized polymer article; wherein said plurality of graphene sheets comprise single or few-layer graphene sheets selected from the group consisting of native graphene materials having substantially 0% non-carbon elements or non-native graphene materials having 0.001 wt. ene, doped graphene, chemically functionalized graphene, or combinations thereof. The apparatus of claim 16 , further comprising a movable carrier for carrying the at least one polymer part and contacting the at least one polymer part with the polymer dispersion to produce the at least one graphene-coated polymer part and/or contacting the at least one graphene-coated polymer part with the plating solution to obtain the surface metallized polymer article. The apparatus of claim 16 , further comprising drying, heating or curing providing means in operative relationship with said graphene deposition chamber for partially or completely removing said first liquid medium from said at least one graphene-coated polymer part to produce said at least one graphene-coated polymer part comprising said plurality of graphene sheets bonded to said surface of said at least one polymer part. The device as described in item 16 of the scope of the patent application, wherein the plating solution includes an electroless plating solution, an electrochemical plating solution or an electrolytic solution.