ONE-POT ORGANIC POLYMERIC SURFACE ACTIVATION AND NANOPARTICLE REDUCTION

Abstract

Methods for attaching a reducible nanomaterial to an organic polymer are described herein. A method includes subjecting a reaction mixture that includes the reducible nanomaterial and the organic polymer to a reducing agent under reaction conditions sufficient to reduce the nanomaterial, activate the organic polymer, and attach the reduced nanomaterial to the organic polymer during the reaction.

Claims

1. A method for attaching a reducible nanomaterial to an organic polymer, the method comprising subjecting a reaction mixture comprising the reducible nanomaterial and the organic polymer to a reducing agent under reaction conditions sufficient to reduce the nanomaterial, activate the organic polymer, and attach the reduced nanomaterial to the organic polymer during the reaction.

2. The method of claim 1, further comprising obtaining the reaction mixture by depositing the reducible nanomaterial on the organic polymer.

3. The method of claim 2, wherein the reaction mixture is treated with the reducing agent after the reducible nanomaterial has been deposited on the organic polymer or during deposition of the reducible nanomaterial on the organic polymer.

4. The method of claim 1, wherein the reducible nanomaterial is an oxygen-containing carbon nanostructure, a defect-containing carbon nanotube, a transition metal compound, or a transition metal oxide.

5. The method of claim 4, wherein the reducible nanomaterial comprises additional nanostructures, wherein the nanostructures and/or additional nanostructures are nanorods, nanowires, nanoparticles, quantum dots, or any combination thereof.

6. The method of claim 5, wherein the additional nanostructures comprise a metal oxide, a metal, a bi-metallic compound, a tri-metallic compound, an alloy, a carbon-based compound, a carbide, a chalcogenide, or any combination thereof.

7. The method of claim 4, wherein the oxygen-containing carbon nanostructure is graphene oxide.

8. The method of claim 4, wherein the transition metal compound or the transition metal oxide comprises vanadium.

9. The method of claim 1, wherein the organic polymer is a thermoplastic polymer or blend thereof.

10. The method of claim 1, wherein the reducing agent is a nitrogen containing compound, wherein the nitrogen containing compound comprises is a mono-amine, a di-amine, a polyamine, a hydrazine, a hydrazine monohydrate, a di-imide, or mixtures thereof.

11. The method of claim 1, wherein the nanomaterial has not previously been reduced or activated.

12. The method of claim 1, wherein the organic polymer is in the form of an organic polymeric substrate and the reduced nanomaterial is attached to the surface of the substrate after the reaction.

13. The method of claim 12, wherein the substrate is in the form of a film, sheet, or a fiber mesh.

14. The method of claim 1, wherein the reduced nanomaterial is covalently attached to the organic polymer or the reduced material is attached to the organic polymer via hydrogen bonds or via a combination of hydrogen bonds and covalent bonds after the reaction.

15. The method of claim 1, wherein the reaction mixture is an aqueous mixture.

16. A polymeric material having reduced graphene oxide attached to the surface of an organic polymer, wherein the polymeric material is prepared by the process of claim 1.

17. The polymeric material of claim 16, wherein the polymeric material is comprised in an electronic device.

18. The polymeric material of claim 16, wherein the polymeric material is an electrode.

19. The polymeric material of claim 18, wherein the electrode is in a capacitor.

20-25. (canceled)

26. The method of claim 1, wherein the reducing agent is hydrazine monohydrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] FIG. 1 is a non-limiting chemical structure of a graphene oxide compound.

[0028] FIG. 2 is a schematic of an embodiment of a method to produce the polymeric material of the present invention.

[0029] FIG. 3 is a non-limiting chemical structure of a reduced graphene oxide compound attached to an organic polymer.

[0030] FIG. 4 is a schematic of an embodiment of a method to produce the polymeric material of the present invention.

[0031] FIGS. 5A and 5B depict a schematic of an embodiment of a method to prepare the polymeric material that includes reducible material decorated with the nanostructures.

[0032] FIG. 6 depicts a schematic of a roll-to roll process to make a flexible laminate that includes the polymeric material of the present invention.

[0033] FIG. 6A is an enlarged top view of the flexible laminate of FIG. 6.

[0034] FIG. 7A shows an FTIR spectrum for a PET blank.

[0035] FIG. 7B shows an FTIR spectrum for a PET substrate coated with reduced graphene oxide made using the method of the present invention.

[0036] FIG. 8A shows the FTIR spectra for graphene oxide dispersed on PET.

[0037] FIG. 8B shows the comparison of the carbonyl stretch region for FIG. 8A and FIG. 7B.

[0038] FIG. 9A is an enlarged region of the carbonyl stretch region from around 1725 cm.sup.−1 of the FIG. 8B FTIR spectra.

[0039] FIG. 9B is an enlargement of the carbonyl stretch region around 1620 cm.sup.−1 of the FIG. 8B FTIR spectra.

[0040] FIGS. 10A and 10B are blank PET substrate (10A: transmission mode optical image; 10B: reflection mode optical image).

