Enhanced performance of biodegradable poly(butylene succinate)/graphene oxide nanocomposites via in situ polymerization

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were facilely prepared via in situ polymerization. The properties of the nanocomposites were studied using FTIR, XRD, and (1)H NMR, and the state of dispersion of GO in the PBS matrix was examined by SEM. The crystallization and melting behavior of the PBS matrix in the presence of dispersed GO nanosheets have been studied by DSC and polarized optical microscopy. Through the mechnical testing machine and DMA, PBS/GO nanocomposites with 3% GO have shown a 43% increase in tensile strength and a 45% improvement in storage modulus. This high performance of the nanocomposites is mainly attributed to the high strength of graphene oxide combined with the strong interfacial interactions in the uniformly dispersed PBS/GO nanocomposites.     

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.     

A facile approach to obtaining PVDF/graphene fibers and the effect of nanoadditive on the structure and properties of nanocomposites

The key factors in the design of nanocomposites include obtaining a good adhesion between components and homogeneous dispersion of the nanoadditive in the polymer matrix. Direct mixing of graphene with polymers which are then processed by melt compounding method results in strong tendency of nanoadditive to agglomerate. The article presents a new approach to obtaining poly(vinylidene fluoride)/graphene (PVDF/rGO) nanocomposites in the form of fibers. This method is characterized by the use of graphene oxide (GO) dispersed in the plasticizer instead of graphene. The combination of the fibers forming process with simultaneous reduction of GO to rGO allowed the authors to obtain nanocomposites with graphene homogeneously dispersed in the polymer matrix. Moreover, addition of graphene resulted in formation of β-phase in the nanocomposites, which is characteristic for PVDF and responsible for pyroelectric and piezoelectric properties of this polymer.     

Morphology, crystallization and mechanical properties of poly(ɛ-caprolactone)/graphene oxide nanocomposites

A series of nanocomposites based on poly(ε-caprolactone) (PCL) and graphene oxide (GO) were prepared by in situ polymerization. Scanning electron microscopy observation revealed not only a well dispersion of GO but also a strong interfacial interaction between GO and the PCL matrix, as evidenced by the presence of some GO nanosheets embedded in the matrix. Effects of GO nanofillers on the crystal structure, crystallization behavior and spherulitic morphology of the PCL matrix were investigated in detail. The results showed that the crystallization temperature of PCL enhanced significantly due to the presence of GO in the nanocomposites, however, the addition of GO did not affect the crystal structure greatly. Thermal stability of PCL remarkably increased with the addition of GO nanosheets, compared with that of pure PCL. Incorporation of GO greatly improved the tensile strength and Young’s modulus of PCL without a significant loss of the elongation at break.     

Segregated reduced graphene oxide polymer composite as a high performance electromagnetic interference shield

Herein, we report the synthesis of a graphene/polymer composite via a facile and straightforward approach for electromagnetic interference (EMI) shielding applications. Polystyrene (PS) beads were added in graphene oxide (GO)/water solution followed by the addition of hydroiodic acid (HI) for in situ reduction of GO. The composite solution (rGO/PS) was filtered, hot compressed and tested for EMI shielding and dielectric measurements. A 2-mm thick segregated rGO/PS sample with 10 wt% filler loading delivered a high EMI shielding effectiveness (SE) of 29.7 dB and an AC electrical conductivity of 21.8 S m^?1, which is well above the commercial requirement for EMI shielding applications. For comparison with the segregated rGO/PS composite, a control polymer composite sample utilizing a thermally reduced graphene oxide was synthesized by following a conventional coagulation approach. The as-synthesized conventional rGO/PS yield an EMI SE of 14.2 dB and electrical conductivity of 12.5 S m^?1. The high EMI shielding of segregated rGO/PS is attributed to the better filler-to-filler contact among graphene layers surrounded by PS beads and also to the better reduction and preservation of graphene structure during reduction process that makes the low temperature chemically reduced segregated rGO/PS approach a viable route compared to high temperature thermally reduced conventional rGO/PS approach.     

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.     

Three-dimensional paper-like graphene framework with highly orientated laminar structure as binder-free supercapacitor electrode

A free-standing paper-like three-dimensional graphene framework(3DGF) with orientated laminar structure and interconnected macropores, was obtained by the hard template-directed ordered assembly. As the sacrificial templates, polystyrene(PS) latex spheres were assembled with graphene oxide(GO) to build up a sandwich type composite film, followed by heat removal of which with a simultaneous reduction of GO. The 3DGF exhibited high specific surface area of 402.5 m2/g, controllable pores and mechanical flexibility, which was employed as the binder-free supercapacitor electrode and shows high specific gravimetric capacitance of 95 F/g at 0.5 A/g, with enhanced rate capability in 3 electrode KOH system.     

