Formation of homogeneous nanocomposite films at ambient temperature via miniemulsion polymerization using graphene oxide as surfactant

A convenient and industrially scalable method for synthesis of homogeneous nanocomposite films comprising poly(styrene‐stat‐butyl acrylate) and nanodimensional graphene oxide (GO) or reduced GO (rGO) is presented. Importantly, the nanocomposite latex undergoes film formation at ambient temperature, thus alleviating any need for high temperature or high pressure methods such as compression molding. The method entails synthesis of an aqueous nanocomposite latex via miniemulsion copolymerization relying on nanodimensional GO sheets as sole surfactant, followed by ambient temperature film formation resulting in homogeneous film. For comparison, a similar latex obtained by physical mixing of a polymer latex with an aqueous GO dispersion results in severe phase separation, illustrating that the miniemulsion approach using GO as surfactant is key to obtaining homogeneous nanocomposite films. Finally, it is demonstrated that the GO sheets can be readily reduced to rGO in situ by heat treatment of the film. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2289–2297     

Nanocrystalline cellulose acetate (NCCA)/graphene oxide (GO) nanocomposites with enhanced mechanical properties and barrier against water vapor

Highly flexible nanocomposite films of nanocrystalline cellulose acetate (NCCA) and graphene oxide (GO) were synthesized by combining NCCA and GO sheets in a well-controlled manner. By adjusting the GO content, various NCCA/GO nanocomposites with 0.3–1 wt% GO were obtained. Films of these nanocomposites were prepared using the solvent casting method. Microscopic and X-ray diffraction (XRD) measurements demonstrated that the GO nanosheets were uniformly dispersed in the NCCA matrix. Mechanical properties of the composite films were also studied. The best GO composition of the samples tested was 0.8 wt%, giving tensile strength of 157.49 MPa, which represents a 61.92 % enhancement compared with NCCA. On the other hand, the composite films showed improved barrier properties against water vapor. This simple process for preparation of NCCA/GO films is attractive for potential development of high-performance films for electrical and electrochemical applications.     

Perfluorinated polymer film with functional group prepared by radiation-induced grafting

A perfluorinated vinyl ether monomer, 2-bromotetrafluoroethyl trifluorovinyl ether (BrTFF) was grafted into crosslinked poly(tetrafluoroethylene) (cPTFE) films by γ-rays irradiation under different conditions. The irradiation with absorbed doses more than 550 kGy gave the poly(BrTFF) grafted cPTFE membranes with grafting yields of more than 20%. FTIR spectra and SEM-EDS testified that BrTFF was successfully grafted into cPTFE films homogeneously in the film perpendicular direction. TGA analysis of the grafted films indicated that the perfluorinated poly(BrTFF) grafts were phase-separated from the PTFE region due to the crosslinked structure of the cPTFE based film, but the grafted films still had high thermal stability (above 300 °C). DSC measurements showed the decrease of melting temperature, but the increase of both heat of fusion and degree of crystallinity in cPTFE film after grafting. The grafted film, a new kind of perfluorinated polymer with bromine active groups and good mechanical properties, is expected to be modified for new applications.     

ZnO/graphene-oxide nanocomposite with remarkably enhanced visible-light-driven photocatalytic performance

In this work, a high-performance photocatalyst of ZnO/graphene-oxide (ZnO/GO) nanocomposite was synthesized via a facile chemical deposition route and used for the photodegradation of organic dye from water under visible light. The nanocomposite was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, Brunauer-Emmett-Teller N(2) adsorption-desorption analysis, and UV-Vis diffusion reflectance spectroscopy. The ZnO/GO nanocomposite consisting of flower-like ZnO nanoparticles anchored on graphene-oxide sheets has a high surface area and hierarchical porosity, which is benefit to the adsorption and mass transfer of dye and oxygen species. For the photodegradation of organic dyes under visible light, ZnO/GO nanocomposite exhibited remarkably enhanced photocatalytic efficiency than graphene-oxide sheets and flower-like ZnO particles. Moreover, the photocatalytic efficiency of ZnO/GO nanocomposite could be further improved by annealing the product in N(2) atmosphere. The outstanding photocatalytic performance was ascribed to the efficient photosensitized electron injection and repressed charge carriers recombination in the composite with GO as electron collector and transporter, thus leading to continuous generation of reactive oxygen species for the degradation of methylene blue.     