[0041] FIGS. 11A and 11B are PET substrate uniformly coated with graphene nanoplatelets (11A: transmission mode optical image; 11B: reflection mode optical image).

[0042] FIG. 12A is an image of a sample with reduced graphene oxide integrated between two PET substrates of the present invention that shows increased peel resistance between the substrates.

[0043] FIG. 12B is an image of a sample with graphene oxide between two PET substrates, where no reducing treatment was performed. This sample shows negligible peel resistance, where the two substrates separate easily from one another compared to samples shown in FIG. 12A.

[0044] FIGS. 13A and 13B are scanning electron microscope (SEM) images of PET uniformly coated with reduced graphene oxide (or graphene) nanoplatelets at a 20 μm and 4 μm scale respectively.

[0045] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and may herein be described in detail. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0046] The use of nanomaterials attached to polymers or polymeric surfaces has far-reaching implications in today's society. Some non-limiting uses of such composite materials include energy devices, pollution control devices, gas separation devices, electrodes, interconnects in flexible electronic devices, etc.

[0047] As discussed above, the previous processes used to make such materials can be complicated and inefficient. For instance, such processes typically require at least two separate steps that require their own reaction conditions. The first step is typically activation of the polymer or polymeric surface with a functional group. The second step introduces a nanomaterial to the functionalized polymer to create the desired attachment.

[0048] By comparison, the one-pot synthesis processes of the present invention provide distinct advantages when compared to the aforementioned multi-step processes. In the one-pot processes, a mixture of a reducible nanomaterial and an organic polymer can be contacted with a reducing agent. The reducing agent is capable of reducing the nanomaterial and activating the organic polymer such that the reduced nanomaterial attaches to the surface of the organic polymer, while preserving the properties of the reduced nanomaterial. Without wishing to be bound by theory, it is believed that the reduction and activation reactions can occur simultaneously or substantially simultaneously. Notably, it allows reduction of nanomaterials (for example, graphene oxide (GO) to reduced graphene oxide (rGO)) and produces activated moieties on the polymer site that can bond to the reduced nanomaterial in situ.

[0049] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections with reference to the Figures.

A. Materials

[0050] 1. Reducible Nanomaterials

[0051] Reducible nanomaterials are nanomaterials that have the capacity to gain electrons or hydrogen. Non-limiting examples of such materials include oxygen-carbon nanostructures, defect-containing carbon nanotube structures, transition metals compounds, metal oxides, or combinations thereof.

[0052] A non-limiting oxygen-carbon nanostructure includes graphene oxide. Graphene oxide can be prepared by treating graphite using the Hummer or Hummer modified processes (see Chen et. al., “An improved Hummers method for eco-friendly synthesis of graphene oxide”, Carbon, vol. 64, pp. 225-229 (2013), which is incorporated into the present application by reference). Graphene oxide includes many forms of oxidized or substituted carbon, for example, carbonyls, epoxides, alcohols, and carboxylic acids. The actual chemical composition of oxidized graphene varies due to the processing conditions to obtain. A non-limiting structure of graphene oxide is shown as FIG. 1. Other structures are contemplated with various alcohol, carbonyls, carboxylic acids and epoxides are contemplated. Graphene oxide is commercially available from many sources. The graphene oxide can be combined with a solvent (e.g., water or non-reactive solvent). A non-limiting example of a graphene oxide solution is an aqueous solution of graphene oxide colloids. A non-limiting example of a source of graphene oxide is Sigma-Aldrich® (Milwaukee, Wis., USA) or Graphenea (San Sebastian, SPAIN).

[0053] Defect-containing carbon nanotube structures include single cylindrical wall and multi-walled nanotubes that contain atomic vacancies or a rearrangement of the carbon bonds. A rearrangement of the carbon bonds can be referred to as a Stone-Wales (SW) defect. Defect-containing carbon nanotube structures can have larger absorption energies and charge transfer energies than those of pristine carbon nanotubes. Non-limiting examples of defects include vacancy in the lattice (mono- or di-vacancy), result of a knock-on damage, originated by chemisorbant or physiosorbent adduct, or defects that are caused by mechanical processes (see P. G. Collins, Defects and Disorder in Carbon Nanotubes, University of California at Irvine, Irvine, USA; see also P. G. Collins, Defects and Disorder in Carbon Nanotubes in Oxford Handbook of Nanoscience and Technology: Frontiers and Advances, Narlikar, A. V. & Fu, Y. Y.Eds. (Oxford Univ. Press, Oxford, 2009), both of which are incorporated by reference). Defects in carbon nanotubes are typically characterized by a combination of electrochemical (such as conductance), spectroscopic (such as Raman), and microscopic (such as scanning tunneling microscopy, optical light microscopy and transmission electron microscopy) techniques (P. G. Collins (2009)). Commercial sources of such carbon nanotubes include Nanocyl SA (Sambreville, Belgium), Cnano Technology Limited (San Francisco, Calif., USA), and Hyperion Catalysis International Inc. (Cambridge, Mass., USA).

