TWI720365B - Graphene-mediated metal-plated polymer article and production method - Google Patents

Abstract

Provided is a surface-metalized polymer article comprising a polymer component having a surface, a first layer of multiple graphene sheets, multiple functionalized graphene sheets having a first chemical functional group, multiple functionalized carbon nanotubes having a second chemical group functional group, or a combination, which are coated on the polymer component surface, and a second layer of a metal deposited on the first layer, wherein the multiple functionalized graphene sheets may contain single-layer or few-layer graphene sheets and/or the multiple functionalized carbon nanotubes may contain single-walled or multiwalled carbon nanotubes, and wherein the multiple functionalized graphene sheets or functionalized carbon nanotubes are bonded to the polymer component surface with or without an adhesive resin.

Description

Graphene-mediated metal-plated polymer product and production method

The present disclosure generally relates to the field of metallization of the surface of polymer parts, and more specifically, to graphene- and/or carbon nanotube-realized metal-plated polymer products, their production methods, and products containing the same.

Metallized plastics are often used for decorative purposes. For example, metalizing the surface of plastics such as acrylonitrile-butadiene-styrene (ABS) and ABS-polycarbonate blends for sanitary fittings, car accessories, furniture, hardware, jewelry, and buttons/knobs . These manufactured products can be metalized to give the surface 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 metalized for functional purposes. For example, to shield electromagnetic interference (EMI), plastic-based electronic components can be metallized. In addition, the surface properties of polymer parts can be changed in a controlled manner by metal coating.

Products made of non-conductive polymers (such as plastic, rubber, polymer matrix composite materials, etc.) can be metalized by an electroless metallization process. In a typical manufacturing process, the article is first cleaned and etched, then treated with a precious metal (such as palladium), and finally metalized in a metalizing solution. The etching step typically involves the use of chromic acid or chromosulfuric acid. The etching step is used to improve The surface wettability of the product makes the surface of the product easy to accept the subsequent metalization with the corresponding solution in the subsequent processing steps, and is used to make the final deposited metal adhere to the polymer surface well.

In the etching step, chromium sulfuric acid is used to etch the surface of the polymer product to form surface cavities, and metal is deposited and adhered to these surface cavities. After the etching step, the surface of the polymer part is activated by means of an activating agent (or activator) that typically contains a precious metal, and then metallization is performed using electroless plating. Subsequently, a thicker metal layer can be deposited electrolytically.

Etching solutions based on chromium sulfuric acid are toxic and should therefore be replaced when possible. For example, an etching solution based on chromium sulfuric acid can be replaced with an etching solution containing permanganate. It has been established for a long time that permanganate is used in alkaline medium for metallization of circuit boards as electronic circuit carriers. Since the hexavalent state (manganate) produced in oxidation is water-soluble and has sufficient stability under alkaline conditions, similar to trivalent chromium, manganate can be electrolytically oxidized back to the original oxidant. In this case it is permanganate. For the metallization of ABS plastics, alkaline permanganate solutions have been found to be inappropriate, because it is impossible to obtain sufficient adhesion strength between the metal layer and the plastic substrate in this way. The adhesion strength is determined in the "peel test" and should have a value of at least 0.4 N/mm.

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

Therefore, there is an urgent need for industrial-scale metallization of the surface of polymer parts without the use of chromic acid, chromic sulfuric acid or alkali metal permanganate.

Another major problem of the prior art metallization process is the following point of view: In the etching step Later, the surface of the polymer part must be activated by means of an activating agent, which typically contains a precious metal (e.g. palladium). It is known that precious metals are rare and expensive. In an alternative process [L. Naruskevicius et al. "Process for metallizing a plastic surface" [process for metallizing a plastic surface], US Patent No. 6712948 (March 30, 2004)], the chemically etched The plastic surface is treated with a metal salt solution containing cobalt salt, silver salt, tin salt, or lead salt. However, the activated plastic surface must be further treated with a sulfide solution. The entire process is slow, cumbersome and expensive.

Therefore, another urgent need is to perform industrial-scale metallization of the surface of polymer parts without using expensive noble metals in the activation reagent or even without using an activation step if all possible.

This application requires U.S. patent application number 15/813,996 filed on November 15, 2017, U.S. patent application number 15/914,224 filed on March 7, 2018, and U.S. patent application number filed on March 15, 2018 The priority of 15/922,024, these patent applications are hereby incorporated by reference.

The present disclosure provides a polymer product with a metalized surface, the polymer product comprising: a polymer part having a surface; a plurality of graphene sheets coated on the surface of the polymer part, that is, having a first chemical functional group A functionalized graphene sheet, a first layer of a plurality of functionalized carbon nanotubes with a second chemical functional group (same or different from the first functional group), or a combination thereof; and deposited on the first layer The metal-plated second layer, wherein the plurality of functionalized graphene sheets may include single-layer or few-layer graphene sheets or the plurality of functionalized carbon nanotubes include single-wall or multi-wall carbon nanotubes, and The plurality of functionalized graphene sheets or functionalized carbon nanotubes are bonded to the surface of the polymer component with or without a binder resin. The first layer 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 from 0.5 nm to 1.0 mm, and more preferably from 1 nm to 10 μm. The unexpected use is also described in this article A simple and effective method can easily and easily produce such metal-plated polymer products.

In some embodiments, the first or second chemical functional group is selected from alkyl or aryl silane, alkyl or aralkyl group, hydroxyl group, carboxyl group, amine group, sulfonate group ) ( _{--SO 3} H), aldehydic group, quinoidal, fluorocarbon, or a combination thereof.

及其組合。 Alternatively, the first or second functional group includes a derivative of an azide compound selected from the group consisting of: 2-azidoethanol, 3-azidoprop-1-amine , 4-(2-azidoethoxy)-4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropionate, chloroformate, methyl azide Ester (azidocarbonate), dichlorocarbene, carbene, aryne, azene, (R-)-oxycarbonyl azene, where R=any of the following groups:

And its combination.

In certain embodiments, the first or second functional group is selected from the group consisting of hydroxyl, peroxide, ether, ketone, and aldehyde. In some embodiments, the functionalizing agent contains a functional group selected from the group consisting of SO ₃ H, COOH, NH ₂ , OH, R'CHOH, CHO, CN, COCl, halogen Root (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 and Mg--X; wherein y is an integer equal to or less than 3, and R'is hydrogen, alkyl, aryl, cycloalkyl or aralkyl Group, cyclic aryl or poly(alkyl ether), R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cyclic aryl, X is halide, and Z is Carboxylate or trifluoroacetate, and combinations thereof.

The first or second functional group may be selected from the group consisting of: amidoamine, polyamide, aliphatic amine, modified aliphatic amine, cycloaliphatic amine, aromatic amine, acid anhydride, ketone Amine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), polyethylenepolyamine, polyamine epoxy adduct, phenol hardener , Non-brominated curing agent, non-amine curing agent, and combinations thereof.

In some embodiments, the first or second 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 protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme The functional group of the transition state analog of the inhibitor or enzyme substrate or selected from 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', and w is an integer greater than 1 and less than 200.

The doped graphene preferably includes nitrogen-doped, boron-doped, phosphorus-doped graphene, or a combination thereof.

The metalized polymer product can 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 some embodiments, the graphene sheet includes native graphene, and the first layer includes a binder resin that chemically bonds the graphene sheet to the surface of the polymer component. In some alternative embodiments, the graphene sheet comprises a non-native graphene material having a non-carbon element content of from 0.01% to 20% by weight, and these non-carbon elements include those selected from oxygen, fluorine, chlorine, bromine, Elements of iodine, nitrogen, hydrogen, or boron.

The polymer component may include plastic, rubber, thermoplastic elastomer, polymer matrix composite material, rubber matrix composite material, or a combination thereof. In certain embodiments, the polymer component includes thermoplastics, thermosetting resins, interpenetrating networks, rubber, thermoplastic elastomers, natural polymers, or combinations thereof. Together. In some preferred embodiments, the polymer component comprises a plastic selected from the group consisting of: acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate Ester, polyamide or nylon, polystyrene, high impact polystyrene (HIPS), polyacrylate, polyethylene, polypropylene, polyacetal, polyester, polyether, polyether ether, polyether ether ketone (PEEK), polyethere, polyphenylene oxide (PPO), polyvinyl chloride (PVC), polyimide, polyimide, polyurethane, polyurea, or a combination thereof.

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

The graphene sheet can be further modified with nano-scale particles or coatings (having a diameter or thickness from 0.5nm to 100nm) 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 to be plated.

In some embodiments, the surface of the polymer component only contains small openings or holes with a diameter or depth of <0.1 μm before depositing the first layer of graphene sheet.

In some embodiments, a plurality of graphene sheets are bonded to the surface of the polymer part with an adhesive resin, with an adhesive and a resin ranging from 1/5000 to 1/10, preferably from 1/1000 to 1/100. Graphene weight ratio.

The present disclosure also provides a method for producing a polymer product with a metalized surface, the method comprising: (a) chemically, physically or mechanically treating the surface of the polymer part to prepare a surface-treated polymer part; (b) Provide a graphene dispersion comprising a plurality of graphene sheets dispersed in a liquid medium, contact the surface-treated polymer part with the graphene dispersion and promote the deposition of the graphene sheets onto the surface-treated polymer On the surface of the component, where the graphene sheets are bonded to the surface to form a layer of bonded graphene sheets; and (c) depositing metal chemically, physically, electrochemically, or electrolytically on the layer of the bonded graphene sheets Layer to form a metalized polymer product on the surface. These graphenes The sheet may include graphene, native graphene, graphene oxide, non-native graphene, doped graphene, chemically functionalized graphene, and combinations thereof.

In some embodiments, step (a) includes the step of subjecting the surface of the polymer component to a grinding process, an etching process, or a combination thereof. In some embodiments, step (a) includes the step of subjecting the surface of the polymer component 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 a 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) includes the step of subjecting the surface of the polymer part to an etching treatment using an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof under mild etching conditions, wherein the etching is performed at a sufficiently low temperature The temperature is low enough for a short period of time so as not to produce micro-holes with an average size greater than 0.1 μm.

