Rubber composites based on graphene nanoplatelets,expanded graphite,carbon nanotubes and their combination: A comparative study

Solution styrene butadiene rubber (S-SBR) composites reinforced with graphene nanoplatelets (GnPs), expanded graphite (EG), and multiwalled carbon nanotubes (MWCNTs) were prepared and the electrical and various mechanical properties were compared to understand the specific dispersion and reinforcement behaviours of these nanostructured fillers. The electrical resistivity of the rubber composite gradually decreased with the increase of filler amount in the composite. The electrical percolation behaviour was found to be started at 15 phr (parts per hundred rubber) for GnP and 20 phr for EG filled systems, whereas a sharp drop was found at 5 phr for MWCNT based composites. At a particular filler loading, dynamic mechanical analysis and tensile test showed a significant improvement of the mechanical properties of the composites comprised of MWCNT followed by GnP and then EG. The high aspect ratio of MWCNT enabled to form a network at low filler loading and, consequently, a good reinforcement effect was observed. To investigate the effect of hybrid fillers, MWCNT (up to 5 phr) were added in a selected composition of EG based compounds. The formation of a mixed filler network showed a synergistic effect on the improvement of electrical as well as various mechanical properties.     

Thermo-mechanical properties of poly(vinylidene fluoride) modified graphite/poly(methyl methacrylate) nano composites

Poly(methyl methacrylate) (PMMA) nano composites were synthesized by melt compounding technique. Different graphite loadings were investigated, including some treated with poly(vinylidene fluoride) (PVDF). A homogeneous dispersion of graphite throughout the PMMA matrix was observed under microscopic analysis. Thermo-gravimetric analysis showed the incorporation of graphite resulted in improvement of thermal stability of neat PMMA. Dynamic mechanical thermal analysis also showed a significant improvement in the storage modulus over the temperature range of 25–150 °C. Coating the graphite with a small amount of PVDF was found to further extend the improvement in the modulus of the PMMA nano composite at 1 wt.% graphite loading.     

Structure and creep response of toughened and nanoreinforced polyamides produced via the latex route: Effect of nanofiller type

Ternary composites composed of polyamide-6 (PA-6), hydrogenated nitrile rubber (HNBR) and sodium fluorohectorite (FH) or boehmite alumina (BA) were produced by melt blending with latex precompounding. The latter served for the predispersion of the FH and BA nanoparticles. The related masterbatch (MB) was produced by mixing the HNBR latex with water dispersible BA or water swellable FH. The dispersion of the nanofillers in the composites was studied by scanning and transmission electron microscopy techniques (SEM and TEM, respectively) and discussed. The thermomechanical and creep properties of the composites were determined in short-time creep tests (performed at various temperatures) and dynamic mechanical thermal analysis (DMTA), respectively. The melt flow of the composites was characterized in a plate/plate rheometer. PA-6/HNBR/FH composites produced by the MB technique outperformed the PA-6/HNBR/BA systems in respect to most of the mechanical and viscoelastic characteristics. This was attributed to the preferred location of FH in the PA-6 matrix and to its higher aspect ratio compared to BA.     

Reinforcement and migration of nanoclay in polychloroprene/ethylene-propylene-diene-monomer rubber blends

This communication demonstrates, an approach of compatibilization between polychloroprene (CR) and ethylene propylene diene monomer rubber (EPDM) by using nanoclay as a compatibilizer and, simultaneously, as a very strong reinforcing nano-filler. With the incorporation of less than 9 wt.% nanoclay, the dynamic storage modulus above the glass transition region of such a blend increases from ∼2 MPa to ∼54 MPa. This tremendous reinforcing as well as the compatibilization effect of the nanoclay was understood by thermodynamically driven preferential framework-like accumulation of exfoliated nanoclay platelets in the phase border of CR and EPDM, as observed i.e. from transmission electron microscopy. The extra-ordinary improvement of dynamic modulus can also be understood by a very strong filler-filler networking that we observed in strain sweep experiments. Moreover, we found that the compatibilized blends exhibit an extra dynamic-mechanical relaxation process at higher temperatures (∼T_g + 130 K). The suggested method for compatibilization of incompatible rubber blends offers routes to the design of new rubber based technical products for diversified applications.     