[0054] Transition metals compounds and transition metal oxides include compounds containing metals from Groups IIIB, IVB, VB, VIB, VIIIB, VIII, IB and IIB (Columns 3-12) of the Periodic Table, preferably metals from Group V (Column 5), most preferably, vanadium. Non-limiting examples of metal oxides include vanadium pentoxide (V.sub.2O.sub.5), ammonium metavanadate (NH.sub.4VO.sub.3), molybdenum trioxide, ammonium molybdate (VI), tungsten trioxide, ammonium tungstate. Transition metal compounds or transition metal oxides are available from commercial sources. A non-limiting example of a source of transition metal compounds or transition metal oxides is Sigma-Aldrich® (Milwaukee, Wis., USA).

[0055] The reducible material can include nanostructures deposited on the surface of the reducible material. The nanostructures can be any shape or size (e.g., nanowires, nanoparticles, nanorods, or quantum dots). A non-limiting example is graphene oxide decorated on one or both surfaces with nanoparticles. In some embodiments, the reducible material can be decorated with nanostructures. Such nanostructures can include metal oxide, metal, bi-metallic compounds, tri-metallic compounds, metal alloys, carbon-based compounds, carbides, chalcogenides, or any combination thereof. Non-limiting examples of additional nanostructures include ZnO nanoparticles, Au nanorods, Pt nanoparticles, and CdSe/ZnS core/shell quantum dots. Nanostructures are commercially available from commercial sources. Non-limiting examples of sources of nanostructures are Sigma-Aldrich® (Milwaukee, Wis., USA) and Nanosys® (Milpitas, Calif., USA).

[0056] 2. Organic Polymers

[0057] The organic polymer can be any organic polymer, copolymer, terpolymer, cross-linked polymers, or a polymer blend comprising a polymer, copolymer, terpolymer, cross-linked polymers, or combinations thereof. In a particular aspect, the polymers have not gone any treatments to functionalize, oxidize, or reduce the carbon, oxygen, or nitrogen moieties in the polymers. In a preferred aspect, the organic polymers are a thermoplastic polymer or a blend of thermoplastic polymers. Thermoplastic polymers include polyethylene terephthalate (PET), a polycarbonate (PC) family of polymers, polybutylene terephthalate (PBT), poly(1,4-cyclohexylidene cyclohexane-1,4-dicarboxylate) (PCCD), glycol modified polycyclohexyl terephthalate (PCTG), poly(phenylene oxide) (PPO), polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polymethyl methacrylate (PMMA), polyethyleneimine (PEI) and its derivatives, polyetherimide and its derivatives, thermoplastic elastomer (TPE), terephthalic acid (TPA) elastomers, poly(cyclohexanedimethylene terephthalate) (PCT), polyethylene naphthalate (PEN), polyamide (PA), polystyrene sulfonate (PSS), sulfonated polysulfone family of polymers, polyether ether ketone (PEEK), or combinations or blends thereof. In some embodiments, the organic polymer is polypropylene, polyethylene terephthalate, polyethyleneimine, or polyethylene, or blends thereof. In certain embodiments, the organic polymer is polypropylene or polyethylene terephthalate. In some aspects, the polypropylene polymer is biaxially oriented polypropylene (BOPP). In some embodiments, the polymer can be a polymeric substrate in which its surface is patterned. The nanomaterial can then be attached to the pattern in the surface area via the processes of the present invention. The polymer can be functionalized with functional groups either in the polymer back bone or pendant such as esters, carbonates, amides, etherimides, acids, hydroxyl, etc. that can react with amine such as amino silanes, hydrazine, halogenated amines, etc. The polymers that do not have such chemistry can be pre-conditioned. For example, such as flame-treated polyolefins (e.g., polyethylene).

[0058] 3. Reducing Agents

[0059] The reducing agent can be any substance capable of reducing the functional groups of the nanomaterial and activating the organic polymer. In a preferred aspect, the reducing agent is a nitrogen containing compound. Nitrogen containing compounds include mono-amines, di-amines, polyamines, hydrazines, hydrazine monohydrate, di-imides, or mixtures thereof. In a preferred embodiment, the reducing agent is hydrazine monohydrate. Mono-amines include compounds having one nitrogen atom, for example, primary amines and secondary amines, with primary amines being preferred. Non-limiting examples of mono-amines include alkyl amines, ethylamine, propylamine, 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA), aralkyl amines, benzyl amine, aromatic amines, aniline, naphthylamine. toluidines, N,N-dimethyl-p-toluidine. Diamines include compounds that have two (2) nitrogen atoms. Examples of diamines include alkyl amines, ethylenediamine, aryl amines, phenyl diamine, and hydrazines. Examples of hydrazine compounds include hydrazine monohydrate. Amines and diamines are commercially available from numerous suppliers. A non-limiting example of a commercial supplier is Sigma-Aldrich® (Milwaukee, Wis., USA).