Synthesis and characterization of graphene oxide/modified poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) nanocomposite

In this study, the graphene oxide/poly(N-isopropylacrylamide) nanocomposite modified with 2-mercaptoethanol (GO/MPNIPAM) was synthesized in three stages. N-Isopropylacrylamide polymerization was firstly performed in the presence of azobisisobutyronitrile as an initiator, which was discovered by Homer, and 2-mercaptoethanol as a modifier. Then, the graphene oxide/modified polymer nanocomposite was synthesized by the covalent interactions between carboxylic acids of the graphene oxide and hydroxyl groups of the modified polymer during the esterification reaction. The GO/MPNIPAM nanocomposite includes some percentage of the polymer that improves solubility and stability of the GO sheets in physiological applications; due to the interaction between the MPNIPAM and the modified GO polymer, a bridge-like connection is formed between the GO sheets and the process that leads to remove a large number of hydrophilic groups on the GO nanocomposite and therefore, the GO/MPNIPAM is well dissolved in organic solvents. This property is beneficial for anti-cancer drug delivery as well as π–π interactions between the nanocomposite and aromatic drugs. The nanocomposite is not a toxic material for human body at all and has high capacity for drug delivery. Structure and morphology of the nanocomposite were studied by FTIR, SEM, XRD, UV, TGA and Raman analysis. The analysis done by X-ray diffraction pattern confirmed the presence of graphene oxide in nanocomposites and improved crystalline polymer in nanocomposites.     

Spectroscopic and Discharge Studies on Graphene Oxide Doped PVA/PVP Blend Nanocomposite Polymer Films

Graphene oxide (GO) nanoparticles were synthesized by modified Hummers method. The synthesized GO nanoparticles were incorporated in polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend polymers for the preparation of nanocomposite polymer films by solution cast technique. Different characterizations such as XRD, UV–Vis and FTIR were carried-out on to the prepared nanocomposite polymer films. The thermal analysis of the films was studied by DSC. The morphology of PVA/PVP:GO polymer films confirms GO was exfoliated within the PVA/PVP matrix and also reveals the heterogeneous phase of nanocomposite polymer electrolyte systems. From the conductivity studies the highest conductivity of PVA/PVP: GO (0.45: 0.3) was found to be 8.05 × 10^–4 S/cm at room temperature. Solid state battery has been fabricated with the configuration of Mg⁺/(PVA/PVP:GO)/(I₂ + C + electrolyte) and its cell parameters were calculated for a constant load of 100 kΩ.     

Surface modified graphene oxide/poly(vinyl alcohol) composite for enhanced hydrogen gas barrier film

A series of novel polyethyleneimine (PEI) modified graphene oxide (PEI-mGO) filled poly(vinyl alcohol) (PVA) nanocomposite (PEI-mGO/PVA) films were prepared by solution-casing for hydrogen gas barrier applications. Hydrophilic PEI was used to simultaneously reduce and modify graphene oxide sheets, thereby facilitating a homogeneous dispersion of PEI-mGO in the PVA matrix. The effects of PEI-mGO on the morphology and properties of the nanocomposite films were examined by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and field emission scanning electron microscopy. Analogous GO/PVA composites were also prepared and characterized for comparative purposes. The PEI-mGO/PVA nanocomposites showed higher thermal and mechanical stability as well as remarkable improvement in hydrogen gas barrier properties compared to the PVA film; specifically, the PEI-mGO/PVA film having 3.0 wt% of PEI-mGO content exhibited almost 95% decrease in GTR and permeability values compared to PVA film.     