The graphene sheet can be further modified with nano-scale particles or coatings of catalytic metal having a diameter or thickness ranging from 0.5nm to 100nm, the catalytic metal being selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead , Bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof.

In some embodiments, step (b) includes immersing or immersing the surface-treated polymer part in the graphene dispersion, and removing the surface-treated polymer part from the graphene dispersion to achieve Graphene sheets are deposited on the surface of the surface-treated polymer part, wherein the graphene sheets are bonded to the surface to form a layer of bonded graphene sheets. Alternatively, the graphene dispersion can be simply sprayed onto the surface of the polymer part to allow the liquid components to evaporate and the binder (if present) to solidify or solidify.

In the disclosed method, step (c) may include immersing the polymer component in a metalizing bath. In a preferred procedure, step (c) includes immersing the polymer part containing the combined layers of a plurality of functionalized graphene sheets or carbon nanotubes in an electroless plating bath containing a metal salt dissolved in a liquid medium And withdraw from it to achieve the step of metallization of the polymer component.

In some embodiments, the graphene dispersion further includes a binder resin having a weight ratio of binder to graphene ranging from 1/5000 to 1/10.

Alternatively, the surface of the polymer part is not subjected to pretreatment (in contrast to the chemical etching step normally required in prior art methods). The method for producing a polymer product with a metallized surface includes: (A) providing a graphene dispersion containing a plurality of graphene sheets dispersed in a liquid medium, contacting the surface of the polymer component with the graphene dispersion and Facilitate the deposition of the graphene sheets onto the surface of the polymer component, wherein the graphene sheets are bonded to the surface to form a layer of bonded graphene sheets; and (B) chemically on the layer of the bonded graphene sheets , Physically, electrochemically or electrolytically depositing a metal layer to form a polymer product with a metalized surface.

The graphene sheet can be further modified with nano-scale particles or coatings of catalytic metal having a diameter or thickness ranging from 0.5nm to 100nm, the catalytic metal being selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead , Bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof.

The graphene dispersion may further include a binder resin having a weight ratio of binder to graphene from 1/5000 to 1/10.

The liquid medium may include permanganic acid, phosphoric acid, nitric acid, or a combination 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 (A) may include immersing or immersing the surface-treated polymer part in the graphene dispersion, and removing the surface-treated polymer part from the graphene dispersion, so as to realize the deposition of the graphene sheet on the graphene dispersion. On the surface of the surface-treated polymer part, where graphene sheets are bonded to the surface to form a layer of bonded graphene sheets.

Step (B) may include immersing the polymer part in a metalizing bath to complete electroless plating or electroless plating. The high conductivity of the deposited graphene sheet enables the electroplating of one or more metal layers on the surface of the graphene-coated polymer part. Alternatively, physical vapor deposition, sputtering, Plasma deposition and so on to complete the final metallization process.

The present disclosure also provides a continuous method for producing polymer products with metalized surfaces. The method includes: (a) continuously immersing a polymer article into a graphene dispersion containing a plurality of graphene sheets dispersed in a liquid medium for a period of soaking time, and then removing the polymer article from the dispersion Exit, so that the graphene sheet can be deposited on the surface of the polymer product to form a graphene-attached polymer product; (b) continuously move the graphene-attached polymer product to a dry or carbon nanotube ( CNT) heating zone to enable graphene sheets to be bonded to the surface to form a graphene-covered polymer product; and (c) the graphene-covered polymer product is continuously moved into the metallization zone, where the metal In the chemical zone, a metal layer is chemically, physically, electrochemically or electrolytically deposited on the surface of the graphene-covered polymer product to form the polymer product with the surface metallization.

In some preferred embodiments, the method further includes an additional step of continuously moving the polymer article to the surface treatment zone to treat the surface of the polymer article before step (a). The additional step may include subjecting the surface of the polymer article to a grinding process, an etching process, or a combination thereof. In certain embodiments, the additional step includes subjecting the surface of the polymer article to an etching treatment using an etchant selected from an acid, an oxidizing agent, a metal salt, or a combination thereof. In certain preferred embodiments, the additional step includes subjecting the surface of the polymer article to an etching treatment that does not use chromic acid or chromic sulfuric acid.

In some embodiments, the additional step includes subjecting the surface of the polymer article to an etching treatment under mild etching conditions using an etchant selected from the group consisting of acids, oxidants, metal salts, or combinations thereof, wherein the etching is performed at a sufficiently low temperature. The temperature is carried out for a short enough period of time so as not to generate micro-holes having an average size greater than 0.1 μm.

The method may further include the step of modifying the graphene sheets with nano-scale particles or coatings of catalytic metal having a diameter or thickness ranging from 0.5 nm to 100 nm, the catalytic metal being selected from the group consisting of cobalt, nickel, copper, iron, Manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof.

The liquid medium may include permanganic acid, phosphoric acid, nitric acid, or a combination thereof dissolved in the liquid medium. The liquid medium may include an acid, an oxidizing agent, a metal salt, or a combination thereof dissolved in the liquid medium.

In some embodiments, the graphene dispersion further includes a binder resin having a weight ratio of binder to graphene ranging from 1/5000 to 1/10.

The present invention also provides metallized graphene dispersions for polymer surfaces. In some embodiments, the graphene or carbon nanotube dispersion comprises a plurality of functionalized graphene sheets (having a first chemical functional group) and/or functionalized carbon nanotubes (having a A second chemical functional group that is the same as or different from the first functional group), wherein the plurality of graphene sheets comprise single-layer or few-layer graphene sheets or the plurality of functionalized carbon nanotubes comprise single-wall or multi-wall carbon Nanotubes, and wherein the graphene or carbon nanotube dispersion further comprises one or more species selected from the following: (i) a binder resin dissolved or dispersed in the liquid medium, wherein the binder is combined with graphene or The weight ratio of the binder to the carbon nanotube is from 1/5000 to 1/10; (ii) an etchant selected from acid, oxidant, metal salt, or a combination thereof; (iii) having a diameter from 0.5nm to 100nm Or thickness of nano-scale particles or coatings of catalytic metal selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or Combination; or (iv) its combination. Preferably, the graphene dispersion or the CNT dispersion only contains species (i), and does not contain (ii) or (iii).

Preferably, in the graphene or CNT dispersion, nano-scale particles or coatings of catalytic metal are deposited or modified on the surface of multiple functionalized graphene sheets or multiple functionalized carbon nanotubes.

In the graphene or CNT dispersion, the acid may be selected from permanganic acid, phosphoric acid, nitric acid, chromic acid, chromium sulfuric acid, or a combination thereof. However, other more environmentally friendly acids such as carboxylic acid, acetic acid and ascorbic acid are preferred.

The preferred first chemical functional group or the preferred second chemical functional group have been discussed earlier in this section.

Figure 1 shows a flow chart of the most commonly used process for the production of graphene oxide sheets, which requires chemical oxidation/intercalation, washing, and high-temperature expansion procedures.

Figure 2 shows a flow chart of a continuous method of metallizing the surface of a polymer article. All procedures can be performed in a continuous manner.

Figure 3 is a schematic diagram of graphene-mediated metallized polymer parts

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

The term "graphene sheet" means a material that contains one or more flat sheets of bonded carbon atoms densely packed in a hexagonal lattice, in which the carbon atoms are bonded by strong in-plane covalent bonds Together, and also contains a complete ring structure that runs through most of the interior. Preferably, at least 80% of the internal aromatic bonds are intact. In the c-axis (thickness) direction, these graphene planes can be weakly joined together by Van der Waals force. Graphene sheets may contain non-carbon atoms, such as OH and COOH functional groups, on their edges or surfaces. The term graphene sheet includes native graphene, graphene oxide, reduced graphene oxide, halogenated graphene (including fluorinated graphene and chlorinated graphene), nitrided graphene, hydrogenated graphene, doped graphene, functional Graphene, and combinations thereof. Typically, non-carbon elements account for 0% to 25% by weight of the graphene sheet. Graphene oxide may contain up to 53% by weight of oxygen. The term "doped graphene" encompasses graphene with less than 10% of non-carbon elements. The non-carbon element may include hydrogen, oxygen, nitrogen, magnesium, iron, sulfur, fluorine, bromine, iodine, boron, phosphorus, sodium, and combinations thereof. The graphene sheet may include a single-layer graphene or a few-layer graphene, where the few-layer graphene is defined as a graphene sheet crystal formed by less than 10 graphene planes. The graphene sheet may also include graphene nanoribbons. "Native graphene" covers stone with essentially 0% non-carbon elements Ink vinyl film. "Nanographene sheet crystal" (NGP) refers to a graphene sheet having a thickness from less than 0.34nm (single layer) to 100nm (multilayer).

The term "substantially" and its variants are defined as largely but not necessarily fully specified (as understood by those skilled in the art), and in a non-limiting embodiment, generally Refers to the range within 10%, within 5%, within 1%, or within 0.5% of the reference range.

Other objects, features and advantages of the present invention may become apparent from the following drawings, descriptions and examples. However, it should be understood that although these drawings, descriptions and examples indicate specific embodiments of the present invention, they are only given in an illustrative manner and are not meant to be limiting. In other embodiments, features from specific embodiments may be combined with features from other embodiments.

The present disclosure provides a polymer product with a metalized surface, the polymer product comprising: a polymer part having a surface; a plurality of functionalized graphene sheets having a first chemical functional group coated on the surface of the polymer part , A first layer of a plurality of functionalized carbon nanotubes with a second chemical functional group, or a combination of the two; and a second layer of metal plated deposited on the first layer, wherein the plurality of functionalized The graphene sheet includes single-layer or few-layer graphene sheets and/or the plurality of functionalized carbon nanotubes include single-wall or multi-wall carbon nanotubes, and wherein the plurality of functionalized graphene sheets or functionalized carbon nanotubes The rice tube is bonded to the surface of the polymer part with or without binder resin, as shown in Figure 2. The first layer (graphene or CNT layer) 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 (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. This metal-plated polymer article can be easily and easily produced using the unexpectedly simple and effective method also described herein. Functionalized graphene sheets are surprisingly able to be bonded to the surface of many types of polymer parts without the use of binder resins.