Electrochemical‐Reduction‐Assisted Assembly of a Polyoxometalate/Graphene Nanocomposite and Its Enhanced Lithium‐Storage Performance

Herein, we present an electrochemically assisted method for the reduction of graphene oxide (GO) and the assembly of polyoxometalate clusters on the reduced GO (rGO) nanosheets for the preparation of nanocomposites. In this method, the Keggin‐type H₄SiW₁₂O₄₀ (SiW₁₂) is used as an electrocatalyst. During the reduction process, SiW₁₂ transfers the electrons from the electrode to GO, leading to a deep reduction of GO in which the content of oxygen‐containing groups is decreased to around 5 %. Meanwhile, the strong adsorption effect between the SiW₁₂ clusters and rGO nanosheets induces the spontaneous assembly of SiW₁₂ on rGO in a uniformly dispersed state, forming a porous, powder‐type nanocomposite. More importantly, the nanocomposite shows an enhanced capacity of 275 mAh g^?1 as a cathode active material for lithium storage, which is 1.7 times that of the pure SiW₁₂. This enhancement is attributed to the synergistic effect of the conductive rGO support and the well‐dispersed state of the SiW₁₂ clusters, which facilitate the electron transfer and lithium‐ion diffusion, respectively. Considering the facile, mild, and environmentally benign features of this method, it is reasonable as a general route for the incorporation of more types of functional polyoxometalates onto graphene matrices; this may allow the creation of nanocomposites for versatile applications, for example, in the fields of catalysis, electronics, and energy storage.     

One-pot synthesis of reduced graphene oxide-cadmium sulfide nanocomposite and its photocatalytic hydrogen production

Reduced graphene oxide (RGO)-cadmium sulfide (CdS) nanocomposites were successfully prepared by a one-pot solvothermal process without pretreatment of graphene oxide (GO) and a precipitation process, in which GO needs to be pre-reduced by hydrazine. The as-obtained RGO-CdS nanocomposites were used as photocatalysts for hydrogen production under visible light irradiation, and it was found that the product derived from the one-pot solvothermal process showed much better photoactivity than that from the precipitation method.     

Aniline as a dispersing and stabilizing agent for reduced graphene oxide and its subsequent decoration with Ag nanoparticles for enzymeless hydrogen peroxide detection

An aqueous dispersion of reduced graphene oxide (rGO) has been successfully prepared via chemical reduction of graphene oxide (GO) by hydrazine hydrate in the presence of aniline for the first time. The noncovalent functionalization of rGO by aniline leads to a rGO dispersion that can be very stable for several months without the observation of any floating or precipitated particles. Several analytical techniques including Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) have been used to characterize the resulting rGO. Taking advantages of the fact reducing ability of aniline toward AgNO(3), we further demonstrated the subsequent decoration of rGO with Ag nanoparticles (AgNPs) by in situ chemical reduction of silver salts. It was found that such AgNP/rGO nanocomposites exhibit good catalytic activity toward the reduction of hydrogen peroxide (H(2)O(2)), leading to an enzymeless sensor with a fast amperometric response time of less than 2s. The linear detection range is estimated to be from 100 μM to 80 mM (r=0.9991), and the detection limit is estimated to be 7.1 μM at a signal-to-noise ratio of 3.     

Effects of functionalized graphenes on the isothermal crystallization of poly(L-lactide) nanocomposites

The effects of graphene oxide(GO) with polar groups and functionalized GO(f GO) with nonpolar groups on the isothermal crystallization of poly(L-lactide)(PLLA) were compared. Functionalized GO was obtained by grafting octadecylamine and characterized by FTIR, WAXD and TGA. Isothermal crystallization kinetics of PLLA/GO and PLLA/f GO nanocomposites were investigated by combining DSC data and Avrami equation. The results showed that f GO could improve PLLA crystallization rate more obviously than GO. By analyzing the morphology obtained from POM, SEM and TEM, it was found f GO with large layer space dispersed better in PLLA and supplied more nucleation sites than GO. Therefore, for the multilayer graphene, increasing the layer spaces is important to improve its dispersion in polymers, which will cause the crystal kinetics changing of polymers.     

