Decomposition properties of PVA/graphene composites during melting-crystallization

Abstract The thermal decomposition of PVA and PVA composites during the melting-crystallization process is still unclear due to indistinct changes in chemical compositions. Using graphene as a model, the decomposition properties of PVA and PVA-graphene composites were systematically analyzed under multiple melting-crystallization cycles. And a series of isothermal decomposition experiments around the melting-crystallization temperature were carried out to simulate the corresponding decomposition kinetics. Based on multiple cycle melting-crystallization, the weight loss of PVA and PVA/graphene composites was successfully quantified. Further morphology investigation and chemical structure analysis indicated that the decomposition was non-uniformly distributed, rendering the possibility of crystallization for PVA and PVA/graphene composites after multiple heating-cooling cycles. In addition, isothermal decomposition analysis based on reduced time plot approach and model-free iso-conversional method indicated that Avrami-Eroffev model could well match the decomposition process of the neat PVA and PG-0.3 composite, while the Avrami-Eroffev and first order models could precisely forecast the decomposition of PG-0.9 composite. Both analyses during multiple cycle melting-crystallization and isothermal decomposition demonstrated that graphene served as decomposition accelerator in the whole thermal decomposition process, and particularly the decomposition of neat PVA and PVA/graphene composites was highly related to the band area ratios of C-H and O-H vibrations in Fourier transform infrared (FTIR) spectrum.

Shrinkage induced stretchable micro-wrinkled reduced graphene oxide composite with recoverable conductivity

A novel thermo-mechanical shrinking method is reported to fabricate a three dimensional (3D) stretchable and highly conductive micro-wrinkled reduced graphene oxide (MWrGO) supported on an elastic polydimethylsiloxane (PDMS) substrates. This 3D rGO architecture not only increases the specific area for more electrons to pass through but also bestows stretchability to the conductive pathway. The structural change of micro-wrinkles has been monitored by an in situ straining microscopy. The electrical conductivity of the samples remained fairly constant and stayed above 25 S/m under low deformation (no more than 30% strain) for up to 500 mechanical stretching-release cycles. Additionally, the MWrGO/PDMS composite can be stretched bi-axially because the shrinking process itself is isotropic. This MWrGO based stretchable composite with stable electrical properties and long life span could form a new platform of stretchable electronics.

Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation

A novel tri-block copolymer poly(oxopentanoate ethyl methacrylate)-block-poly(pyridyl disulfide ethyl acrylate)-block-poly(ethylene glycol acrylate) [poly(OEMA-b-PDEA-b-PEGA)], retaining active keto groups and pyridyl disulfide (PDS) side functionalities, was synthesized as a drug delivery vehicle using reversible addition-fragmentation chain transfer (RAFT) polymerization method. One mimic drug pyridine-2-thione (PT) was introduced into the monomer, PDEA for copolymerization. The other mimic drug O-benzylhydroxylamine (BHA) was conjugated with tri-block copolymer via efficient oxime coupling chemistry, followed by the attachment onto graphene via π-π stacking interaction to obtain a graphene/tri-block copolymer composite. 1H NMR, UV-vis absorption spectroscopy, fluorescence spectroscopy, gel permeation chromatography (GPC), atomic force microscope (AFM) and transmission electron microscope (TEM) were used to verify the successful step-wise preparation of the tri-block copolymer and drug loaded composite. In vitro release behaviors of BHA and PT from graphene/tri-block copolymer composite via dual drug release mechanisms were investigated. BHA can be released under acid environment, while PT will be released in the presence of reducing agents, such as dithiothreitol (DTT) or glutathione (GSH). It can be envisioned that this novel composite could be exploited as a novel intracellular drug delivery system via dual release mechanisms.

Reinforcement and deformation behaviors of polyvinyl alcohol/graphene/montmorillonite clay composites

We report the synergistic reinforcement and deformation of polyvinyl alcohol (PVA)/graphene/montmorillonite clay (MMT) composites with the tensile properties being improved greatly. Particularly, the tensile strength and modulus of PVA composite with 0.9 wt% graphene and 0.3 wt% of MMT were improved by more than 58% and 43% when compared to the neat PVA, respectively, and were at least 10% higher than the enhanced sum of dual PVA composites with 0.9 wt% graphene and 0.3 wt% MMT. This reinforcement was resulted from the good dispersion and effective interfacial interactions as confirmed from morphology investigation, increased glass transition temperature and the shift of O-H stretching. When there were no fillers i.e. in situ reduced graphene (IRG) or MMT or their loading was low, high alignment of PVA could be observed, with increased crystallinity, melting point, lamellae thickness but narrowed crystallite size distribution. The synergistic reinforcement of PVA achieved from combined incorporation of IRG and MMT will pave the way for the development of stronger PVA composites in various applications.