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

及其組合。 Alternatively, the first or second functional group includes a derivative of an azide compound selected from the group consisting of: 2-azidoethanol, 3-azidoprop-1-amine , 4-(2-azidoethoxy)-4-oxobutanoic acid, 2-azidoethyl-2-bromo-2-methylpropionate, chloroformate, methyl azide Ester (azidocarbonate), dichlorocarbene, carbene, aryne, azene, (R-)-oxycarbonyl azene, where R=any of the following groups:

And its combination.

In certain embodiments, the first or second functional group is selected from the group consisting of hydroxyl, peroxide, ether, ketone, and aldehyde. In some embodiments, the functionalizing agent contains a functional group selected from the group consisting of SO ₃ H, COOH, NH ₂ , OH, R'CHOH, CHO, CN, COCl, halogen Root (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 and Mg--X; wherein y is an integer equal to or less than 3, and R'is hydrogen, alkyl, aryl, cycloalkyl or aralkyl Group, cyclic aryl or poly(alkyl ether), R" is fluoroalkyl, fluoroaryl, fluorocycloalkyl, fluoroaralkyl or cyclic aryl, X is halide, and Z is Carboxylate or trifluoroacetate, and combinations thereof.

The first or second functional group may be selected from the group consisting of: amidoamine, polyamide, aliphatic amine, modified aliphatic amine, cycloaliphatic amine, aromatic amine, acid anhydride, ketone Amine, diethylene Triamine (DETA), Triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), Polyethylenepolyamine, Polyamine Epoxy Adduct, Phenol Hardener, Non-brominated Curing Agent , Non-amine curing agents, and combinations thereof.

In some embodiments, the first or second 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 protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen or enzyme substrate, enzyme The functional group of the transition state analog of the inhibitor or enzyme substrate or selected from 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', and w is an integer greater than 1 and less than 200.

The present disclosure also provides a method for metalizing polymer surfaces (for example, surfaces of non-conductive plastics). Within the scope of the method, according to the embodiments of the present disclosure, the plastic surface of one plastic product or the plastic surfaces of several plastic products are metalized.

Coating the surface of polymer parts with metal (also known as polymer plating or polymer metallization) is becoming more and more important. Through the polymer electroplating method, a laminate that combines the advantages of polymer and metal is produced. Compared with metal parts, the use of polymer parts can achieve significant weight savings. Electroplating of polymer moldings is usually performed for modification purposes, EMI masking, or surface property modification.

This section starts with the description of the most common prior art process used to produce metallized plastic products. Then focus on the problems related to the prior art process. After that, the disclosed manufacturing process and the resulting product that overcome all these problems will be discussed.

In the prior art manufacturing process for metallized polymer parts, these parts are usually fixed in a frame and in contact with a variety of different processing fluids in a specific process sequence. As the first step, the plastic is typically pretreated to remove impurities, such as grease, from the surface. Subsequently, an etching process is used to roughen the surface to ensure sufficient adhesion of the subsequent metal layer to the polymer surface. In the etching operation, it is particularly important to form a uniform structure in the form of depressions (such as surface openings or micro-holes) on the plastic surface. Subsequently, The roughened surface is treated with an activator to form a catalytic surface for subsequent chemical metallization or electroless plating. For this purpose, ion-generating activators or colloidal systems are used.

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

After activation, the metastable solution of the metalization bath is typically used to chemically metalize the plastic part. These baths usually contain a metal to be deposited in the form of a salt in an aqueous solution and a reducing agent for the metal salt. When the chemical metallization bath comes into contact with a metal core (such as a palladium seed) on the plastic surface, metal is formed by reduction, and the metal is deposited on the surface as a firmly adhered layer. The chemical metallization step is generally used to deposit copper, nickel or nickel alloys with phosphorus and/or boron.

The chemically metallized polymer surface can then be further electrolytically deposited with a metal layer. Typically, electrolytic deposition of a copper layer or another nickel layer is performed before the electrochemical application of the required modified chromium layer.

There are several major issues related to this prior art process used to produce metallized polymer articles:

1) The process is cumbersome 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).物) or polycarbonate. Chromium-sulfuric acid is very toxic and requires special precautions during the etching process, after treatment, and disposal. Due to the chemical process in the etching process (e.g. the used Reduction of chromium compounds), chromium-sulfuric acid etchant is used up and usually cannot be reused.

3) The key process step of plastic electroplating is to produce micro-holes so that the metal can adhere to the plastic surface. These micro-holes are used as the starting point for metal core growth in the subsequent metallization step. Generally, these microcavities have a size of about 0.1 μm to 10 μm. In particular, these micro-holes show a depth in the range from 0.1 μm to 10 μm (that is, the extent from the surface of the plastic toward the inside). Unfortunately, surface cavities may be stress concentration sites, which can weaken the strength of plastic parts.

4) After etching or roughening the plastic surface, first activate the surface with colloidal palladium or ion-generating palladium. In the case of the colloidal process, this activation is followed by the removal of the protective tin colloid, or in the case of the ion generation process, the activation is followed by reduction to elemental palladium. Subsequently, copper or nickel is chemically deposited on the plastic surface as a conductive layer. After that, electroplating or metallization is performed. In practice, this direct metallization of the plastic surface is only suitable for certain plastics. If it is impossible to sufficiently roughen the plastic or form suitable micro-holes by etching the plastic surface, the functional and firm adhesion of the metal layer to the plastic surface cannot be ensured. Therefore, in the prior art manufacturing process, the amount of plastic that can be coated is greatly limited.

5) Noble 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 some embodiments, the method includes: (a) optionally treating the surface of the polymer part to prepare a surface-treated polymer part (this procedure is optional because the graphene dispersion itself can pre-process the polymer物surface); (b) providing a graphene dispersion or CNT dispersion containing a plurality of functionalized graphene sheets or functionalized CNT dispersed in a liquid medium, so that the surface-treated polymer part is dispersed with the graphene Body or CNT dispersion contact, and enabling the graphene sheets to be deposited on the surface of the surface-treated polymer component, wherein the functionalized graphene sheets and/or CNTs are bonded to the surface to form bonded graphene And (c) depositing a metal layer chemically, physically, electrochemically or electrolytically on the surface of the graphene/CNT-bonded polymer component to form a surface metalized polymer Products. Step (a) is optional in the disclosed method.

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 polymer component may be selected from polyethylene, polypropylene, polybutene, polyvinyl chloride, polycarbonate, acrylonitrile-butadiene-styrene (ABS), polyester, polyvinyl alcohol, polyvinylidene Vinyl 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

Diazole, polybenzo

Azole, polybenzodi

Azole, polythiazole, polybenzothiazole, polybenzodithiazole, poly(paraphenylene vinylene), polybenzimidazole, polybenzimidazole, copolymers thereof, polymer blends thereof, or combination.

In some 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 media 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 situations, the entire process requires only three simple steps.

In some embodiments, step (a) may include the step of subjecting the surface of the polymer component to a grinding process, an etching process, or a combination thereof. In some embodiments, step (a) includes the step of subjecting the surface of the polymer component 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 a 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) includes the step of subjecting the surface of the polymer part to an etching treatment using an etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof under mild etching conditions, wherein the etching is performed at a sufficiently low temperature The temperature is low enough for a short period of time so as not to produce micro-holes with an average size greater than 0.1 μm.

The mild etching mentioned in this disclosure means that "etching" or treating the plastic surface with an etching solution occurs at a low temperature and/or at a low etching solution concentration in a short period of time. When one of the aforementioned three conditions is met, mild etching conditions can be achieved. The low temperature mentioned in this disclosure means that the maximum temperature is 40°C, preferably Is <30°C, and most preferably from 15°C to 25°C. At the above-mentioned low temperature, the pretreatment with the etching solution is performed in 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, if the selected treatment time is appropriately short, mild etching conditions can also be achieved at temperatures exceeding 40°C. According to an embodiment of the present disclosure, the etching treatment is performed at a temperature of 40° C. to 95° C., preferably 50° C. to 70° C., for a treatment time of 15 seconds to 5 minutes, preferably 0.5 minutes to 3 minutes. In fact, 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 prior art process mentioned above, no roughening of the polymer surface or generation of micro-holes in the polymer surface is performed. The microcavities produced by etching according to the prior art process generally 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 so that only small openings or holes are generated in the polymer surface, and these small openings or holes have a diameter and especially a depth of <0.1 μm, preferably <0.05 μm. In this respect, depth means the degree of openings/channels from the surface of the polymer to the inside of the polymer. Therefore, the classic etching in the case of the prior art process is not performed here. In the process of the present disclosure in which step (a) is eliminated, the liquid medium in the graphene dispersion can generally produce openings or pores having a size of <0.1 μm. Contrary to what is suggested by the previous technical teaching content, we unexpectedly observed that the graphene-mediated metallization method of the present disclosure does not require the generation of micro-holes with a size greater than 0.1 μm. This method works even on highly smooth surfaces.

In step (a), an etching solution and/or plasma treatment or plasma etching, ion bombardment, etc. can be used to achieve the etching treatment.

Preferably, the etching solution used for etching contains at least one oxidizing agent. Gentle etching within the scope of the present disclosure also means that the oxidant is used in a low concentration. Permanganate and/or peroxodisulfate and/or periodate and/or peroxide can be used as oxidizing agent. According to an embodiment of the present disclosure, etching is performed by an acid etching solution, the acid etching solution containing at least one oxidizing agent. The oxidant and/or acid can be Or an alkaline solution (discussed below) is added to the graphene dispersion instead of using a separate etching solution, and as such, step (a) and step (b) are basically 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 preferable to use an acid etching solution which contains only phosphoric acid or mainly phosphoric acid and only a small amount 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 preferable to use potassium permanganate. The alkaline aqueous solution may contain lye. The type of etching solution used depends on the type of polymer to be processed. The preferred concentration of the oxidant 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 permanganate or persulfate. The etching solution may contain 0.1 mol/l to 0.5 mol/l periodate or hydrogen peroxide. The preferred ratio of permanganate 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.

