Transparent uv-shielding films from organic small molecule-intercalated layered double hydroxide nanoplatelets/polymer composite

In this study, layered double hydroxide (LDH) with nitrate as the interlayer anion has been partially exfoliated in dimethyl sulfoxide (DMSO). Atomic force microscopy (AFM) images showed that both the lateral size and the thickness of the LDH nanoplatelets were decreased after DMSO treatment. Formation of transparent LDH suspension in DMSO was observed. Taking this advantage, we have prepared transparent LDH/ethylene-vinyl alcohol copolymer (EVOH) nanocomposite films using DMSO as the processing solvent. Organic small molecules, UV absorbers, were intercalated into the LDH interlayers to incorporate the UV-shielding property into the transparent composite films. The thermal stability of UV absorbers was considerably improved after intercalation, which was attributed to the electrostatic interaction between the guest UV absorbers and the host LDH layers. The prepared composite films were flexible and exhibited excellent UV-shielding capability, but had transmittance as high as 90% in the visible region. The effect of LDH filler on thermal and mechanical properties of the composite films was also examined.

The role of SEBS in tailoring the interface between the polymer matrix and exfoliated graphene nanoplatelets in hybrid composites

Nanocomposites of polypropylene (PP) and polypropylene/styrene-(ethylene-co-butylene)-styrene triblock copolymer (SEBS) blends with exfoliated graphene nanoplatelets (xGnP) were prepared by melt-mixing method. The incorporation of xGnP increased the stiffness and crystallinity of PP at the expense of toughness and the molecular mobility. The effect of addition of SEBS on the mechanical, viscoelastic, thermal degradation and crystallization properties of PP/xGnP composites was studied. The addition of SEBS into PP transformed the phase structure and distribution of xGnP in the PP matrix. SEM micrographs revealed that SEBS polymer chains formed a coating over the graphene nanoplatelets, which strengthened the interface between the filler and the matrix, and improved the dispersion and distribution of the filler throughout the matrix.

Partial exfoliation of layered double hydroxides in DMSO : a route to transparent polymer nanocomposites

Layered double hydroxides (LDHs), either having nitrate counter anions or intercalated with organic molecules, have been for the first time partially exfoliated in dimethyl sulfoxide (DMSO) to form a transparent suspension. Atomic force microscopy (AFM) images showed that both the lateral size and the thickness of the LDH nanoplatelets were decreased after the exfoliation. The organic-LDHs maintained their intercalation characteristics, i.e. the thermal stability improvement of the incorporated organic anions, after the exfoliation in DMSO. Transparent ethylene-vinyl alcohol copolymer (EVOH) nanocomposite films containing partially exfoliated LDHs intercalated with UV absorbers were prepared using DMSO as the processing solvent. As the first reported example of a highly transparent LDH/polymer composite, the obtained composite film had a visible light transmittance of 90% (comparable to that of the pure matrix), was flexible and exhibited an excellent UV-shielding capability and thermal stability.

High N-content holey few-layered graphene electrocatalysts: Scalable solvent-less production

Few layered nitrogen doped graphene (NG) attracts great interest in energy storage and conversion applications due to its electronic and catalytic properties. However, its bulk production cannot be envisioned by the current synthetic methods. Here we report a facile, solvent-less, low cost and high yield process for the synthesis of NG. Mechanochemical solid-state exfoliation allows scalable synthesis of holey and crumple nitrogen-doped few-layered graphene from graphite with controlled high concentration N doping and a high surface area through ball-milling. By adjusting the ratio of starting materials, the nitrogen content can be modulated from 4.87 to 17.83 at.%. Furthermore, the types of nitrogen-containing species in few-layered graphene can also be controlled. The resultant NG exhibits superior oxygen reduction reaction performance and more reliable stability than commercial Pt/C catalysts. This journal is

Graphene networks and their influence on free-volume properties of graphene-epoxidized natural rubber composites with a segregated structure: rheological and positron annihilation studies

Epoxidized natural rubber-graphene (ENR-GE) composites with segregated GE networks were successfully fabricated using the latex mixing combined in situ reduced technology. The rheological behavior and electrical conductivity of ENR-GE composites were investigated. At low frequencies, the storage modulus (G′) became frequency-independent suggesting a solid-like rheological behavior and the formation of GE networks. According to the percolation theory, the rheological threshold of ENR-GE composites was calculated to be 0.17 vol%, which was lower than the electrical threshold of 0.23 vol%. Both percolation thresholds depended on the evolution of the GE networks in the composites. At low GE concentrations (<0.17 vol%), GE existed as individual units, while a "polymer-bridged GE network" was constructed in the composites when GE concentrations exceeded 0.17 vol%. Finally, a "three-dimensional GE network" with percolation conductive paths was formed with a GE concentration of 0.23 vol%, where a remarkable increase in the conductivity of ENR-GE composites was observed. The effect of GE on the atom scale free-volume properties of composites was further studied by positron annihilation lifetime spectroscopy and positron age momentum correlation measurements. The motion of ENR chains was retarded by the geometric confinement of "GE networks", producing a high-density interfacial region in the vicinity of GE nanoplatelets, which led to a lower ortho-positronium lifetime intensity and smaller free-volume hole size.