The high renaissance properties of porous three dimensional graphene using one step reduction and its application in flexible conductor

 A super conductive graphene with continuous three dimensional (3D) porous structures that can potentially be used as flexible conductors has been produced by one step reduction of graphene oxide (GO) film. The high renaissance properties have been demonstrated by mechanical and electrical results where a noticeable increase in the electrical conductivity to 3850 S/cm has been demonstrated after embedding the 3D graphene foam into nearly insulated polydimethylsiloxane (PDMS). The graphene integrated PDMS film has a higher strain up to 100% elongation compared with the strain of only 60% for PDMS. Fourier transform infrared (FTIR) and x-ray photoemission spectroscopy (XPS) results reveal that most oxidized groups have been removed, which contributes to the renaissance of most outstanding properties of graphene because of the recovery of sp2 carbon structures.

Reinforcing effects of graphene oxide on portland cement paste

Abstract: In this experimental study, the reinforcing effects of graphene oxide (GO) on portland cement paste are investigated. It is discovered that the introduction of 0.03% by weight GO sheets into the cement paste can increase the compressive strength and tensile strength of the cement composite by more than 40% due to the reduction of the pore structure of the cement paste. Moreover, the inclusion of the GO sheets enhances the degree of hydration of the cement paste. However, the workability of the GO-cement composite becomes somewhat reduced. The overall results indicate that GO could be a promising nanofillers for reinforcing the engineering properties of portland cement paste.

Graphene and graphitic derivative filled polymer composites as potential sensors

Graphite and numerous graphitic-derived micro- and nano-particles have gained importance in current materials science research. These two-dimensional sheets of sp(2)-hybridized carbon atoms remarkably influence the properties of polymers. Graphene mono-layers, graphene oxides, graphite oxides, exfoliated graphite, and other related materials are derived from a parental graphite structure. In this review, we focus primarily on the role of these fillers in regulating the electrical and sensing properties of polymer composites. It has been demonstrated that the addition of an optimized mixture of graphene and or its derivatives to various polymers produces a record-high enhancement of the electrical conductivity and achieved semiconducting characteristics at small filler loading, making it suitable for sensor manufacture. Promising sensing characteristics are observed in graphite-derived composite films compared with those of micro-sized composites and the properties are explained mainly based on the filler volume fraction, nature and rate of dispersion and the filler polymer interactions at the interface. In short, this critical review aims to provide a thorough understanding of the recent advances in the area of graphitic-based polymer composites in advanced electronics. Future perspectives in this rapidly developing field are also discussed.

Probing the tunable surface chemistry of graphene oxide

The determination of oxygen content, hydrophobicity and reduction efficiency of graphene oxide (GO) are difficult tasks because of its heterogeneous structure. Herein, we describe a novel approach for the detailed understanding of the surface chemistry of GO by studying the interactions between [Ru(bpy)3](2+) and GO.

Mechanical properties of graphene films enhanced by homo-telechelic functionalized polymer fillers via π-π Stacking interactions

© 2015 Elsevier Ltd. All rights reserved. Most researches on graphene/polymer composites are focusing on improving the mechanical and electrical properties of polymers at low graphene content instead of paying attention to constructing graphene's macroscopic structures. In current study the homo-telechelic functionalized polyethylene glycols (FPEGs) were tailored with π-orbital-rich groups (namely phenyl, pyrene and di-pyrene) via esterification reactions, which enhanced the interaction between polyethylene glycol (PEG) molecules and chemical reduced graphene oxide (RGO) sheets. The π-π stacking interactions between graphene sheets and π-orbital-rich groups endowed the composite films with enhanced tensile strength and tunable electrical conductivity. The formation of graphene network structure mediated by the FPEGs fillers via π-π stacking non-covalent interactions should account for the experimental results. The experimental investigations were also complemented with theoretical calculation using a density functional theory. Atomic force microscope (AFM), scanning electron microscope (SEM), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), UV-vis and fluorescence spectroscopy were used to monitor the step-wise preparation of graphene composite films.