B. Methods For Making Polymeric Material

[0060] In some embodiments, attaching a reducible nanomaterial to an organic polymer includes subjecting a reaction mixture that includes the reducible nanomaterial and the organic polymer to a reducing agent under reaction conditions sufficient to reduce the nanomaterial, activate the organic polymer, and attach the reduced nanomaterial to the organic polymer during the reaction. An organic polymer can be obtained and mixed with the reducible nanomaterial in a suitable solvent in a single reaction vessel (“one-pot”). The organic polymer can be patterned prior to mixing the organic polymer with the nanomaterial. In some embodiments, the reducible material can be decorated with nanostructures. In embodiments, when the organic polymer is BOPP, the polymer can be treated with flame or corona plasma discharge. In a non-limiting embodiment, the organic polymer and nanomaterial are mixed in the absence of solvent. A suitable solvent can include water, alcohols, ethanol, glycol, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) or mixtures thereof. In some embodiments, the reducing agent is the solvent, for example, the organic polymer and the nanomaterial are mixed in hydrazine monohydrate. The mixture can be heated to a temperature suitable to allow the reducing agent to react with the organic polymer and the nanomaterial. The temperature can be from 25 to 500° C., 50 to 250° C., or 75 to 100° C., or the refluxing temperature of the solvent.

[0061] 1. Deposition of the Reducible Nanomaterial on the Surface of a Polymer

[0062] FIG. 2 is a schematic of a method for forming the polymer material of the present invention. The reducible nanomaterial 202 can be deposited on the surface of polymer 204. The reducible nanomaterial 202 can include nanostructures deposited on the surface (see, FIG. 5). The deposition can be done through chemical vapor deposition, transfer tape, roll-to-roll, or any other known deposition method. In some embodiments, the organic polymer, for example, BOPP, nanomaterial, and reducing agent are subject to a plasma discharge under a reducing agent atmosphere. As shown in FIG. 2, organic polymer 202 includes reducible nanomaterial (“nanomaterials”) 204. As shown in FIG. 2, the reducible nanomaterials 204 are positioned in grooves 206 that have been patterned on the surface of the polymer 202. The polymer 202 with deposited reducible nanomaterials 204 can enter the reaction unit 208 via inlet 210. The polymer 202 with deposited reducible nanomaterials can be obtained from a third party or the deposition can occur offsite or in another unit of a manufacturing facility. The reducing agent can enter reaction unit 208 through inlet 212. In some embodiments, the reducing agent can be put in the reaction unit 208 and the polymer 202 with deposited reducible nanomaterials 204 can then be added to the reaction unit 208. The polymer 202 with deposited reducible nanomaterials 204 can be heated in the presence of the reducing agent until the reducible nanomaterial is reduced and the polymeric material 214 having reduced nanoparticles 216 is formed. In some instances, a majority or substantially all of the reduced nanomaterials 216 are attached to the surface of polymer 202. The polymeric material 214 can exit the reaction unit 208 via polymeric outlet 218. FIG. 3 is a contemplated structure of the polymeric material 214 when the reduced nanomaterial is reduced graphene oxide. As shown in FIG. 3, an oxygen atom of the reduced graphene oxygen is bonded to the polymer. The amount of reduction can be controlled by reaction time and/or the amount of reducing agent. In one embodiment, the reducing agent is applied to the surface of the polymer and then the reducible nanomaterials are deposited on the surface of the polymer. Upon heating the organic polymer 206, reducible nanomaterials 204, and reducing agent in the reaction unit 208, the reducing agent, organic polymer, and reducible nanomaterials react such that the reducible nanomaterial attaches or covalently bonds to the organic polymer.

[0063] 2. Spray Coating of Reducible Nanomaterial

[0064] FIG. 4 is a schematic of a method for forming the polymer material of the present invention. An organic polymer stream can enter the reaction unit 208 via organic polymer stream inlet 402. A reducible nanomaterial stream (e.g., an aqueous solution of the reducible nanomaterials such as, for example, graphene oxide colloids, or graphene oxide flakes) can enter the reaction unit via reducible nanomaterial stream inlet 404 and be deposited on the organic polymer 206. As shown in FIG. 4, the reducible nanomaterials are being applied using spray device 406. In some embodiments, the organic polymer and the reducible nanomaterials enter the reaction unit 208 in one stream or the two streams can be combined prior to enter the reaction unit. The reducing agent (e.g., an aqueous stream reducing agent such as, for example, hydrazine hydrate) can enter reaction unit 208 through reducing inlet 212. In some embodiments, the reducing agent can be put in the reaction unit 208 and prior to the polymer stream and reducible nanomaterial entering the reaction unit 208. In some embodiments, the reducing agent is applied to the organic polymer followed by a coating of the reducible material (with or without deposited nanostructures). The polymer 206 with deposited reducible nanomaterials 204 can be heated in the presence of the reducing agent until the reducible nanomaterial is reduced and the polymeric material 214 having reduced nanoparticles 216 is formed. In some instances, substantially all of the reduced nanomaterials 216 are attached to the surface of polymer 206. The polymeric material 214 can exit the reaction unit 208 via polymeric material outlet 218. In a particular embodiment, reaction unit 208 is plasmatron and the polymer 206 and reducible nanomaterial 204 are subject to plasma radiation under a reducing agent atmosphere while in the plasmatron. In some embodiments, the polymer is a mesh, a sheet, a film, or a bead. As shown in FIG. 4, polymeric material 214 includes reduced nanomaterial (e.g., graphene flakes) 408 attached or linked to the polymeric mesh 410.