Gentle etching can also be achieved by using a dilute persulfate aqueous solution or a periodate solution or a dilute peroxide aqueous solution (used as a separate etching solution or as part of a graphene dispersion). Preferably, the gentle etching process using the etching solution is performed while stirring the solution. After gentle etching, the plastic surface is rinsed in water for, for example, 1 minute to 3 minutes. According to a preferred embodiment of the present disclosure, the treatment with the metal salt solution is performed at a temperature of <30°C, preferably between 15°C and 25°C (including room temperature). In practice, the treatment with the metal salt solution is carried out without stirring. The preferred treatment time is 30 seconds to 15 minutes, preferably 3 minutes to 12 minutes. Preferably, a metal salt solution is used, which has a pH 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 help of ammonia, and it is preferable to use an alkali metal salt solution. It is also possible to use metal salt solutions containing one or more amines. For example, the metal salt solution may contain monoethanolamine and/or triethanolamine. Use metal Salt solution treatment means that it is preferable to immerse the surface of the polymer part in a metal salt solution.

In certain embodiments, step (b) includes soaking or immersing the surface-treated polymer component in the graphene or CNT dispersion, and removing the surface-treated polymer from the graphene or CNT dispersion Component to achieve the deposition of graphene sheets on the surface of the surface-treated polymer component, wherein the graphene sheets or CNTs are bonded to the surface to form a layer of bonded graphene sheets. Alternatively, the graphene dispersion or CNT dispersion can be simply sprayed onto the surface of the polymer part to evaporate the liquid component and cure or solidify the binder (if present).

If present, the binder resin layer may be formed of a binder resin composition containing a binder resin as a main component. The binder resin composition may include a curing agent, a coupling agent, and a binder resin. Examples of the binder resin may include ester resins, urethane resins, urethane resins, acrylic resins, and urethane acrylate resins, particularly including neopentyl glycol (NPG), ethylene glycol (EG), isophthalic acid And terephthalic acid ester resin. Based on 100 parts by weight of the binder resin, the curing agent may be present in an amount of 1 to 30 parts by weight. The coupling agent may include an epoxy silane compound.

The curing of the adhesive layer can be performed via heat, UV or ionizing radiation. This may involve heating the layer coated with the heat-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.

Dipping, coating (for example, doctor blade coating, bar coating, slot die coating, comma coating, reverse roll coating, etc.), roll-to-roll process, inkjet printing, screen printing, etc. can be used. Micro-contact, gravure coating, spraying, ultrasonic spraying, electrostatic spraying, and flexographic printing bring the surface of the polymer part into contact with graphene or CNT dispersion. The thickness of the hard coat layer or the adhesive layer is usually about 1 nm to 10 μm, preferably 10 nm to 2 μm.

For heat-curable resins, the multifunctional epoxy monomer may preferably be selected from diglycerol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether Glyceryl ether, pentaerythritol polyglycidyl ether (for example, pentaerythritol tetraglycidyl ether), or a combination thereof. The bifunctional or trifunctional epoxy monomer can be selected from the group consisting of: trimethylolethane triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, Triphenylolmethane (triphenylolmethane) triglycidyl ether, triphenol triglycidyl ether, tetrahydroxyphenylethane triglycidyl ether, tetrahydroxyphenylethane tetraglycidyl ether, p-aminophenol triglycidyl ether , 1,2,6-Hexanetriol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, glycerol ethoxytriglycidyl ether, castor oil triglycidyl ether, propoxylated triglycidyl ether Alcohol triglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, dipropylene glycol diglycidyl ether Ether, polypropylene glycol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, (3,4-epoxycyclohexane) methyl 3,4-epoxycyclohexyl Formate and mixtures.

In certain embodiments, the heat-curable composition of the present disclosure advantageously further contains 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 to produce a satisfactory final hard coat.

UV radiation curable resins and lacquers that can be used in the adhesive layer used in the present disclosure are photopolymerizable monomers and oligomers derived from polyfunctional compounds (such as acrylate and methacrylate oligomers ( The term "(meth)acrylate" as used herein refers to those of acrylate and methacrylate)), such as polyols having (meth)acrylate functional groups 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 bis(meth)acrylate ) Acrylic esters and mixtures thereof, and derived from low molecular weight polyester resins, polyether resins, epoxy resins, polyurethane resins, alkyd resins, spiroacetal resins, epoxy acrylates, polybutadiene resins, and polysulfides Alcohol-polyene resin Acrylate and methacrylate oligomers.

UV polymerizable monomers and oligomers are coated (for example after exiting from immersion) and dried, and then exposed to UV radiation to form an optically transparent cross-linked wear-resistant layer. The preferred UV curing dose is between 50 mJ/cm ² and 1000 mJ/cm ² .

UV curable resins are typically also ionizing radiation curable. The ionizing radiation curable resin may contain a relatively large amount of reactive diluent. Reactive diluents that can be used herein include monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, vinyl toluene, and N-vinylpyrrolidone; and Multifunctional 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 include immersing the graphene-bonded polymer component in a metalizing bath. The high conductivity of the deposited graphene sheets easily enables the electroplating of one or more metal layers on the surface of graphene or CNT-coated polymer parts.

Alternatively and advantageously, the final metallization step can be accomplished by using an electroless plating method that does not use expensive noble metal solutions. This step may include immersing (immersing) the graphene or CNT-coated polymer part in an electroless plating bath containing a metal salt dissolved in a liquid medium (a salt of a metal such as Cu, Ni, or Co is expected) (For example, CuSO ₄ soluble in water or NiNO ₃ soluble in water). Such impregnation typically requires a contact time of from 3 seconds to 30 minutes.

The copper metal plating bath (or nickel plating bath) may contain a copper salt (or Ni salt) and an additive consumption inhibiting compound. Additive consumption inhibiting compounds may include methyl sulfene, methyl sulfide, tetramethylene sulfene, thioglycolic acid, 2(5H) thiophenone, 1,4-dithio, trans-1,2-dithio, tetramethylene Hydrothiophene-3-one, 3-thiophene methanol, 1,3,5-trithiophene, 3-thiopheneacetic acid, thiotetronic acid, crown sulfide, tetrapyrid, dipropyl trisulfide, Bis(3-triethoxysilylpropyl tetrasulfide, dimethyl tetrasulfide, methanethiosulfuric acid Methyl ester, (2-sulfonate ethyl) methane, p-tolyl disulfide, p-tolyl disulfide, bis(phenylsulfonyl) sulfide, 4-(chlorosulfonyl) benzoic acid, isopropyl Sulfonyl chloride, 1-propanesulfonyl chloride, lipoic acid, 4-hydroxybenzenesulfonic acid, phenylvinyl sulfonate, or mixtures thereof.

Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. can be selected to complete the final metallization process.

All these procedures can be performed in a continuous manner. Figure 2 shows a continuous process for producing a polymer article with a metallized surface. The method includes: (a) continuously immersing a polymer article into a graphene dispersion containing a plurality of graphene sheets dispersed in a liquid medium for a period of soaking time, and then removing the polymer article from the dispersion Exit, so that the graphene sheet can be deposited on the surface of the polymer product to form a graphene-attached polymer product; (b) continuously move the graphene-attached polymer product to a drying or heating zone to make The graphene sheet can be bonded to the surface to form a graphene-covered polymer product; and (c) the graphene-covered polymer product is continuously moved into the metallization zone, where the metal layer Chemically, physically, electrochemically, or electrolytically deposited on the surface of the graphene-covered polymer product to form the surface metalized polymer product.

In some embodiments, step (a) includes (or previously) subjecting the surface of the polymer article to a grinding process, an etching process, or a combination thereof. In some embodiments, step (a) includes the step of subjecting the surface of the polymer component to an etching treatment using an etchant selected from an acid, an oxidizing agent, a metal salt, or a combination thereof.

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 nanotube or carbon nanofiber ( 1-D nanographite material), graphene (2-D nanographite material) and graphite (3-D graphite material). Carbon nanotube (CNT) refers to a tubular structure grown with single or multi-wall. Carbon nanotubes (CNT) and carbon nanofibers (CNF) have a diameter of about several nanometers to several hundred nanometers. Its longitudinal, hollow structure gives the material unique mechanical, electrical and chemical properties. CNT or CNF are one-dimensional nanocarbon or 1-D nanographite materials.

As early as 2002, our research team pioneered the development of graphene materials and related production processes: (1) BZJang and WCHuang, "Nano-scaled Graphene Plates [Nano-scaled Graphene Plates]", US patent number 7,071,258 (July 4, 2006), an application filed on October 21, 2002; (2) BZJang et al. "Process for Producing Nano-scaled Graphene Plates [Process for Producing Nano-scaled Graphene Plates]" , U.S. Patent Application No. 10/858,814 (June 3, 2004) (U.S. Patent Publication No. 2005/0271574); and (3) BZJang, A. Zhamu and J. Guo, "Process for Producing Nano-scaled Platelets and Nanocomposites [Process for the production of nano-scale lamellae and nanocomposites]", U.S. Patent Application No. 11/509,424 (August 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。 A single-layer graphene sheet is composed of carbon atoms occupying a two-dimensional hexagonal lattice. Multilayer graphene is a platelet composed of more than one graphene plane. Individual single-layer graphene sheets and multi-layer graphene sheet crystals are collectively referred to herein as nanographene sheet crystals (NGP) or graphene materials. NGP includes primary graphene (essentially 99% of carbon atoms), micrographene oxide (<5% by weight of oxygen), graphene oxide (

5 wt% oxygen), microfluorinated graphene (<5 wt% fluorine), fluorinated graphene (

5 wt% fluorine), other halogenated graphenes, and chemically functionalized graphenes.

It has been found that NGP has a series of unusual physical, chemical and mechanical properties. For example, it was found that graphene exhibits the highest inherent strength and highest thermal conductivity of all existing materials. Although graphene's actual electronic device applications (for example, replacing Si as the skeleton in transistors) are not expected to occur within the next 5-10 years, it is used as a nanofiller in composite materials and as an electrode material in energy storage devices. The application is coming soon. The availability of a large number of processable graphene sheets is critical to the successful development of graphene composites, energy and other applications.