Forming behavior and workability of 6061/B4CP composite during hot deformation

Compression tests of 6061/B₄C_P composite have been performed in the compression temperature range from 300 °C to 500 °C and the strain rate range from 0.001 s⁻¹ to 1 s⁻¹. The flow behavior and processing map have been investigated using the corrected data to elimination of effect of friction. The processing maps exhibited two deterministic domains, one was situated at the temperature between 300 °C and 400 °C with strain rate between 0.003 s⁻¹ and 0.18 s⁻¹ and the other was situated at the temperature between 425 °C and 500 °C with strain rate between 0.003 s⁻¹ and 0.18 s⁻¹.The estimated apparent activation energies of these two domains, were 129 kJ/mol and 149 kJ/mol, which suggested that the deformation mechanisms were controlled by cross-slip and lattice self-diffusion respectively. The optimum parameters of hot working for the experimental composite were 350 °C - 0.01 s⁻¹ and 500 °C - 0.01 s⁻¹. In order to exactly predict dangerous damaging mechanism under different deformation conditions exactly, Gegel’s criterion was applied to obtain processing map in the paper. The result showed that the processing map used Gegel’s criterion can be effectively to predict the material behavior of the experimental composite.     

Micromechanics modeling of fatigue failure mechanisms in a hybrid polymer matrix composite

Initiation of fatigue damage for a hybrid polymer matrix composite material was studied via 3-Dimensional viscoelastic representative volume element modeling in order to gain further understanding. It was found that carbon fiber reinforced composites perform better in fatigue loading, in comparison to glass fiber reinforced composites, due to the fact that the state of stress within the matrix material was considerably lower for carbon fiber reinforced composites eliminating (or at least prolonging) fatigue damage initiation. The effect of polymer aging was also evaluated through thermal aging of neat resin specimens. Short-term viscoelastic material properties of unaged and aged neat resin specimens were measured using Dynamic Mechanical Analysis. With increasing aging time a corresponding increase in storage modulus was found. Increases in the storage modulus of the epoxy matrix subsequently resulted in a higher state of predicted stress within the matrix material from representative volume element analyses. Various parameters common to unidirectional composites were numerically investigated and found to have varying levels of impact on the prediction of the initiation of fatigue damage.     

Reinforcing potential of micro- and nano-sized fibers in the starch-based biocomposites

Starch-based biocomposites reinforced with jute (micro-sized fiber) and bacterial cellulose (BC) (nano-sized fiber) were prepared by film casting. Reinforcement in the composites is essentially influenced by fiber nature, and amount of loading. The optimum amount of fiber loading for jute and bacterial cellulose in each composite system are 60 wt% and 50 wt% (of starch weight), respectively. Mechanical properties are largely improved due to the strong hydrogen interaction between the starch matrix and cellulose fiber together with good fiber dispersion and impregnation in these composites revealed by SEM. The composites reinforced with 40 wt% or higher bacterial cellulose contents have markedly superior mechanical properties than those reinforced with jute. Young’s modulus and tensile strength of the optimum 50 wt% bacterial cellulose reinforced composite averaged 2.6 GPa and 58 MPa, respectively. These values are 106-fold and 20-fold more than the pure starch/glycerol film. DMTA revealed that the presence of bacterial cellulose (with optimum loading) significantly enhanced the storage modulus and glass transition temperature of the composite, with a 35 °C increment. Thermal degradation of the bacterial cellulose component occurred at higher temperatures implying improved thermal stability. The composites reinforced with bacterial cellulose also had much better water resistance than those associated with jute. In addition, even at high fiber loading, the composites reinforced by bacterial cellulose clearly retain an exceptional level of optical transparency owing to the effect of the nano-sized fibers and also good interfacial bonding between the matrix and bacterial cellulose.     