[0065] 3. Reducible Nanomaterial With Deposited Nanostructures on the Surface of a Polymer

[0066] In some instances, the polymeric material can be made by coating a polymeric substrate with a reducing agent and the reducible nanomaterials with deposited nanostructures. The coating of the reducing agent and/or reducible nanomaterials as described above in Section B(2) or using other known coating methods (e.g., dip coating). FIGS. 5A and 5B depict a schematic of method 500 to prepare the polymeric material that includes reducible material decorated with the nanostructures. Referring to FIG. 5A a polymeric sheet or film 502 can be coated with an aqueous solution reducing agent RA (e.g., hydrazine (NH.sub.2NH.sub.2)) and then coated with an aqueous reducible nanomaterial 214 deposited with nanostructures 504. Referring to FIG. 5B a polymeric bead 506 can be coated with a reducing agent RA (e.g., hydrazine (NH.sub.2NH.sub.2)) and then coated with a reducible nanomaterial 214 deposited with nanostructures 504. In some embodiments, the polymeric bead 506 can include nano- or microparticles (e.g., metal oxides) or polymer brush architectures. The coated polymeric sheet, film or bead can be heated to about 75° C. to 85° C. until the reaction between the polymer, reducible nanomaterial and the reducing agent is complete (e.g., 8 to 12 hours). The reducing agent reacts with the reducible material and the polymer and forms linker (L), which links or attaches the polymer material (e.g., polymeric film/sheet 502 or polymeric bead 506) to the reduced material 216. For example, hydrazine NH.sub.2NH.sub.2 can react with the carboxylic acid of graphene oxide and a carboxylic acid functional group of a polymer to form an acylated hydrazide shown below.

##STR00001## [0067] where P is the polymeric substrate

[0068] Without wishing to be bound by theory, it is believed that one or more pathways can produce the polymeric material. A first pathway can include stepwise reactions of the reducing agent with the organic polymer material and/or the nanomaterials to form intermediates that react to form the polymeric material. A first pathway can include the reducing agent reacting with the organic polymer to form a polymer-reducing agent intermediate. The polymer reducing agent intermediate can react with the reducible nanomaterial and form the polymeric material 214. A second pathway can include the reducing agent reacting with the nanomaterial to form a reducible nanomaterial-reducing agent intermediate. The reducible nanomaterial-reducing agent intermediate can react with the polymer to form the polymeric material 214. A third pathway can include the formation of the two intermediates which then react or form the polymeric material 214.

[0069] The reducible nanomaterial can undergo 1 to 100%, 10%, 20%, 50%, 75%, 80%, 90%, or 100% reduction. In some embodiments, the reduced nanomaterial includes a mixture of reduced and unreduced sites, however, the amount of reduction of the nanomaterial is sufficient to allow attachment of the reduced nanomaterial to the surface of the polymer. A ratio of reduced and unreduced sites in the reduced nanomaterial 216 can range from 0.0001:100 to 1:99, or 10:90, 20:80, or 50:50. In a non-limiting example, polymeric material 214 includes reduced graphene oxide as the reduced nanomaterial. The reduced graphene oxide can have a mixture of reduced and unreduced sites.

[0070] The nanocomposites of such polymer structures with graphene, or graphene heterostructures, wrapped around the polymer can be treated to remove the encapsulated polymer (e.g., heat treated in an oxidizing atmosphere) to result in hollow graphene-based architectures. This approach provides a significantly less complicated method for hollow graphene architectures preparation as compared to conventional methods, which typically require multiple templating and acid/base etching steps. Such architectures will be useful for catalysis, sensors, plasmonics, electrodes, and energy storage.

C. Uses of the Produced Polymeric Material

[0071] The produced polymeric materials of the present invention can be used in a wide range of applications and electronic devices.

[0072] By way of example, the process of the present invention can be used to create either or both of the upper and lower electrodes for a single device or can be used to create cathodes and anodes for a single device. By way of example only, the materials of the present invention can be incorporated into a wide variety of devices, including any device that currently makes use of transparent conductors (such as metal oxide films) or reflective conductors or both. For instance, the following devices are contemplated: (i) Electronic display devices including an electroluminescent (EL) device (e.g., an organic light emitting display (OLED)), an electrophoretic display (e-paper), an electrochromic device, a liquid crystal display device (e.g., transflective liquid crystal display (LCD) devices) or an electrowetting display device; (ii) Photovoltaic cells, for instance amorphous silicon (a-Si) cells; (iii) Light irradiation devices and decorative illumination devices, for instance, devices containing light-emitting elements such as light-emitting diodes and semiconductor lasers; (iv) Electromagnetic radiation shield devices; (v) Any device which requires a reflective electrode; and (vi) Electronic device e.g., a transistor, a resistor, a logic device, sensors, antennas, integrated circuits, electroluminescence devices, memory elements or a field effect device.