Recently, we reviewed the process of producing NGP and NGP nanocomposites [Bor Z.Jang and A Zhamu, "Processing of Nano Graphene Platelets (NGPs) and NGP Nanocomposites: A Review [Nanographene platelets (NGP) and The addition of NGP nanocomposites Engineering: Review]", J. Materials Sci. [Journal of Materials Science] 43 (2008) 5092-5101].

A very useful method (Figure 1) requires the treatment of natural graphite powder with intercalating agents and oxidizing agents (for example, concentrated sulfuric acid and nitric acid, respectively) to obtain graphite intercalation compound (GIC) or actually graphite oxide (GO). [William S. Hummers, Jr. et al., Preparation of Graphitic Oxide [Preparation of Graphitic Oxide], Journal of the American Chemical Society [American Chemical Society], 1958, page 1339. ] Before intercalation or oxidation, graphite has an inter-graphene spacing of approximately 0.335nm ( L _d =½ d ₀₀₂ =0.335nm). In the case of intercalation and oxidation treatment, the inter-graphene spacing is increased to a value typically greater than 0.6 nm. This is the first expansion stage that the graphite material undergoes during the chemical route. The resulting GIC or GO is then subjected to further expansion (often referred to as expansion ) using a thermal shock exposure method or a graphene layer exfoliation method assisted by solution-based ultrasonic treatment.

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 expand or expand GIC or GO to form expanded or further expanded The graphite is typically in the form of "graphite worms" composed of graphite flakes that are still interconnected with each other. This thermal shock procedure can produce some separated graphite flakes or graphene flakes, but usually most of the graphite flakes remain interconnected. Typically, air milling, mechanical shearing, or ultrasonic treatment in water is then used to subject the expanded graphite or graphite worms to a flake separation treatment. Therefore, Method 1 basically requires three different procedures: first expansion (oxidation or intercalation), further expansion (or "puffing"), and separation.

In the solution-based separation method, the expanded or puffed GO powder is dispersed in water or an aqueous alcohol solution and subjected to ultrasonic treatment. It is important to note that in these processes, 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), super Sonic processing. Alternatively, the GO powder dispersed in water is subjected to ion exchange or lengthy purification procedures in such a way that the repulsive force between the ions existing in the interplane space exceeds the van der Waals force between graphene, resulting in graphite The olefin layer is separated.

In the above example, the starting material used to prepare graphene sheets or NGP is graphite material, The material can be selected from the group consisting of: natural graphite, artificial graphite, graphite oxide, graphite fluoride, graphite fiber, carbon fiber, carbon nanofiber, carbon nanotube, mesophase carbon microbeads (MCMB) or carbon Microspheres (CMS), soft carbon, hard carbon, and combinations thereof.

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

In order to reduce the time required to generate the precursor solution or suspension, the graphite can be oxidized to a certain extent for a short period of time (for example, 30 minutes to 4 hours) to obtain 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 to 60 seconds, to obtain expanded graphite or graphite worms, making them as needed (but preferably It is) subjected to mechanical shearing (for example, using a mechanical shearing machine or ultrasonic wave generator) to break the graphite flakes that make up the graphite worm. Then the separated graphene flakes (after mechanical shearing) or unbroken graphite worms or individual graphite flakes are re-dispersed in water, acid or organic solvent and ultrasonically processed to obtain a graphene dispersion.

The primary graphene material is preferably produced by one of the following three processes: (A) intercalation of the graphite material with a non-oxidizing agent, and then thermal or chemical expansion treatment in a non-oxidizing environment; (B) subjecting the graphite material to super Critical fluid environment for infiltration and expansion between graphene layers; or (C) dispersing 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 A graphene dispersion is obtained.

In procedure (A), a particularly preferred step includes (i) using the graphite material selected from alkali metals (such as potassium, sodium, lithium or cesium), alkaline earth metals, or alloys, mixtures, or mixtures of alkali metals or alkaline earth metals, or Eutectic non-oxidant intercalation; and (ii) chemical expansion treatment (for example, by immersing potassium intercalation graphite in an ethanol solution).

In procedure (B), a preferred step includes immersing the graphite material in a supercritical fluid such as carbon dioxide (for example, at a temperature T>31°C and a pressure P>7.4MPa) and water (for example, at T>374°C and P>22.1MPa) for a period of time sufficient to penetrate (temporarily intercalate) the graphene layers. Then a sudden decompression is performed after this step to expand each graphene layer. Other suitable supercritical fluids include methane, ethane, ethylene, hydrogen peroxide, ozone, water oxides (water containing a high concentration of dissolved oxygen), or mixtures thereof.

In the procedure (C), a preferred step includes (a) dispersing particles of graphite material in a liquid medium containing a surfactant or dispersant to obtain a suspension or slurry; and (b) the suspension Or the slurry is exposed to ultrasonic waves of a certain energy level (a process commonly referred to as ultrasonic treatment) for a long enough time to produce separated graphene sheets dispersed in a liquid medium (e.g., water, alcohol, or organic solvent) ( Non-oxidized NGP) graphene dispersion.

It is possible to produce NGP with an oxygen content of not more than 25% by weight, preferably less than 20% by weight, and more preferably less than 5%. Typically, the oxygen content is between 5% and 20% by weight. The oxygen content can be determined using chemical element analysis and/or X-ray photoelectron spectroscopy (XPS).

The layered graphite material used in the prior art process for the production of GIC, graphite oxide and subsequent expanded 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 can be selected from the group consisting of: natural graphite, artificial graphite (for example, highly oriented pyrolytic graphite, HOPG), graphite oxide, graphite fluoride, graphite fiber, carbon fiber, carbon nanofiber, carbon nanofiber Tubes, mesophase carbon microspheres (MCMB) or carbonaceous microspheres (CMS), soft carbon, hard carbon, and combinations thereof. All these materials contain graphite crystallites. These graphite crystallites are produced by Van der Waals consists of stacked or bonded graphene plane layers. In natural graphite, multiple graphene plane stacks (where the graphene plane orientation varies with stacks) are gathered together. In carbon fibers, graphene planes are usually oriented in a preferred direction. Generally speaking, soft carbon is a carbonaceous material obtained by carbonization of liquid aromatic molecules. Their aromatic rings or graphene structures are substantially parallel to each other, thereby enabling further graphitization. Hard carbon is a carbonaceous material obtained from aromatic solid materials (for example, polymers such as phenolic resin and polyfurfuryl alcohol). Their graphene structure is relatively randomly oriented, and therefore it is difficult to achieve further graphitization even at a temperature higher than 2,500°C. However, graphene sheets do exist in these carbons.

Here, fluorinated graphene or graphene fluoride is used as an example of the halogenated graphene material group. There are two different methods that have been followed to produce fluorinated graphene: (1) Fluorination of pre-synthesized graphene: This method requires a fluorinating agent such as XeF ₂ or F-based plasma treatment by mechanical Puffing or graphene prepared by CVD growth; (2) Puffing of multilayer fluorinated graphite: Both mechanical expansion and liquid phase puffing of fluorinated graphite can be easily achieved [F.Karlicky et al. " Halogenated Graphenes: Rapidly Growing" Family of Graphene Derivatives "[halogenated graphene: a rapidly growing family of graphene derivatives] ACS Nano[ACS Nano], 2013, 7(8), p. 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 between F ₂ and graphite at high temperature leads to covalent fluorinated graphite (CF) _n or (C ₂ F) _n , while at low temperature the graphite intercalation compound (GIC) C _x F(2

x

twenty four). The carbon atoms in (CF) _n are sp3 hybridized and therefore the fluorocarbon layer is corrugated, consisting of trans-connected cyclohexane chairs. In (C ₂ F) _n , only half of the C atoms are fluorinated, and each pair of adjacent carbon sheets are connected by covalent CC bonds. The systematic study of the fluorination reaction shows that the obtained F/C ratio largely depends on the fluorination temperature, the partial pressure of fluorine in the fluorinated gas and the physical properties of the graphite precursor, including the degree of graphitization, particle size and Specific surface area. In addition to fluorine (F ₂ ), other fluorinating agents can be used, although most of the existing literature relates _{to fluorination with F 2} gas (sometimes in the presence of fluoride).

In order to expand the layered precursor material into a single graphene layer or a few layers, The attraction between adjacent layers must be overcome and these layers must be further stabilized. 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 includes ultrasonic treatment of fluorinated graphite in a liquid medium to produce fluorinated graphene sheets dispersed in the liquid medium. The resulting dispersion can be directly used for graphene deposition on the surface of polymer parts.

The nitridation of graphene can be performed by exposing graphene materials (such as graphene oxide) to ammonia at high temperatures (200°C-400°C). Nitride graphene can also be formed by a hydrothermal method at a lower temperature; for example, by sealing GO and ammonia in an autoclave and then raising the temperature to 150°C-250°C. Other methods of synthesizing nitrogen-doped graphene include nitrogen plasma treatment on graphene, arc discharge between graphite electrodes in the presence of ammonia, ammonolysis of graphene oxide under CVD conditions, and graphite oxide at different temperatures Hydrothermal treatment of olefin and urea.

For the purpose of limiting the scope of the patent application of this application, NGP or graphene materials include single-layer and multi-layer (typically less than 10 layers, few layers of graphene) native graphene, graphene oxide, reduced graphene oxide (RGO), Discrete fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated graphene, nitrided graphene, chemically functionalized graphene, doped graphene (for example, doped with B or N)的片/片晶。 Native graphene has substantially 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 for native graphene, all graphene materials have 0.001% to 50% by weight of non-carbon elements (for example, O, H, N, B, F, Cl, Br, I, etc.). These materials are referred to herein as non-native graphene materials. The graphene disclosed in the present disclosure may contain native or non-native graphene, and the disclosed method allows this flexibility. These graphene sheets can all be chemically functionalized.

The graphene sheet has a considerable proportion of edges corresponding to the edge plane of the graphite crystals. The carbon atoms on the edge plane are reactive and must contain certain heteroatoms or groups to satisfy the carbon valence. In addition, there are many types of functional groups (such as hydroxyl groups and carboxyl groups), which are naturally present on the edges or surfaces of graphene sheets produced by chemical or electrochemical methods. Using methods known in the art, many chemical functional groups (such as -NH ₂ etc.) can be easily imparted to the edges and/or surfaces of graphene.