The impact of fluorinated MWCNT additives on the enhanced dynamic mechanical properties of e-beam-cured epoxy

Multi-walled carbon nanotubes were embedded into e-beam-cured epoxy resin to improve the mechanical properties of epoxy resin. The surfaces of these carbon nanotubes were modified using a fluorination treatment to improve their dispersion and adhesion in epoxy resin. The dynamic mechanical properties of epoxy/carbon nanotube composites were investigated at various heating rates and frequencies. As an effect of fluorination treatment, the semi-ionic bond of C–F on the surface of multi-walled carbon nanotubes played an important role in the improved dispersion and adhesion of carbon nanotubes into the epoxy resin. The storage modulus and loss modulus of the composites increased with higher applied frequency. The activation energy of the composites was increased by the effects of a higher heating rate due to the slow heat transfer in the epoxy/carbon nanotube composites. Eventually, the dynamic mechanical properties of the investigated epoxy were significantly improved by the carbon nanotubes dispersed therein via the fluorination treatment.     

Fabrication and degradation of poly(l-lactic acid) scaffolds with wool keratin

As a natural protein, wool keratin was used to improve the cell affinity of poly(l-lactic acid) (PLLA). Small keratin particles were prepared from keratin solution by the spray-drying process. Keratin particles were blended with PLLA/1,4-dioxane solution and paraffin micro-spheres which were used as progens. After the mixture was molded and dried, the paraffin micro-spheres were removed by cyclohexane. PLLA/keratin scaffolds with controlled pore size and well interconnectivity were fabricated. Keratin releasing rate was detected by Fourier transform infrared (FTIR) after the scaffold was immersed into PBS up to 4 weeks. The surface chemical structure was examined by X-ray photoelectron spectroscope (XPS). The results suggested that the keratin could be held into the scaffold which was expected to improve the interactions between osteoblasts and the polymeric scaffolds.     

Tropical wood polymer nanocomposite (WPNC): The impact of nanoclay on dynamic mechanical thermal properties

In this study, wood polymer nanocomposites (WPNCS) were manufactured from five Malaysian tropical wood species by vacuum-impregnation attended by in situ polymerization using phenol–formaldehyde resin and montmorillomite nanoclay. Percentage weight gain and density of wood polymer nanocomposites depended on wood species. Thermo-mechanical properties of wood samples were investigated by the dynamic mechanical thermal analysis (DMTA) over the temperature range of −100 °C to 200 °C. The intrinsic properties of the components, morphology of the system and the nature of interface between the phases were also determined through DMTA test. Storage modulus (E′) of WPNC samples exhibited significant improvement over the temperature range, in both glassy region and rubbery plateau in relation to their corresponding raw wood samples and wood polymer composites (WPCs). Furthermore, damping (loss tan δ) peaks of all wood species were lowered by PF-Nanoclay system treatment, an indication of improved surface interphase of wood. Dynamic Young’s modulus (E_d) of wood was also calculated using free–free vibration testing. A significant increment was obtained for the PF-Nanoclay impregnated WPNC samples.     

Effect of kneading process conditions on the particle fineness and the polydispersity in nanocomposites

This paper is part of a series of publications that cover the entire process chain to produce nanocomposites. The associated papers are published in the chronological sequence and broach the issues of: “production and dispersing of nanoparticles”, “characterisation of the liquid and reactive matrix” as well as “resulting composite properties by experimental and simulation methods”. Nevertheless, all resulting composite properties are strongly dependent on the method of particle incorporation and on the particle size distribution. Therefore, this study focuses on the optimisation of the dispersion referring to finest particles, smallest particle size distribution, shortest dispersing time and lowest specific energy. In order to prepare the matrix suspension, nano-fillers were dispersed conducting shear mixing techniques in a high performance laboratory kneader. As carrier fluid epoxy resin and a corresponding anhydride hardener system were chosen. Tests were performed using neat and surface modified alumina particles at different levels of particle concentrations. The particle size distribution was determined using dynamic light scattering directly after the dispersing process. Additionally each sample was characterised after 1, 3 and 7 days. Since similar examinations were performed for all formulations, a statement on the influence of re-agglomeration processes and the role of surface modification can be derived. By correlating the progress of the dispersing process to the mass fraction and the particle size distribution, the dispersion process can be evaluated regarding the dispersing time, specific energy and product quality. However, an optimum polydispersity can be found between 25 and 30 wt.%, even if the finest average particle size is reached at higher mass fractions around 45 wt.%. Silane modified alumina particles in epoxy resin constitute the most stable system against re-agglomeration, although the finest particles and the smallest specific energy are attained in non-modified systems. Moreover it can be concluded, that resulting properties of the cured composite are strongly related to the aspired optimisation, e.g. product fines, particle size distribution, required energy input and stability.     