[0073] In some embodiments, the polymeric material can be a fiber mesh integrated with graphene. The reducing agent (e.g., hydrazine) based one-step treatment can be utilized to coat graphene and link the flakes to the surface of fibers, bridge fibers, and uniformly disperse and integrate flakes within the fiber mesh. This method can overcome problems associated with high temperature in-situ growth of graphene using copper-coated mesh structures. Apart from that, the physically-mixed graphene flakes (in fiber mesh) due to less z-direction strength impart low shear strength to such composites. This shear strength can be significantly improved by utilizing the methods as described in this application. Being a single-step and water-based functionalization process, the challenges of multi-step and non-specific functionalization approaches can be overcome. For example, polymer fiber mesh integrated with reduced graphene oxide made using the methods described herein can be useful for optical fiber protection coatings, functional coatings, masking for printed electronics, lightening protection system, smart textile, sensors, and high-strength and light-weight structural material. Coatings can include optical fiber protection coatings, functional coatings, and masks for printed electronics. Functional coating can include coatings with a capability to send chemical and biological agents, humidity, brine, stress; gas barrier coatings and thermally or electronically conductive coatings.

[0074] In other aspects of the invention, the polymeric material of the present invention can be used as a pollution control and mitigation platform by catalyzing the destruction of undesired gases such as SOx and NOx. In some aspects of the invention, the polymeric material is used in a gas separation surface where two gases can be separated based on differential absorption rate to the surface.

[0075] The polymeric material can be used in a roll-to roll process to produce polymer sheets, membranes, films or the like. FIG. 6 depicts a schematic of a roll-to roll process 600 to make a flexible nano-laminate 602 that includes reduced nanomaterial 604 (e.g., reduced graphene). In this approach, a first rolled sheet of polymeric material 606 containing the reduced nanomaterial 604 can be rolled in conjunction with second rolled sheet of incoming polymeric material 608 using rollers 610, 612 and 614. As the two sheets 606 and 608 merge, they can be hot-pressed or fused to result in a flexible nano-laminate 602 using rollers 616 and 618 with uniformly-dispersed reduced nanomaterial 604 in the middle of fused sheets 606 and 608. FIG. 6A is a top view of the laminate with the top sheet 608 removed. The second rolled polymeric material can include the same or different polymers than the first rolled sheet. In some embodiments, the second rolled polymeric material can include a same or different reduced nanomaterial than the first rolled polymeric material. Such polymer nanocomposites or nano-laminates are advantageous for applications where anisotropic properties are desired. These properties could be thermal, mechanical, electrical, and optical. Such flexible nano-laminates or nanocomposite films could be utilized for paper or flexible electronics.

EXAMPLES

[0076] The present invention will be described in greater detail by way of prophetic examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

Synthesis of Polymeric Material with Reduced Graphene

[0077] Graphene oxide nanocolloids (2 mg of graphene oxide nanocolloids/1 mL of water) were purchased from Sigma-Aldrich® (USA). Hydrazine hydrate (55% diluted) was purchased from Acros Organics (USA), and PET was bought in the form of transparency slides. A slide of PET was cleaned with water and dried. The dried sheet was coated with a diluted hydrazine hydrate (1 ml, 60 mM of hydrazine in water) at room temperature to produce a hydrazine coated PET substrate. The hydrazine coated PET substrate was further coated with a drop of the aqueous graphene oxide nanocolloid solution (2 mg/ml). The hydrazine/graphene oxide coated PET substrate was dried in an oven at 80° C. for overnight. The samples were characterized by Fourier Transform Infrared (FTIR) spectroscopy and optical microscopy. The procedure was repeated 3 times to produce 3 samples. FTIR was conducted on the 3 different samples and for each sample more than 5 points were generated for analysis.

Example 2: Comparative Example

PET with Hydrazine

[0078] In order to evaluate the deoxygenation or reduction of graphene oxide during the process of coating on PET substrate, a comparative experiment was conducted. A slide of PET was cleaned with water and dried. The dried sheet was coated with a diluted hydrazine hydrate (1 ml, 60 mM of hydrazine in water) at room temperature to produce a hydrazine coated PET substrate. The hydrazine coated PET substrate was dried in an oven at 80° C. for overnight. The samples were characterized by Fourier Transform Infrared (FTIR) spectroscopy and optical microscopy.

Example 3

FTIR Interpretation

[0079] Table 1 lists the FTIR peaks of: a untreated PET slide, standard PET stretches, Comparative Example 1 (hydrazine-treated PET) stretches, standard terathalic dihydrazide stretches, Example 1 (PET with reduced graphene oxide), standard graphene oxide stretches, standard reduce graphene oxide stretches, and standard hydrazine hydrated stretches.