Multifunctional properties of epoxy nanocomposites reinforced by aligned nanoscale carbon

The present paper compares improvements to the fracture energy and electrical conductivity of epoxy nanocomposites reinforced by one-dimensional carbon nanofibres (CNFs) or two-dimensional graphene nanoplatelets (GNPs). The focus of this investigation is on the effects of the shape, orientation and concentration (i.e. 0.5, 1.0, 1.5 and 2.0 wt%) of nanoscale carbon reinforcements on the property improvements. Alignment of the nano-reinforcements in the epoxy nanocomposites was achieved through the application of an alternating current (AC) electric-field before gelation and curing of the epoxy resin. Alignment of the nano-reinforcements increased the electrical conductivity and simultaneously lowered the percolation threshold necessary to form a conductive network in the nanocomposites. Nano-reinforcement alignment also increased greatly the fracture energy of the epoxy due to a higher fraction of the nano-reinforcement participating in multiple intrinsic (e.g. interfacial debonding and void growth) and extrinsic (e.g. pull-out and bridging) toughening mechanisms. A mechanistic model is presented to quantify the contributions from the different toughening mechanisms induced by CNFs and GNPs to the large improvements in fracture toughness. The model results show that one-dimensional CNFs are more effective than GNPs at increasing the intrinsic toughness of epoxy via void growth, whereas two-dimensional GNPs are more effective than CNFs at improving the extrinsic toughness via crack bridging and pull-out.

Epoxy nanocomposites with aligned carbon nanofillers by external electric fields

This paper presents systematic studies on aligning carbon nanofillers in epoxy by external fields, either electric fields or magnetic fields, to create nanocomposites with greatly improved mechanical and electrical properties. Carbon nanofibers (CNFs) and graphene nanoplatelets (GnPs) were observed to align along the field direction in the epoxy resin. Compared to the unmodifed epoxy and those with randomly-oriented carbon nanofillers, the nanocomposites with aligned carbon nanofillers showed significantly higher fracture toughness and electrical conductivity along the direction of the external field. Compared with randomly-oriented nanofillers, aligned GnPs and CNFs produced 40% and 27% improvement in fracture energy at 1.0 wt%, bringing the total increase in fracture energy over the neat polymer to more than 10 times. Several key toughening mechanisms were identified through fractographic analysis, which was used to develop predictive models to quantify the increases in the value of GIc as a result of 1-D and 2D carbon nanofillers. The present findings suggest that aligning carbon nanofillers presents a very promising technique to create multi-scale reinforcement with greatly increased electric conductivity and fracture toughness.

A novel route for tethering graphene with iron oxide and its magnetic field alignment in polymer nanocomposites

We present a new route of tethering graphene nanoplatelets (GNPs) with Fe3O4 nanoparticles to enable their alignment in an epoxy using a weak magnetic field. The GNPs are first stabilised in water using polyvinylpyrrolidone (PVP) and Fe3O4 nanoparticles are then attached via co-precipitation. The resultant Fe3O4/PVP-GNPs nanohybrids are superparamagnetic and can be aligned in an epoxy resin, before gelation, by applying a weak magnetic field as low as 0.009 T. A theoretical model describing the alignment process is presented and used to quantify the effects of key parameters on the time needed for the alignment process. Compared to the unmodified epoxy, the resulting epoxy polymer nanocomposites containing randomly-oriented Fe3O4/PVP-GNPs nanohybrids exhibit significantly improved electrical conductivities by up to three orders of magnitude and fracture energies by up to 300%. The alignment of the Fe3O4/PVP-GNPs nanohybrids in the epoxy polymer nanocomposites transverse to the direction of crack propagation further increased the fracture energy by 50%, and the electrical conductivity by seven fold in the alignment direction, compared to the nanocomposites containing randomly-oriented nanohybrids.

Development of hybrid composites for automotive applications: effect of addition of SEBS on the morphology, mechanical, viscoelastic, crystallization and thermal degradation properties of PP/PS-xGnP composites

In this article, we report on a simple and cost effective approach for the development of light-weight, super-tough and stiff material for automotive applications. Nanocomposites based on PP/PS blend and exfoliated graphene nanoplatelets (xGnP) were prepared with and without SEBS. Mechanical, crystallization and thermal degradation properties were determined and correlated with phase morphology. The addition of xGnP to PP/PS blend increased the tensile modulus at the expense of toughness. The presence of xGnP increased the enthalpy of crystallization and enthalpy of fusion of PP in the blends, without affecting segmental mobility and thermal stability. Addition of polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) improved the toughness of PP/PS blends, but decreased the stiffness. The incorporation of xGnP into this ternary blend generated a super-tough material with improved stiffness and tensile elongation, suitable for automotive applications. It is observed that the presence of SEBS diminished the tendency of agglomeration of xGnP and their unfavorable interactions with thermoplastics, which in turn reduced the internal friction in the matrix.