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 in 1 and 5), R is selected from SO ₃ H, COOH, NH ₂ , OH, R'CHOH, CHO, CN, COCl, 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 and Mg--X ; Wherein y is an integer equal to or less than 3, R'is hydrogen, alkyl, aryl, cycloalkyl or aralkyl, cycloaryl or poly(alkyl ether), R" is fluoroalkyl, fluorine Substituted aryl, fluorocycloalkyl, fluoroaralkyl, or cycloaryl, X is halide, and Z is carboxylate or trifluoroacetate.

In order to make NGP or CNT an effective reinforcing filler in epoxy resins, the functional group -NH ₂ is of particular interest. For example, diethylene triamine (DETA), a commonly used curing agent for epoxy resins, has three -NH ₂ groups. If DETA is contained in the impact chamber, one of the three -NH ₂ groups can be bonded to the edge or surface of the graphene sheet, and the remaining two unreacted -NH ₂ groups will be available for subsequent interaction with Epoxy reaction. This arrangement provides a good interface bond between the NGP (graphene sheet) of the composite material and the matrix resin.

Other useful chemical functional groups or reactive molecules can be selected from the following group consisting of: amidoamines, polyamides, aliphatic amines, modified aliphatic amines, cycloaliphatic amines, aromatic amines , Acid anhydride, ketimine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), hexamethylenetetramine, polyethylene polyamine , Polyamine epoxy adducts, phenol hardeners, non-brominated hardeners, non-amine hardeners, and combinations thereof. These functional groups are multifunctional and have the ability to react with at least two chemical species from at least two ends. Most importantly, they can be bonded to the edge or surface of graphene using one of their ends, and can react with epoxy or epoxy at one or two other ends in the subsequent epoxy curing stage .

[NGP]--R _m described above can be further functionalized. The obtained graphene sheet includes a composition having the following formula: [NGP]--A _m , where A is 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 protein, peptide, amino acid, enzyme, antibody, nucleotide, oligonucleotide, antigen , Or appropriate functional groups of enzyme substrates, enzyme inhibitors or transition state analogs of enzyme substrates or selected from 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', and w is an integer greater than 1 and less than 200. CNTs can be similarly functionalized.

NGP and CNT can also be functionalized to produce a composition having the formula: [NGP]--[R'--A] _m , where m, R', and A are as defined above. The composition of the present disclosure also includes NGP on which certain cyclic compounds are adsorbed. These include the composition of substances with the following formula: [NGP]--[X--R _a ] _m , where a is zero or a number less than 10, and X is a polynuclear aromatic part, a polyheteronuclear aromatic part or a metal Polyheteronuclear aromatic moiety, and R is as defined above. The preferred cyclic compounds are planar. More preferable cyclic compounds for adsorption are porphyrin and phthalocyanine. The adsorbed cyclic compound can be functionalized. Such compositions include compounds having the formula [NGP]--[X--A _a ] _m , where m, a , X and A are as defined above.

The functionalized NGP or CNT of the present disclosure can be directly prepared by sulfonation, electrophilic addition to the surface of deoxygraphene platelets or CNT, or metalization. Graphene platelets or CNTs can be processed before contacting with the functionalizing agent. Such processing can include dispersing platelets or CNTs in a solvent. In some instances, the platelets or CNTs can then be filtered and dried before contacting. A particularly useful type of functional group is the carboxylic acid moiety. If the NGP is prepared from the acid intercalation route discussed above, these carboxylic acid moieties are naturally present on the surface of the NGP. If carboxylic acid functionalization is required, the NGP can be subjected to oxidation by chlorate, nitric acid, or ammonium persulfate.

Carboxylic acid functionalized graphite platelets or CNT systems are particularly useful because they can serve as a starting point for the preparation of other types of functionalized NGPs or functionalized CNTs. For example, alcohol or amide can easily Connect with the acid to obtain a stable ester or amide. If the alcohol or amine is part of a di- or multi-functional molecule, the O- or NH- linkage leaves other functional groups as side groups. These reactions can be carried out 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. [American Chemical Society] 96, 1839 (1965), which is incorporated herein by reference in its entirety. The amine group can be directly introduced onto the graphite platelets by treating the platelets with nitric acid and sulfuric acid to obtain nitrated platelets, and then chemically reducing the nitrated form with a reducing agent such as sodium dithionite to obtain amine functionalization的片晶。 The lamellae.

The resulting graphene dispersion or CNT dispersion may 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. If necessary, a binder resin can also be added. In these cases, surface cleaning, etching, and graphene coating can be completed in one step. It is possible to simply immerse the polymer part in the graphene solution for several seconds to several minutes (preferably from 5 seconds to 15 minutes), and then withdraw the polymer part from the graphene-liquid dispersion. After removing the liquid (for example via natural or forced evaporation), the graphene sheet is naturally coated and bonded to the surface of the polymer part.

In some embodiments, the graphene sheet, functionalized graphene sheet, or CNT may be pre-coated or modified with nano-scale particles of a catalytic metal that can catalyze the subsequent chemical metalization process. The catalytic metal is preferably in the form of discrete nano-scale particles or coatings having a diameter or thickness from 0.5 nm to 100 nm, and is preferably selected from cobalt, nickel, copper, iron, manganese, tin, zinc , Lead, bismuth, silver, gold, palladium, platinum, alloys thereof, or combinations thereof. Alternatively, the catalytic metal may initially be in the form of a precursor (e.g., as a metal salt), which is subsequently converted to nanoscale metal deposited on the surface of the graphene.

Therefore, the present disclosure also provides metallized graphene dispersions or CNT dispersions for polymer surfaces. The graphene or CNT dispersion comprises a plurality of functionalized graphene sheets and/or functionalized carbon nanotubes dispersed in a liquid medium, wherein the plurality of graphene sheets comprise single-layer or few-layer graphene sheets or all The plurality of functionalized carbon nanotubes include single-wall or multi-wall carbon nanotubes, and wherein the graphene or carbon The nanotube dispersion further comprises one or more species selected from the following: (i) a binder resin dissolved or dispersed in the liquid medium, wherein the weight ratio of the binder to the graphene or the binder to the carbon nanotube Is from 1/5000 to 1/10; (preferably from 1/1000 to 5/100); (ii) an etchant selected from acid, oxidant, metal salt, or a combination thereof; (iii) having from 0.5 Nano-scale particles or coatings of catalytic metal with a diameter or thickness of from nm to 100 nm, the catalytic metal selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, Its alloy, or its combination; or (iv) its combination.

Once the graphene sheet and CNT are bonded on the surface of the polymer part, step (c) in the disclosed method may include immersing the graphene or CNT-bonded polymer part in a metalization bath for electroless plating of metal (Chemical metallization). Very unexpectedly, the graphene surface itself (even without transition metals or precious metals) is catalytic for converting some metal salts into metals deposited on the graphene or CNT surface. This will eliminate the need to use expensive noble metals (such as palladium or platinum) as nuclei for the subsequent chemical growth of metal crystals, as required by prior art processes.

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

Alternatively, physical vapor deposition, sputtering, plasma deposition, etc. can be selected to complete the final metallization process.

Therefore, the disclosed method produces a polymer article with a metalized surface, the polymer article comprising: a polymer part having a surface, a plurality of functionalized graphene sheets and/or a plurality of functionalized graphene sheets coated on the surface of the polymer part A first layer of functionalized CNT, and a second layer of metal plated deposited on the first layer, wherein the plurality of functionalized graphene sheets include single-layer graphene sheets or few-layer graphene sheets (2-10 Graphene planes), and the CNT includes single-wall or multi-wall CNT, and wherein the plurality of graphene sheets are bonded to the surface of the polymer component with or without a binder resin.

The first layer typically has a thickness 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 from 0.5 nm to 1.0 mm, and more preferably from 1 nm to 10 μm. The doped graphene preferably includes nitrogen-doped, boron-doped, phosphorus-doped graphene, or a combination thereof. The graphene sheet contains native graphene, and the first layer contains a binder resin that chemically bonds the graphene sheet to the surface of the polymer part. In some alternative embodiments, the graphene sheet comprises a non-native graphene material having a non-carbon element content of from 0.01% to 20% by weight, and these non-carbon elements include those selected from oxygen, fluorine, chlorine, bromine, Elements of iodine, nitrogen, hydrogen, or boron.

As some examples, polymer products with metalized surfaces can be selected from faucets, shower heads, pipes, pipes, connectors, adapters, sinks (such as kitchen or bathroom sinks), bathtub covers, spouts, sink covers, bathroom accessories, kitchens Tools, car body parts, car decoration parts, car decoration accessories, electronic equipment shells, furniture, hardware, jewelry, buttons and knobs.

The polymer component may include plastic, rubber, thermoplastic elastomer, polymer matrix composite material, rubber matrix composite material, or a combination thereof. In certain embodiments, the polymer component comprises thermoplastics, thermosetting resins, interpenetrating networks, rubber, thermoplastic elastomers, natural polymers, or combinations thereof. In some preferred embodiments, the polymer component comprises a plastic selected from the group consisting of: acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polycarbonate Ester, polyamide or nylon, polystyrene, polyacrylate, polyethylene, polypropylene, polyacetal, polyester, polyether, polyether ether, polyether ether ketone (PEEK), polyether, polyphenylene ether (PPO), polyvinyl chloride (PVC), polyimide, polyimide, polyurethane, polyurea, or a combination thereof.

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

The functionalized graphene sheet or CNT can be further modified with nano-scale particles or coatings (having a diameter or thickness 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 to be plated. The catalytic metal particles or coating are covered by at least one layer of metal plating.

In some embodiments, the surface of the polymer component only contains small openings or holes with a diameter or depth of <0.1 μm before depositing the first layer of graphene sheet.

In some embodiments, a plurality of graphene sheets are bonded to the surface of the polymer part with an adhesive resin, with an adhesive and a resin ranging from 1/5000 to 1/10, preferably from 1/1000 to 1/100. Graphene weight ratio.