Acetone‐Induced Graphene Oxide Film Formation at the Water–Air Interface

Graphene oxide (GO) is an amphiphilic soft material, which can accumulate at the water–air interface. However, GO sheets diffuse slowly in the aqueous phase because of their large size. It is still challenging to form high quality GO films in a controllable and simple way. In this study, we showed that GO sheets can quickly migrate to the water–air interface and form thin films when a suitable amount of acetone is directly mixed with a GO aqueous dispersion. The film formation rate and surface coverage of GO sheets depend on the volume of acetone added, GO dispersion concentration, and formation time. Among several organic solvents, acetone has its advantage for GO film formation owing to its three properties: a nonsolvent to GO aqueous dispersions, miscible with a GO aqueous dispersion, and fast evaporation. Furthermore, we have found that the film formation also is governed by the size of GO sheets and their oxygen content. Although smaller GO sheets could migrate to the water–air interface faster, the overlapping of small GO sheets and the increase in contact resistance is not desirable. A higher oxygen content in GO sheets could also result in smaller GO sheets. Multilayer GO films can be obtained through layer‐by‐layer dip‐coating. These findings open opportunities in developing simple scalable GO film fabrication processes.     

Preparation and characterization of polyvinyl alcohol/β‐cyclodextrin/GO‐Ag nanocomposite with improved antibacterial and strength properties

In this work, new hydrogel films based on polyvinyl alcohol (PVA) and β‐cyclodextrin (β‐CD) were prepared with the aim of studying their ability as an antibacterial and drug carrier system. Gallic acid (GA) was used as an antibacterial drug which was encapsulated into the β‐CD cavity, and finally, β‐CD inclusion complex (GA/βCD‐IC) was prepared. On the other hand, silver nanoparticles (AgNPs) were synthesized on the graphene oxide (GO) surface (GO‐Ag), and the obtained GO‐Ag was used to enhance the antibacterial properties and mechanical strength of their films. FT‐IR and DSC analysis approved the formation of cross‐linking with glutaraldehyde between the PVA and β‐CD. Hydrogel films were characterized using XRD and SEM. The disc diffusion method showed the antibacterial activity for the films containing GO‐Ag and GA. Due to the good strength, elasticity, WVP, and swelling ability, PVA/GA/βCD‐IC/GO‐Ag can be proposed as a potential antibacterial drug delivery system.     

Efficient reduction of graphene oxide catalyzed by copper

We report that copper thin films deposited on top of graphene oxide (GO) serve as an effective catalyst to reduce GO sheets in a diluted hydrogen environment at high temperature. The reduced GO (rGO) sheets exhibit higher effective field-effect hole mobility, up to 80 cm(2) V(-1) s(-1), and lower sheet resistance (13 kΩ □(-1)) compared with those reduced by reported methods such as hydrazine and thermal annealing. Raman and XPS characterizations are addressed to study the reduction mechanism on graphene oxide underneath copper thin films. The level of reduction in rGO sheets is examined by Raman spectroscopy and it is well correlated with hole mobility values. The conductivity enhancement is attributed to the growth of the graphitic domain size. This method is not only suitable for reduction of single GO sheets but also applicable to lower the sheet resistance of Langmuir-Blodgett assembled GO films.     

Mechanical properties and degradation studies of poly(D,L‐lactide‐co‐glycolide) 50:50/graphene oxide nanocomposite films

Poly(D,L‐lactide‐co‐glycolide) 50:50 (PLGA)/graphene oxide (GO) nanocomposite films were prepared with various GO weight fractions. A significant enhancement of mechanical properties of the PLGA/GO nanocomposite films was obtained with GO weight fractions. The incorporation of only 5 wt% of GO resulted in an ~2.5‐fold and ~4.7‐fold increase in the tensile strength and Young's modulus of PLGA, respectively. The thermomechanical behaviors of composite films were investigated by dynamic mechanical analysis. Results indicated that the values of T_g and storage moduli of the PLGA/GO composites were higher than those of the pristine PLGA. The improvement in oxygen barrier properties of composites was presumably attributed to the filler effect of the randomly dispersed GO throughout the PLGA matrix. In this work, we also studied in vitro biodegradation behavior. PLGA/GO composite films were hydrolyzed at 37°C for periods up to 49 days. Because of the presence of GO nanosheets, degradation of composite films took place more slowly with increasing GO amounts. Copyright © 2013 John Wiley & Sons, Ltd.     