TABLE-US-00001 TABLE 1 Std hydrazine Std PET Comparative Std terathalic Std GO Std rGO hydrated PET Blank stretches.sup.1 Example 1 dihydrazide.sup.2 Example 2 stretches.sup.3 stretches.sup.3 and stretches.sup.4 2953.37 cm.sup.−1, 3100-2800 3315 (N—H, 3327, 3213, 3428.92 3400 (O—H 3400 (O—H 3340 2050.90 (aromatic primary 3071, 3061, (shifted due stretch) stretch), (stretching and aliphatic amides) 3050, 3036 to mix of N—H significantly mode of —C—H) and O—H suppressed aliphatic —CH2— stretch) due to in ethylene deoxygenation glycol of GO segment in amorphous regions, changes with crystallinity) 1979.99 (too Doublet at 1490 (aromatic 1629, 1616, 2952.33, 1720 (C═O 1720 (C═O 1613 weak, 2960 and ring) 1608, 1544, 2883.55 (CH.sub.2 stretch) stretch) possible 2910 1492, 1343, and CH contaminant) (stretching 1292, 1246, vibrations.sup.5 mode of 1240, 1187, associated to aliphatic 1143, 1106, remaining —CH2— 1017 COOH in ethylene groups in GO) glycol and overlap with segment in stretching amorphous mode of regions, aliphatic —CH2— changes with in ethylene crystallinity) glycol segment in amorphous regions, changes with crystallinity) 1713.14 (ester 1720 (ester 1340 (C—N) 930, 889, 882, 2324.41, 1600 1461 C═O, depends C═O) 738, 714, 641, 2160.71, (skeletal on 631, 503, 497, 2139.64, vibrations crystallinity) 2050.84, from 1979.33 unoxidized (weak, graphitic possible domains) contaminant, also observed in blank PET) 1578.82, 1300 (ester 1628 (C═O) 1711.65 1220 (C—OH 1360 1504.42 group) (C═O stretch, stretching) (crystallinity shifted from extent) blank PET). This shift could be attributed to amide 1 and amide 2 bands. 1470.41 1100 1290 (N—N) 1578.61, 1060 (C—O 1060 (C—O 1285 (crystallinity (methylene) 1505.18 (due stretching) stretching, extent, trans to PET, remaining form of shifted from carboxyl ethylene blank PET, groups) glycol both peaks segment) become stronger). This could attributed to N—H stretch due to amide bonds or secondary amide groups).sup.6 1453.06 (cis 1470, 1340, 1470.46 (due 1074 form of 975, 845 - to PET) ethylene transform of glycol ethylene segment glycol 1409.16, segment 1340.71 1450, 1370, 1453.64 (due 894 (crystallinity 1040, 898 - to PET) extent and cis for of influence on ethylene resonance on glycol the segment teraphthalate group, in- plane alignment of carbonyl groups with benzene ring 1241.28 1042 (anti- 1408.99 427 (stretching symmetrical (This peak is vibrations of C—O stretch shifted from ester groups, of cis form blank PET —C—O—C═O) and could be attributed to C—N stretch in amide bonds) 1096.80 (ester 1341.73 (due C—O—C bond, to PET) cis isomer of ethylene glycol segment) 1017.21 (in- 1240.90 (due plane bending to PET) of the C—H bonds of a 1,4-di-substrituted aromatic ring 969.16, 1096.94 (due 871.57, to PET) 846.60, 792.45 (conformation of ethylene glycol unit) 722.80, 1045.55 (C—O 631.61, stretching) 601.65 (out of plane bending of C—H, in-plane bending of C-bonds of benzene ring) 530.66, 1017.17, 505.53, 969.47, 435.24 (could 871.55, be attributed 846.09, to teraphthalic 792.58, dihydrazide 722.75, and remaining 631.66, hydrazine 601.68, hydrate) 530.06, 506.1, 437.59 (could be attributed to PET, teaphthalic hydrazide, and hydrazine hydrate) .sup.1Chen et al., European Polymer Journal, 2012, 48, 1586-1610. .sup.2Soni et al., Journal of Applied Polymer Science, 2009, 113, 1090-1096. .sup.3Choi et al., Journal of Materials Chemistry, 2010, 20, 1907-1912. .sup.4http://www.hanhonggroup.com/ir/ir_en/RB01060076.html .sup.5Basirun et al., Nanoscale Research Letters, 2013; 8, 397. .sup.6Tripathi et al., Synthesis of High-Quality Graphene through Electrochemical Exfoliation of Graphite in Alkaline Electrolyte, arXiv: 1310.7371