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

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

MCMB (Mesophase Carbon Microbeads) is supplied by China Steel Chemical Co. (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 grams) was intercalated with acid solution (4:1:0.05 ratio of sulfuric acid, nitric acid and potassium permanganate) for 48 hours. After the reaction was completed, the mixture was poured into deionized water and filtered. The intercalated MCMB was washed repeatedly in a 5% solution of HCl to remove most of the sulfate ions. The sample was then washed repeatedly with deionized water until the pH of the filtrate was neutral. The slurry was dried and stored in a vacuum oven at 60°C for 24 hours. The dried powder sample is 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 were mixed with water and ultrasonically processed at 60W power for 10 minutes to obtain a graphene dispersion.

A small amount was sampled, dried, and studied by TEM, which showed that most of the NGP is between layer 1 and layer 10. The oxygen content of the produced graphene powder (GO or RGO) ranges from 0.1% to about 25%, depending on the expansion temperature and time.

Several graphene dispersions are added with various acids, metal salts and oxidant species for polymerization The metalization of the compound.

Example 2 : Oxidation and expansion of natural graphite

According to the method of Hummers [US Patent No. 2,798,878, July 9, 1957], it is prepared by oxidizing graphite flakes with sulfuric acid, sodium nitrate and potassium permanganate at a ratio of 4:1:0.05 at 30°C for 48 hours. oxidised graphite. After the reaction was completed, the mixture was poured into deionized water and filtered. The sample was then washed with a 5% HCl solution to remove most of the sulfate ions and residual salts, and then repeatedly washed with deionized water until the pH of the filtrate was approximately 4. The intention is to remove all sulfuric acid and nitric acid residues from the graphite interstices. 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 in a horizontal tube furnace preset at 1,050°C to obtain highly expanded graphite. The expanded graphite and 1% surfactant were dispersed in water in a flat-bottomed flask at 45°C, and the resulting suspension was subjected to ultrasonic treatment for a period of 15 minutes to obtain the dispersion of graphene oxide (GO) flakes body.

Example 3 : Preparation of primary graphene

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

Example 4 : 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) consists of the intercalation compound C ₂ F. x ClF ₃ preparation. HEG is further fluorinated by chlorine trifluoride vapor to produce fluorinated highly expanded graphite (FHEG). The pre-cooled Teflon reactor was filled with 20 mL-30 mL of pre-cooled liquid ClF ₃ , and then the reactor was closed and cooled to liquid nitrogen temperature. Subsequently, no more than 1 g of HEG was put into a container _{with holes for ClF 3} gas to enter the reactor. After 7-10 days, a gray beige product _{with the approximate formula C 2 F was formed.} The GF flakes are then dispersed in a halogenated solvent to form a suspension.

Example 5 : Preparation of Nitride Graphene

The graphene oxide (GO) synthesized in Example 2 was finely ground with different ratios 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 are named N-1, N-2, and N-3, respectively, and the nitrogen of these samples is determined by elemental analysis. The contents are 14.7wt.%, 18.2wt.% and 17.5wt.%, respectively. These nitrided graphene sheets remain dispersible in water.

Example 6: Graphene-bound/activated ABS

The first group of several ^{ABS plastic rectangular strips each with a surface of 50 cm 2} were immersed in an etching solution composed of _{4M H 2} SO ₄ and 3.5M CrO ₃ at 70° C. for 3 minutes. Rinse these strips with water. On a separate basis, a second set of several strips of the same size was used, but no etching was performed.

The two sets of samples were immersed in the RGO-water solution prepared in Example 1 for a period of 30 seconds at 40°C, and then removed from the solution and dried in the air. Subsequently, the RGO-bonded ABS strip was copper-plated in a sulfuric acid-containing copper electrolyte. We have unexpectedly observed that the disclosed method can successfully metallize ABS and various plastics without etching. The bonding metal layer mediated by the graphene sheet performs equally well in terms of surface hardness, scratch resistance, and durability against heating/cooling cycles.

Comparative example 6a: Pd/Sn activated ABS

The first group of several ^{ABS plastic rectangular strips each with a surface of 50 cm 2} were immersed in an etching solution composed of _{4M H 2} SO ₄ and 3.5M CrO ₃ at 70° C. for 3 minutes. Rinse these strips with water. On a separate basis, a second set of several strips of the same size was used, but no etching was performed.

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

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

The first group of several ^{HIPS plastic rectangular strips each having a surface of 50 cm 2} were immersed in an etching solution composed of _{4M H 2} SO ₄ and 3.5M CrO ₃ at 70° C. for 3 minutes. Rinse these strips with water. On a separate basis, a second set of several strips of the same size was used, but no etching was performed.

Thereafter, the plastic product was sprayed with a native graphene-binder solution containing 5 wt% of graphene sheets and 0.01 wt% of epoxy resin. After removing the liquid medium (acetone) and curing at 150°C for 15 minutes, the graphene sheet was well bonded to the plastic surface.

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

Comparative Example 7a: Sulfide activated high impact polystyrene (HIPS)

The first group of several ^{HIPS plastic rectangular strips each having a surface of 50 cm 2} were immersed in an etching solution composed of _{4M H 2} SO ₄ and 3.5M CrO ₃ at 70° C. for 3 minutes. Rinse these strips with water. On a separate basis, a second set of several strips of the same size was used, but no etching was performed.

Thereafter, the plastic article 30 seconds in an ammonia solution containing 0.5M CuSO _4. 5H ₂ O in the solution having a pH of 9.5 and the temperature 20 ℃. The plastic product was then immersed in distilled water for 20 seconds, and then treated with a _{sulfide solution containing 0.1 M Na 2} S ₂ at 20° C. for 30 seconds. After this treatment, the plastic products are washed again in cold water. After this, electrochemical nickel plating is performed. To this end, the product was treated for 15 minutes in a Watts electrolyte containing 1.2M NiSO ₄ .7H ₂ O, 0.2M NiCl _{2 .6H 2} O and 0.5MH ₃ BO ₃ . The initial current is 0.3A/dm ² , and nickel plating is performed at 40°C. We have observed that in the absence of heavy etching, the use of sulfide seeding methods cannot uniformly metallize the surface of HIPS plastic. In contrast, the graphene-mediated method of the present invention enables almost all kinds of metals to be successfully plated not only on HIPS surfaces but also on any other types of polymer surfaces.

Example 8: Polyurethane-based thermoplastic elastomer (TPE) realized by graphene

Soak the TPE strips in an alkaline aqueous solution containing 5g/L sodium hydroxide and 0.5g/L GO for 15 minutes. The strips are then removed from the solution (actually the graphene dispersion) so that the graphene oxide flakes can be coated on the surface of the TPE while removing water. Rinse the remaining NaOH with water.

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

In contrast, if strong chromium sulfuric acid is not used as an etchant to generate large-size micro-holes (surface voids) with a depth greater than 0.3 μm, the TPE parts cannot be metalized uniformly under the instructions of the Pd/Sn catalyst seed. After immersing the etched TPE sample in a Pd/Sn colloid solution containing 80mg/L palladium, 10g/L tin(II) and 110g/L HCl at 30°C for 10 minutes, the Pd/Sn catalyst deposits To the large surface cavity of TPE.

Example 9: Graphene bonded glass fiber reinforced polyester composite

Catalytic metals can be deposited on the surface of graphene using various processes: physical vapor deposition, sputtering, chemical vapor deposition, chemical reduction/oxidation, electrochemical reduction/oxidation, etc. In this example, Co is used as a representative catalytic metal, and chemical oxidation/reduction from the solution is used to deposit nano particles on the graphene surface.

A cobalt salt solution is used as the metal salt solution. Cobalt (II) salt aqueous solution containing 1g / L to 10g / L of CoSO ₄ .7H ₂ O and an oxidizing agent, i.e. hydrogen peroxide. The graphene oxide flakes are dispersed in the solution to form a dispersion. Heating this dispersion causes at least part of the cobalt (II) to be _{oxidized by H 2} O ₂ to cobalt (III), which is deposited on the graphene surface when further heated. The 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 performed in Watts electrolyte at 30°C to 40°C for a treatment time of 10 minutes to 15 minutes. Watts electrolyte contains 1.2M NiSO ₄ .7H ₂ O, 0.2M NiCl _{2 .6H 2} O and 0.5MH ₃ BO ₃ .

Example 10: Functionalized graphene- and CNT-bound polyether ether ketone (PEEK) and other polymer components

The first group of several ^{PEEK plastic rectangular strips each having a surface of 50 cm 2} were immersed in an etching solution composed of _{4M H 2} SO ₄ and 3.5M CrO ₃ at 70° C. for 3 minutes. Rinse these strips with water. Separately, a second set of several strips of the same size was used, but no etching was performed.

Subsequently, the plastic product was dipped into a functionalized graphene/CNT-binder dispersion containing 5 wt% of graphene sheets or carbon nanotubes (CNT) and 0.01 wt% of epoxy resin or polyurethane. The chemical functional groups involved in this study include azide compounds (2-azidoethanol), alkyl silanes, hydroxyl groups, carboxyl groups, amine groups, sulfonic acid groups (--SO ₃ H), and two Ethylene triamine (DETA). These functionalized graphene sheets and CNTs were supplied by Taiwan Graphene Co. in Taipei, Taiwan. After removing the liquid medium (acetone) and curing at 150°C for 15 minutes, the graphene sheets and CNTs were well bonded to the plastic surface.

After this treatment, the graphene-and CNT-combined plastic product is subjected to electroless nickel plating or electroless copper plating. For nickel plating, the functionalized graphene-and CNT-combined product contains 1.2M NiSO ₄ . Treat in a 7H ₂ O electroless plating solution at 40°C for 15 minutes. For plating Cu, the functionalized graphene - CNT- plastic parts and immersed in the ammonia solution containing binding 0.5M CuSO _4. 5H ₂ O in 30 seconds, the solution has a pH value of 9.5 and the temperature 20 ℃.

Similar procedures have been carried out 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 resin.