Physical and mechanical properties of graphene oxide/polyethersulfone nanocomposites

The aim of this study was to investigate physical and mechanical properties of graphene oxide (GO)/polyethersulfone (PES) nanocomposite films. The films were produced by solution casting method. The mechanical properties of composite films were evaluated by tensile test. A significant enhancement in the mechanical properties of neat PES films was obtained incorporating a small amount of GO loading (0.05–1 wt.%). The highest tensile strength was observed at 1 wt.% of GO. Comparisons were made between experimental data and the Halpin–Tsai model predictions for the tensile strength and modulus of GO/PES composites. The effect of an orientation factor on model predictions was also acquired. The hydrophilicity of the nanocomposite was evaluated by assessing contact angle and enhanced wet ability of the films was obtained with increasing the amount of GO up to 1%. The morphology of the nanocomposites was investigated using scanning electron microscopy and transmission electron microscopy and the results revealed a good dispersion of GO in the PES matrix. The thermal behavior of the composite was also studied. Thermal stability of composites was increased by adding the GO. Copyright © 2013 John Wiley & Sons, Ltd.     

Polyacrylamide/reduced graphene oxide-Ag nanocomposite as highly efficient antibacterial transparent film

In this study, preparation and characterization of polyacrylamide/reduced graphene oxide-Ag (PAM/rGO-Ag) nanocomposites as a new nanocomposite film were investigated. First, PAM/GO nanocomposite was synthesized by in situ polymerization strategy. Afterward, highly stable and uniformly distributed silver nanoparticles (Ag NPs) have been obtained with PAM/GO nanocomposite as nanoreactors via in situ reduction of silver nitrate (AgNO₃) using sodium borohydride (NaBH₄) as reducing agent. In addition, the prepared PAM/rGO-Ag nanocomposite was thermally annealed in order to achieve high-performance nanocomposite film with antimicrobial activities. The prepared nanocomposite was characterized by XRD, FT-IR, SEM, TEM and TGA. The obtained results demonstrate that the silver nanoparticles were well decorated and dispersed on the graphene oxide nanosheets. In fact, the GO nanosheets and polyacrylamide chains act as a support and stabilize the Ag nanoparticles. Moreover, antimicrobial activities of the films were also examined, and the films containing well-dispersed and stabilized Ag nanoparticles showed outstanding antibacterial activity.     

Ethanol-assisted graphene oxide-based thin film formation at pentane-water interface

Graphene oxide (GO) can be viewed as an amphiphilic soft material, which form thin films at organic solvent-water interfaces. However, organic solvent evaporation provides little driving force, which results in slow GO transfer in aqueous phase, thus dawdling GO film formation processes for various potential applications. We present an ethanol-assisted self-assembly method for the quick formation of GO or GO-based composite thin films with tunable composition, transmittance, and surface resistivity at pentane-water interface. The thickness of pure GO and reduced GO (rGO) films ranging from ~1 nm to more than 10 nm can be controlled by the concentration of GO in bulk solution. The transmittance of rGO films can be tuned from 72% to 97% at 550 nm while the surface resistivity changes from 8.3 to 464.6 kΩ sq(-1). Ethanol is essential for achieving quick formation of GO thin films. When ethanol is injected into GO aqueous dispersion, it serves as a nonsolvent, compromising the stability of GO and providing driving force to allow GO sheets aggregate at the water-pentane interface. On the other hand, neither the evaporation of pentane nor the mixing between ethanol and water provides sufficient driving forces to allow noteworthy amount of GO sheets to migrate from the bulk aqueous phase to the interface. This method can also be extended to prepare GO-based composites thin films with tunable composition, such as GO/single walled carbon nanotube (SWCNT) composite thin films investigated in this work. Reduced GO/SWCNT composite films show much lower surface resistivity compared to pure rGO thin films. This ethanol-assisted self-assembly method opens opportunities to design and fabricate new functional GO-based hybrid materials for various potential applications.     