Production of highly electro-conductive cellulosic paper via surface coating of carbon nanotube/graphene oxide nanocomposites using nanocrystalline cellulose as a binder

Electro-conductive cellulosic paper has attracted great attention as a promising alternative material in the emerging field of flexible and portable electronic devices. However, the environmentally friendly fabrication of electro-conductive cellulosic paper still remains challenging. Herein, green multi-walled carbon nanotube (MWCNT)/graphene oxide (GO) nanocomposites towards the sustainable development strategy were developed and subsequently used to impart electro-conductivity to cellulosic paper via surface coating process. GO exfoliated from graphite powder was used as a dispersant to improve the dispersion of MWCNTs in water media, and nanocrystalline cellulose (NCC) derived from cotton fibers was employed as a binder for the MWCNT/GO nanocomposites. Effect of NCC amount on the rheological behavior, particle size distribution, sedimentation stability and zeta potential of MWCNT/GO nanocomposites as well as the electro-conductivity and mechanical properties of coated paper was investigated. Results demonstrated that NCC enhanced the dispersion of MWCNT/GO nanocomposites in addition to serving as a binder. Surface coating application of MWCNT/GO nanocomposites was found to impart high electro-conductivity of up to 892 S m^?1 to the cellulosic paper while improving its mechanical properties.     

Synthesis and characterization of polystyrene‐graphite nanocomposites via surface RAFT‐mediated miniemulsion polymerization

Graphite oxide (GO) was prepared and immobilized with dodecyl isobutyric acid trithiocarbonate (DIBTC) reversible addition‐fragmentation chain transfer (RAFT) agent. The hydroxyl groups of GO were attached to the DIBTC RAFT agent through an esterification process. The resultant modified GO was used for the preparation of polystyrene (PS)/graphite nanocomposites in miniemulsion polymerization. The RAFT‐grafted GO (GO‐DIBTC) at various loadings was dispersed in styrene monomer, and the resultant mixtures were sonicated in the presence of a surfactant (sodium dodecylbenzene sulfonate) and a hydrophobe (hexadecane) to form miniemulsions. The stable miniemulsions thus obtained were polymerized using azobisisobutyronitrile as the initiator to yield encapsulated PS‐GO nanocomposites. The molar mass and polydispersity index of PS in the nanocomposites depended on the amount of RAFT‐grafted GO in the system, in accordance with the features of the RAFT polymerization method. The PS‐GO nanocomposites were of exfoliated morphology, as confirmed by X‐ray diffraction and transmission electron microscopy measurements. The thermal stability and mechanical properties of the PS‐GO nanocomposites were better than those of the neat PS polymer. Furthermore, the mechanical properties were dependent on the modified GO content (i.e., the amount of RAFT‐grafted GO). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Simultaneous functionalization and reduction of graphene oxide with polyetheramine and its electrically conductive epoxy nanocomposites

Simultaneous functionalization and reduction of graphene oxide(GO) is realized by refluxing of GO suspension with polyetheramine(D2000) followed by thermal treatment at 120 °C. Compared to GO, the D2000-treated GO(GOD2000) becomes hydrophobic, thermally stable and highly conductive with an electrical conductivity of 11 S/m, which is almost 8 orders of magnitude higher than that of GO. Due to the high conductivity and improved dispersion of GO-D2000, its epoxy nanocomposites exhibit a sharp transition from electrically insulating to conducting with a low percolation threshold of 0.71 vol%. With 3.6 wt% GO-D2000, the glass transition temperature of the epoxy nanocomposite is 27 K higher than that of neat epoxy.     

Covalent polymeric modification of graphene nanosheets via surface‐initiated single‐electron‐transfer living radical polymerization

Graphene nanosheets offer intriguing electronic, thermal, and mechanical properties and are expected to find a variety of applications in high‐performance nanocomposite materials. Dispersal of graphene nanosheets in polymer hosts and precise interface control are challenging due to their strong interlayer cohesive energy and surface inertia. Here, an efficient strategy is presented for growing polymers directly from the surface of reduced graphene oxide (GO). This method involves the covalent attachment of Br‐containing initiating groups onto the surface of hydrazine hydrate reduced GO via a diazonium addition and the succeeding linking of poly(tert‐butyl methacrylate) (PtBMA) chains (71.7 wt % grafting efficiency) via surface‐initiated single‐electron‐transfer living radical polymerization (SET‐LRP) to graphene nanosheets. The resulting materials were characterized by using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of exfoliated graphene sheets. After grafting with PtBMA, the modified graphene sheets still maintained the separated single layers, and the dispersibility was improved significantly. The method is believed to offer possibilities for optimizing the processing properties and interface structure of graphene–polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Ab initio study on the noncovalent adsorption of camptothecin anticancer drug onto graphene, defect modified graphene and graphene oxide