Graphene quantum dots directly generated from graphite via magnetron sputtering and the application in thin-film transistors

This work presents a novel method to prepare graphene quantum dots (GQDs) directly from graphite. A composite film of GQDs and ZnO was first prepared using the composite target of graphite and ZnO via magnetron sputtering, followed with hydrochloric acid treatment and dialysis. Morphology and optical properties of the GQDs were investigated using a number of techniques. The as-prepared GQDs are 4-12 nm in size and 1-2 nm in thickness. They also exhibited typical excitation-dependent properties as expected in carbon-based quantum dots. To demonstrate the potential applications of GQDs in electronic devices, pure ZnO and GQD-ZnO thin-film transistors (TFTs) using ZrOx dielectric were fabricated and examined. The ZnO TFT incorporating the GQDs exhibited enhanced performance: an on/off current ratio of 1.7 × 107, a field-effect mobility of 17.7 cm2/Vs, a subthreshold swing voltage of 90 mV/decade. This paper provides an efficient, reproducible and eco-friendly approach for the preparation of monodisperse GQDs directly from graphite. Our results suggest that GQDs fabricated using magnetron sputtering method may envision promising applications in electronic devices.

A highly conductive porous graphene electrode prepared via in situ reduction of graphene oxide using Cu nanoparticles for the fabrication of high performance supercapacitors

Herein, a new graphene/Cu nanoparticle composite was prepared via the in situ reduction of GO in the presence of Cu nanoparticles which was then utilized as a sacrificing template for the formation of flexible and porous graphene capacitor electrodes by the dissolution of the intercalated Cu nanoparticle in a mixed solution of FeCl3 and HCl. The porous RGO electrode was characterized by atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The as-prepared graphene/Cu nanoparticle composite and the pure graphene film after removal of Cu nanoparticles possessed high conductivity of 3.1 × 10³ S m^-1 and 436 S m^-1 respectively. The porous RGO can be used as the electrode for the fabrication of supercapacitors with high gravimetric specific capacitances up to 146 F g^-1, good rate capability and satisfactory electrochemical stability. This environmentally friendly and efficient approach to fabricating porous graphene nanostructures could have enormous potential applications in the field of energy storage and nanotechnology.

An acetylcholinesterase inhibition biosensor based on a reduced graphene oxide/silver nanocluster/chitosan nanocomposite for detection of organophosphorus pesticides

A sensitive electrochemical acetylcholinesterase (AChE) biosensor based on a reduced graphene oxide (rGO) and silver nanocluster (AgNC) modified glassy carbon electrode (GCE) was developed. rGO and AgNC nanomaterials with excellent conductivity, catalytic activity and biocompatibility offered an extremely hydrophilic surface, which facilitated the immobilization of AChE to fabricate the organophosphorus pesticide biosensor. Carboxylic chitosan (CChit) was used as a cross-linker to immobilize AChE on a rGO and AgNC modified GCE. The AChE biosensor showed favorable affinity to acetylthiocholine chloride (ATCl) and could catalyze the hydrolysis of ATCl. Based on the inhibition effect of organophosphorus pesticides on the AChE activity, using phoxim as a model compound, the inhibition effect of phoxim was proportional to its concentration ranging from 0.2 to 250 nM with a detection limit of 81 pM estimated at a signal-to-noise ratio of 3. The developed biosensor exhibited good sensitivity, stability and reproducibility, thus providing a promising tool for analysis of enzyme inhibitors and direct analysis of practical samples.

One-pot facile synthesis of platinum nanoparticle decorated reduced graphene oxide composites and their application in electrochemical detection of rutin

We report on the synthesis of platinum nanoparticle-reduced graphene oxide (PtNP-rGO) composites and their application as a novel architecture in electrochemical detection of rutin. PtNPs anchored over rGO are synthesized through a facile one-pot synthesis method, where the reduction of GO and in situ generation of PtNPs occurred concurrently. The characterization results of transmission electron microscopy (TEM) demonstrate that PtNPs with small particle sizes are dispersed on the rGO matrix. Electrochemical measurements reveal that a PtNP-rGO modified glass carbon electrode (GCE) directly catalyzes rutin oxidation and displays an enhanced current response compared with a bare GCE. Under the optimal experimental conditions, the peak current was linear with rutin concentration in the range of 5 × 10^-8 to 1 × 10^-5 M with the detection limit of 1 × 10^-8 M (S/N = 3) by differential pulse voltammetry. The proposed method was successfully applied to determine rutin in tablet samples with satisfactory results. This journal is