Hybrid polypyrrole/copper/graphene oxide nanocomposite films synthesized via potentiostatic deposition with enhanced photovoltaic properties

Novel ternary nanocomposites films of Polypyrrole/copper/graphene oxide (PPy/Cu/GO) showed enhanced optical and electronic properties. In this study, PPy/Cu/GO films were synthesized with different GO load (0.0, 0.4, 0.6, and 0.8 wt%) using electrochemical deposition technique. The structural, optical and electrical properties of the composites were evaluated using X-Ray Diffraction (XRD) spectroscopy, UV–visible spectroscopy, Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDX), and four-point probe methods. XRD results reveal that the GO was completely intercalated and dispersed uniformly in the nanocomposites. The results also revealed that the nanocomposite films are crystalline in nature, with distinct peaks corresponding to indexed miller indices. UV-visible analysis revealed that all of the nanocomposites showed good UV absorbance which was significant in the UV–Vis region of ≈450 nm. The energy band gap decreased with increase in GO load and was found within 3.46 to 2.25 eV, across the range of GO load which fall within the range of energy band gap for photovoltaic applications. The SEM results revealed that the nanocomposite films showed unevenly shaped structures with porous surface which increases with increasing GO loading, while the EDX result revealed the presence of carbon, oxygen nitrogen and copper as fundamental elements deposited. The nanocomposites' four-point probe analysis revealed slight increase in conductivity with low GO content. The incorporation of Cu and GO nanoparticles in PPy matrix provides a better balance and thus improved the photovoltaic properties of PPy/Cu/GO making them suitable for photovoltaic applications.     

Polymerization of graphene oxide nanosheet by using of aminoclay: Electrocatalytic activity of its platinum nanohybrids

This study describes the polymerization of graphene oxide (GO) nanosheet to reduced‐GO‐aminoclay (RGC) by covalent functionalization of chemically reactive epoxy groups on the basal planes of GO with amine groups of magnesium phyllosilicate clay (known as aminoclay). The resulting RGC sheets were characterized and applied to support platinum nanostructures at toluene/water interface. Pt nanoparticles (NPs) with diameters about several nanometers were adhered to RGC sheets by chemical reduction of [PtCl₂(cod)] (cod = cis,cis‐1,5‐cyclooctadiene) complex. Catalytic activity of Pt NPs thin films were investigated in the methanol oxidation reaction. Cyclic voltammetry results exhibit that the Pt/reduced‐GO (RGO) and Pt/RGC thin films showed improved catalytic activity in methanol oxidation reaction in comparison to other Pt NPs thin films, demonstrating that the prepared Pt/RGO and Pt/RGC thin films are promising catalysts for direct methanol fuel cell.     

Synergistic modification by mercapto hyperbranched polysiloxane and functionalized graphene oxide on the surface of aramid fiber

With the purpose of improving the interfacial properties of aramid fibers reinforced rubber composites and enhancing the tensile strength of aramid fibers simultaneously, mercapto hyperbranched polysiloxane (HPSi) and functionalized graphene oxide (GO) were used to modify the surface of aramid fibers. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and other characterization methods were performed to confirm the process of synergistic modification. Judging from the results of mechanical property tests, it could be acquired that the tensile strength of modified aramid fiber was increased by 16.8%, which could be ascribed to the wrapping effect of GO sheets. The interfacial properties were assessed by the pull-out tests of composites, and the results showed that the maximum pull-out force after synergistic surface modification was increased by 99.3%, which could be mainly related to additive reaction between double bonds and mercapto groups and the promotion of surface energy. More critically, during pull-out test, aramid fiber bundles might bring a part of shear stress into the grafted GO sheets, namely, GO sheets could convert fracture energy into interfacial energy, which would improve interfacial properties dramatically.     