[0080] FIG. 7A shows an FTIR spectrum for a blank and FIG. 7B shows an FTIR spectrum for a coated PET substrate. FIG. 8A shows the FTIR spectra for graphene oxide dispersed on PET with no chemistry. FIG. 8B shows the comparison of the carbonyl stretch region for FIG. 8A and FIG. 7B. The dotted rectangle indicates the compared region. FIG. 9A is an enlarged region of the FIG. 8B FTIR spectra. FIG. 9B is an enlargement of the carbonyl stretch region (around 1620 cm.sup.−1) for graphene oxide dispersed on PET substrate with no chemistry (top spectra) and hydrazine processed coating of the present invention (Example 1 sample, bottom spectra) of the FIG. 8B FTIR spectra. The dotted rectangle indicates the compared regions. Many of the similarities in the spectra of graphene coated PET and the blank PET could be attributed to the PET substrate and contaminants as indicated in the Table 1 (above). Specific FTIR peaks are attributed to hydrazine-based linkage of reduced graphene oxide nanoplatelets to the PET substrate in a single-step approach. The peak at 3428.92 cm.sup.−1, which was absent in the blank PET, was attributed to a mix of O—H and N—H stretches due to hydrazine attachment on the PET substrate. The peak at 1711.65 cm.sup.−1 was attributed to C═O stretch. This peak was shifted from blank PET stretch at 1713.14 cm.sup.−1 due to ester C═O stretch and also depended on polymer crystallinity. This shift was attributed to amide 1 and amide 2 bands formation on the PET substrate when integrated with the graphene oxide nanoplatelets. Other C═O and C—H stretches corresponding to carboxylic groups (—COOH) were observed as listed in Table 1 (above). Although the samples were washed with copious amounts of water after the binding process, the presence of some of carboxylic or oxygenated groups could be due to unbound graphene oxide on PET substrate. The peaks centered around 1578.61 cm.sup.−1 and 1505.18 cm.sup.−1 were shifted from that of blank PET sample. This shift was attributed to N—H stretch due to amide bonds or secondary amide groups formed during the binding process. Finally, the peak centered around 1408.99 cm.sup.−1 (shifted from blank PET) and was attributed to C—N stretch in amide bonds.

[0081] It was observed that a twin peak present in graphene oxide (˜1710 cm.sup.−1, FIGS. 8B and 9A) converted to single peak. This was a clear indication of loss of C═O groups, which further attested to the formation of reduced graphene oxide during the integration with PET in presence of hydrazine. In addition, the focus was on the region (1500-1700 cm.sup.−1) for carbonyl stretches. This region has been critical for identifying C═O stretches in carbon nanotubes (See, Majumder et al., “Effect of tip functionalization on transport through vertically oriented carbon nanotube membranes.” Journal of the American Chemical Society, 2005, Vol. 127, pp. 9062-9070 and Chopra et al., “Bifunctional carbon nanotubes by sidewall protection.” Advanced Functional Materials, 2005, Vol. 15, pp. 858-864). Disappearance of the shoulder around 1620 cm.sup.−1 (FIG. 9B) is another indication of loss of C═O groups and formation of reduced graphene oxide on PET in presence of hydrazine.

Example 4

Optical Microscopy Interpretation

[0082] A clear or semi-transparent coating on the surface of PET of Example 1 was observed under 500× magnification optical microscope.

[0083] FIGS. 10A and 10B are blank PET substrate (10A: transmission mode optical image; 10B: reflection mode optical image). FIGS. 11A and 11B are PET substrate uniformly coated with graphene nanoplatelets (11A: transmission mode optical image; 11B: reflection mode optical image). The scale bar for all images was 10 μm for all the images. FIGS. 10 A and 10B shows blank PET with defects or contaminants. The PET substrate with the reduced graphene coating was difficult to scratch with a sharp razor and it was determined to be strongly bound to the PET substrate.

Example 5

Peel Test

[0084] Two blank PET sheets were coated with 1 ml of 60 mM hydrazine hydrate. 0.01 wt % graphene oxide was coated on one of the hydrazine-coated PET sheet. The second hydrazine-coated PET sheet was flipped on top of first sheet (with hydrazine and graphene oxide). The sandwiched samples were dried for 24 hours at 80° C. A control PET-graphene oxide-PET sandwich sample was prepared, but without any hydrazine. The dried samples were manually peeled. The sandwich sample with hydrazine treatment (FIG. 12A) was significantly difficult to peel while the control sample (FIG. 2B) did not stick and the two PET sheets were easily separated on drying.

Example 5

Scanning Electron Microscopy

[0085] A small (0.5 cm×0.5 cm) sample from Example 1 was placed on the SEM stub and inserted in the microscope for analysis. Reduced GO nanoplatelets can be seen as dots in the SEM images. FIGS. 13A and 13B are scanning electron microscope (SEM) images of PET uniformly coated with reduced graphene oxide (or graphene) nanoplatelets at a 20 μm and 4 μm scale respectively.

[0086] As shown in the Examples, the methods of the present invention resulted in reduced graphene oxide strongly attached (bonded) to the surface of PET. The experiments with graphene sandwiched between two PET sheets also resulted in strong binding between the sheets.