The application of graphene and related nanomaterials like boron nitride (BN) nanosheets, BN-graphene hybrid nanomaterials, and graphene oxide (GO) for adsorption of anticancer chemotherapeutic camptothecin (CPT) along with the effect on electronic properties prior to functionalization and after functionalization has been reported using density functional theory (DFT) calculations. The inclusion of dispersion correction to DFT is instrumental in accounting for van der Waals π–π stacking between CPT and the nanomaterial. The adsorption of CPT exhibits significant strain within the nanosheets and noncovalent adsorption of CPT is thermodynamically favoured onto the nanosheets. In case of GO, surface incorporation of functional groups result in significant crumpling along the basal plane and the interaction is basically mediated by H-bonding rather than π–π stacking. Docking studies predict the plausible binding of CPT, CPT functionalized graphene and GO with topoisomerase I (top 1) signifying that CPT interacts through π stacking with AT and GC base pairs of DNA and in presence of nano support, DNA bases preferentially gets bound to the basal plane of graphene and GO rather than the edges. At a theoretical level of understanding, our studies point out the noncovalent interaction of CPT with graphene based nanomaterials and GO for loading and delivery of anticancer chemotherapeutic along with active binding to Top1 protein.     

Sulfonated graphene oxide: the new and effective material for synthesis of polystyrene-based nanocomposites

The new sulfonated graphene oxide (S-GO) was prepared and firstly used as effective materials for the synthesis of polystyrene/graphene nanocomposites via Pickering emulsion polymerization. The functionalized, chemically modified GO nanosheets were obtained via facile covalent functionalization with a reactive surfactant, sulfanilic acid. It was found that Pickering emulsion could be formed by simple self-assembly method using the S-GO as a stabilizer (just need 1 wt% relative to the oil phase), which could be adsorbed at the oil–water interface to stabilize the emulsion effectively. After the Pickering emulsion polymerization of styrene, the polystyrene/S-GO nanocomposites were prepared successfully. It is noteworthy that the S-GO not only could be used as a highly effective surfactant for styrene monomers but also could be homogeneously dispersed and incorporated into the polymeric matrix.     

One‐Step Electrodeposition to Layer‐by‐Layer Graphene–Conducting‐Polymer Hybrid Films

One‐step fabrication of graphene–polyaniline (graphene–PANI) hybrid film was facilely achieved by cyclic voltammetric electrolysis of a bath containing both graphene oxide (GO) and aniline, where graphene is obtained by electrochemical reduction of GO and PANI is simultaneously obtained by aniline electropolymerization. As there is no strong attraction between aniline and GO under the electrodeposition conditions, the independent depositions of PANI and reduced GO nanosheets at their greatly differed potentials led to alternate layered graphene–PANI films, with the topmost layer being PANI particles or graphene sheets just by changing the initial scan directions. The two kinds of graphene–PANI hybrid films present excellent but different electrical and electrochemical behaviors.     

Functional Graphene by Thiol‐ene Click Chemistry

Thiol‐ene click reaction was successfully employed for chemical modification of graphene oxide (GO) by one‐step synthesis. Herein, 2,2‐azobis(2‐methylpropionitrile) (AIBN) was used as thermal catalyst and cysteamine hydrochloride (HS?(CH₂)₂?NH₂HCl) was used as thiol‐containing compound, which is incorporated to GO surface upon reaction with the C=C bonds. The hydrochloride acts as protecting group for the amine, which is finally eliminated by adding sodium hydroxide. The modified GO contains both S‐ and N‐containing groups (NS‐GO). We found that NS‐GO sheets form good dispersion in water, ethanol, and ethylene glycol. These graphene dispersions can be processed into functionalized graphene film. Besides, it was demonstrated that NS‐GO was proved to be an excellent host matrix for platinum nanoparticles. The developed method paves a new way for graphene modification and its functional nanocomposites.     

Graphene oxide nanocolloids

Graphene oxide (GO) nanocolloids-sheets with lateral dimension smaller than 100 nm-were synthesized by chemical exfoliation of graphite nanofibers, in which the graphene planes are coin-stacked along the length of the nanofibers. Since the upper size limit is predetermined by the diameter of the nanofiber precursor, the size distribution of the GO nanosheets is much more uniform than that of common GO synthesized from graphite powders. The size can be further tuned by the oxidation time. Compared to the micrometer-sized, regular GO sheets, nano GO has very similar spectroscopic characteristics and chemical properties but very different solution properties, such as surface activity and colloidal stability. Due to higher charge density originating from their higher edge-to-area ratios, aqueous GO nanocolloids are significantly more stable. Dispersions of GO nanocolloids can sustain high-speed centrifugation and remain stable even after chemical reduction, which would result in aggregates for regular GO. Therefore, nano GO can act as a better dispersing agent for insoluble materials (e.g., carbon nanotubes) in water, creating a more stable colloidal dispersion.