Size fractionation of graphene oxide sheets by pH-assisted selective sedimentation

Graphene oxide (GO) sheets prepared by Hummers' method have been separated into two portions with large (f1) or small (f2) lateral dimensions from their aqueous dispersion. This method is based on the selective precipitation of GO sheets with lateral dimensions mostly (>90%) larger than 40 μm(2) at a pH value of 4.0 because of their larger hydrophobic planes and fewer hydrophilic oxygenated groups. The hydrazine reduced Langmuir-Blodgett (LB) films of f1 showed much higher conductivities than those of f2. Furthermore, the thin film of f1 prepared by filtration exhibited a smaller d-space and much higher tensile strength and modulus than those of f2 films. The one-step size fractionation method reported here is simple, cheap, efficient, and environmentally friendly, which can be used for the size fractionation of GO sheets in large scale.     

Functionalization of graphene oxide towards thermo‐sensitive nanocomposites via moderate in situ SET‐LRP

A mild and efficient strategy is presented for growing thermo‐sensitive polymers directly from the surface of exfoliated graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of GO sheets followed by in situ growing poly[poly(ethylene glycol) ethyl ether methacrylate] (PPEGEEMA) via single‐electron‐transfer living radical polymerization (SET‐LRP). Considering the lack of reactive functional groups on the surface of GO, exfoliated GO sheets were subjected to an epoxide ring opening reaction with tris(hydroxymethyl) aminomethane (TRIS) at room temperature. The initiating groups were grafted onto TRIS‐GO sheets by treating hydroxyls with 2‐bromo‐2‐methylpropionyl bromide at room temperature. PPEGEEMA chains were synthesized by in situ SET‐LRP using CuBr/Me₆TREN as catalytic system at 40 °C in H₂O/THF. The resulting materials were characterized using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of GO sheets. After grafting with PPEGEEMA, the modified GO sheets still maintained the separated single layers and the dispersibility was significantly improved. This TRIS‐GO‐PPEGEEMA hybrid material shows reversible self‐assembly and deassembly in water by switching temperature at about 34 °C. Such smart graphene‐based materials promise important potential applications in thermally responsive nanodevices and microfluidic switches. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Pervaporation separation of water-acetic acid mixtures through poly(vinyl alcohol) membranes crosslinked with glutaraldehyde

Poly(vinyl alcohol) (PVA) membranes crosslinked with glutaraldehyde (GA) were prepared by a solution method for the pervaporation separation of acetic acid-water mixtures. In the solution method, dry PVA films were crosslinked by immersion for 2 days at 40°C in reaction solutions which contained different contents of GA, acetone and a catalyst, HCl. In order to fabricate the crosslinked PVA membranes which were stable in aqueous solutions, acetone was used as reaction medium in stead of aqueous inorganic salt solutions which have been commonly used in reaction solution for PVA crosslinking reaction. The crosslinking reaction between the hydroxyl group of PVA and the aldehyde group of GA was characterized by IR spectroscopy. Swelling measurements were carried out in both water and acetic acid to investigate the swelling behavior of the membranes. The swelling behaviour of a membrane fabricated at different GA content in a reaction solution was dependent on crosslinking density and chemical functional groups created as a result of the reaction between PVA and GA, such as the acetal group, ether linkage and unreacted pendent aldehydes in PVA. The pervaporation separation of acetic acid-water mixtures was performed over a range of 70–90 wt% acetic acid in the feed at temperatures varying from 35 to 50°C to examine the separation performances of the PVA membranes. Permeation behaviour through the membranes was analyzed by using pervaporation activation energies which had been calculated from the Arrhenius plots of permeation rates.