We have observed that, in general, even if no etching process is performed, the functionalized graphene-mediated method of the present disclosure can also metalize polymer parts well. In all cases, the metal and polymer part surfaces are well bonded, and these surfaces have an excellent matt appearance and outstanding scratch resistance. If functionalized graphene sheets are included alone or in combination with functionalized CNTs, the metalized surface is generally smoother than when functionalized CNTs are used alone in an impregnated dispersion.

This disclosure has the following unexpected advantages:

1. Even if chromic acid or chromium sulfuric acid is not used, it is possible to achieve strong adhesion between the deposited metal layer and the lightly etched polymer surface through the mediation of functionalized graphene sheets and/or the mediation of functionalized CNTs . These well-bonded metal layers show high temperature cycle resistance and withstand all usual temperature cycle shocks.

2. A variety of chemical functional groups can be attached to the edges or surfaces of media-mediated graphene sheets or carbon nanotubes that enable rapid metallization of polymer parts.

3. The disclosed manufacturing process can be performed under very mild conditions requiring only a short period of time. The best results can be achieved without repeating the process steps normally required in the prior art process.

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

5. An unexpected variety of polymers (not only plastic but also rubber and composite materials) can be effectively metallized. In contrast, with the prior art process, only a limited amount of plastic can be satisfactorily metallized.

6. Since there is no need to etch the plastic surface at high temperature, energy saving can be achieved. Since mild etching conditions are required only when necessary and in rare cases (for example, highly smooth ultra-high molecular weight PE surfaces), a wider range of mild etching solutions can be used; the use of environmentally-restricted chemical solutions is avoided. The need for academic quality.

7. The process or method of the present disclosure may only involve two steps: contacting the surface of the polymer part with graphene or CNT dispersion (such as the dipping step), and contacting the surface of the graphene/CNT-bound polymer part with an electroless plating solution Or electrochemical plating solution contact (for example, another rapid dipping step). In contrast, the prior art process requires many steps: pretreatment, chemical etching, activation, chemical metallization, and electrolytic deposition of multiple metal layers (hence, additional multiple steps).

Claims (22)

A polymer product with a metalized surface, the polymer product comprising: a polymer part having a surface, a first layer of a plurality of graphene sheets coated on the surface of the polymer part, and a first layer deposited on the first A metal-plated second layer on one layer, the second layer is a metal-plated layer composed only of metal-plated, wherein the plurality of graphene sheets comprise selected from primary graphene materials or non-primary graphene materials Single-layer or few-layer graphene sheets, wherein the non-native graphene is selected from graphene oxide, reduced graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated graphene Graphene, nitrided graphene, doped graphene, chemically functionalized graphene, or a combination thereof, and wherein the plurality of graphene sheets are bonded to the surface of the polymer component with or without a binder resin And the first layer has a thickness from 0.34 nm to 30 μm. The polymer product with a metalized surface as described in item 1 of the scope of the patent application, wherein the second layer has a thickness from 0.5 nm to 1.0 mm. According to the first item of the scope of patent application, the surface metallized polymer product, wherein the polymer component comprises plastic, rubber, thermoplastic elastomer, polymer matrix composite material, rubber matrix composite material, or a combination thereof. According to the first item of the scope of patent application, the surface metallized polymer product, wherein the polymer component comprises a thermoplastic, a thermosetting resin, an interpenetrating network, a rubber, a thermoplastic elastomer, a natural polymer, or a combination thereof. The surface metallized polymer product described in the first item of the scope of patent application, wherein the polymer component 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, polyether ether, polyether ether ketone (PEEK), polyether, polyphenylene ether (PPO), polyvinyl chloride (PVC), polyimide, polyimide imine, polyurethane, polyurea, or Its combination. The polymer product with surface metallization as described in item 1 of the scope of patent application, wherein the metal to be plated is selected from copper, nickel, aluminum, chromium, tin, zinc, titanium, silver, gold, rhodium, alloys thereof, or Its combination. As described in the first item of the scope of the patent application, the surface metallized polymer product, wherein the graphene sheet is further modified with nano-scale particles or coatings of catalytic metal having a diameter or thickness from 0.5 nm to 100 nm, The catalytic metal is selected from cobalt, nickel, copper, iron, manganese, tin, zinc, lead, bismuth, silver, gold, palladium, platinum, rhodium, alloys thereof, or combinations thereof, and wherein the catalytic metal is in a chemical composition The above is different from the metal to be plated. According to the first item of the scope of patent application, the surface metallized polymer product, wherein the doped graphene includes nitrogen-doped graphene, boron-doped graphene, phosphorus-doped graphene, or a combination thereof. The polymer product with a metalized surface as described in the first item of the scope of the patent application, wherein the surface of the polymer component only contains small openings or holes with a diameter or depth of <0.1 μm before the first layer is deposited. The surface metallized polymer product as described in the first item of the scope of patent application, wherein the plurality of graphene sheets are bonded to the surface of the polymer component with an adhesive resin, with a ratio of from 1/5000 to 1/10 The weight ratio of binder to graphene. A method for producing a polymer product with a metalized surface as described in item 1 of the scope of the patent application, the method comprising: a) chemically, physically or mechanically treating the surface of a polymer component to prepare a surface-treated polymer Component; b) providing a graphene dispersion containing a plurality of graphene sheets dispersed in a liquid medium, contacting the surface-treated polymer component with the graphene dispersion and promoting the deposition of the graphene sheets to On the surface of the surface-treated polymer component, wherein the graphene sheet is bonded Bonded to the surface to form a layer of bonded graphene sheets; and c) depositing a metal layer chemically, electrochemically, or electrolytically on the layer of bonded graphene sheets to form a polymerized surface metallization Products. A graphene dispersion for metalizing the surface of a polymer by the method described in claim 11, the graphene dispersion comprising a plurality of graphene sheets dispersed in a liquid medium, wherein the The plurality of graphene sheets includes a single-layer or few-layer graphene sheet selected from a primary graphene material having substantially 0% non-carbon elements or a non-primary graphene material having 0.001% to 25% by weight of 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 Heterographene, chemically functionalized graphene, or a combination thereof, and the graphene dispersion further comprises one or more species selected from the following: (i) an etchant selected from an acid, an oxidizing agent, a metal salt, or a combination thereof (Ii) Nano-scale particles or coatings of catalytic metal having a diameter or thickness from 0.5nm to 100nm, the catalytic metal selected from nickel, iron, manganese, tin, lead, bismuth, palladium, alloys thereof, or Combination; or (iii) its combination. A continuous method for producing a polymer product with a metallized surface, the method comprising: a) continuously immersing the polymer product into a graphene dispersion containing a plurality of graphene sheets dispersed in a liquid medium for a period of immersion Time, and then withdraw the polymer article from the dispersion so that graphene sheets can be deposited on the surface of the polymer article to form a graphene-attached polymer article; b) continuously The graphene-attached polymer product is moved to a drying or heating zone, so that the graphene sheet can be bonded to the surface to form a graphene-covered polymer product; and c) the graphene-covered polymer product Move continuously into the metallization zone, in the metallization zone, the metal layer is chemically, electrochemically or electrolytically deposited on the graphene-covered polymer On the surface of the article to form a metalized polymer article on the surface. The method described in item 13 of the scope of patent application further includes an additional step of continuously moving the polymer article to the surface treatment zone to treat the surface of the polymer article before step (a). The method according to claim 14, wherein the additional step includes subjecting the surface of the polymer article to an etching treatment using an etchant selected from the group consisting of acids, oxidizers, metal salts, and combinations thereof. The method according to claim 14, wherein the additional step includes subjecting the surface of the polymer article to an etching treatment without chromic acid or chromium sulfuric acid. The method according to claim 13, wherein the liquid medium further comprises permanganic acid, phosphoric acid, nitric acid, or a combination thereof dissolved in the liquid medium. The method described in item 13 of the scope of the patent application, wherein the graphene dispersion further comprises a binder resin having a weight ratio of the binder to the graphene from 1/5000 to 1/10. The method according to item 13 of the scope of the application, wherein the graphene dispersion comprises a plurality of graphene sheets dispersed in a liquid medium, and wherein the plurality of graphene sheets comprises a non-volatile material having substantially 0% Carbon element primary graphene material or a single-layer or few-layer graphene sheet of non-carbon element non-primary graphene material with 0.001% to 25% by weight, wherein the non-primary graphene is selected from graphene oxide, reduction Of graphene oxide, fluorinated graphene, chlorinated graphene, brominated graphene, iodized graphene, hydrogenated graphene, nitrided graphene, doped graphene, chemically functionalized graphene, or a combination thereof, and The graphene dispersion further includes one or more species selected from the following: (i) a binder resin dissolved or dispersed in the liquid medium, wherein the weight ratio of the binder to the graphene is from 1/5000 to 1/ 10; (ii) An etchant selected from an acid, an oxidizer, a metal salt, or a combination thereof; (iii) A nano-scale particle or coating of a catalytic metal with a diameter or thickness from 0.5 nm to 100 nm, 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 (iv) combinations thereof. A polymer product with a metallized surface, the polymer product comprising: a polymer part having a surface; a plurality of functionalized graphene sheets with a first chemical functional group coated on the surface of the polymer part; A first layer of a plurality of functionalized carbon nanotubes or a combination of the second chemical functional group; and also includes a second layer of metal plated deposited on the first layer, the second layer It is a metal-plated layer composed of metal-plated only, wherein the plurality of functionalized graphene sheets comprise single-layer or few-layer graphene sheets and the plurality of functionalized carbon nanotubes comprise single-wall or multi-wall carbon nanotubes Meter tube, and wherein the plurality of functionalized graphene sheets or functionalized carbon nanotubes are bonded to the surface of the polymer component with or without a binder resin, and the first layer has a thickness from 0.34 The thickness is from nm to 30μm. The polymer product with a metalized surface as described in item 20 of the scope of the patent application, wherein the second layer has a thickness from 0.5 nm to 1.0 mm. The surface metallized polymer product described in the scope of the patent application described in item 20, wherein the first layer comprises a binder resin, and the binder resin connects the functionalized graphene sheet or the functionalized carbon nano The tube is chemically bonded to the surface of the polymer component.

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