Novel polyacrylonitrile/Na-MMT/silica nanocomposite: Co-incorporation of two different form nano materials into polymer matrix

Polyacrylonitrile (PAN)/Na-montmorillonite (Na-MMT)/SiO₂ nanocomposites were synthesized via in-situ emulsion polymerization. The X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) observations show that the Na-MMT layers were exfoliated in polymerization and the nano materials are well dispersed in the polymer matrix. The thermogravimetric analysis (TGA) suggests that co-incorporating Na-MMT and SiO₂ into the polymer matrix significantly enhances the thermal stability of the polymer. At same nano material loading, the PAN/Na-MMT/SiO₂ nanocomposites show superior thermal stability with respect to the PAN/Na-MMT and PAN/SiO₂ nanocomposites. The mechanical properties of the nanocomposites were also examined. It was found that the PAN/Na-MMT/SiO₂ nanocomposites exhibit considerably enhanced moduli compared with the PAN/Na-MMT and PAN/SiO₂ nanocomposites due to the synergistic reinforcing effect.     

Mechanical,flow and electrical properties of thermoplastic polyurethane/fullerene composites: Effect of surface modification of fullerene

Thermoplastic polyurethane (TPU) composites with fullerene loadings varying from 0.5 to 2 weight% were prepared by melt-mixing method. Nitric acid oxidation and silanization were applied to fullerene surface to improve interfacial interactions with TPU matrix. The influence of surface modifications of fullerene on mechanical, melt flow and electrical properties of TPU based composites were investigated. Incorporation of fullerene leads to nearly twofold increase in tensile strength and Young's modulus of the composites in addition to enhancing the flexibility. The best results are obtained in nitric acid and silane modified fullerene containing composites at the lowest concentration (0.5%). Higher MFI values were observed for composites loaded with surface treated fullerenes compared to pristine fullerene because of their better dispersion in TPU. Electrical properties of TPU also improved by the addition of surface modified fullerene particles. Surface oxidation and silanization gave rise to dispersion homogeneity which may be the reason of both tensile strength and strain improvements at the same time.     

High density polyethylene and poly(ethylene terephthalate) in situ sub-micro-fibril blends as a matrix for wood plastic composites

Wood plastic composites were prepared based on in situ formed poly(ethylene terephthalate) (PET) sub-micro-fibril reinforced high density polyethylene (HDPE) matrices, using a two-step reactive extrusion technology. The use of ethylene-glycidyl methacrylate (E-GMA) copolymer improved phase compatibility in the sub-micro-fibril blends (SMFBs) with 75% HDPE and 25% PET. Most of in situ formed PET fibrils were less than 500 nm in diameter. The PET fibrils obviously increased mechanical properties of the blend, especially the moduli. The subsequent addition of 40 wt.% wood flour did not influence the size and morphology of PET fibrils, and the fibrils and wood fibers had a synergic reinforcement effect on composite properties. Compared with the HDPE/wood composites, the SMFB/wood system had 65% higher tensile strength, 95% higher tensile modulus, 42% higher flexural strength, and 64% higher flexural modulus, respectively. The technology offers a way to use engineering plastics (i.e., PET) for high performance WPC manufacturing.     

Composites based on bimodal vinyl ester resins with low hazardous air pollutant contents

Vinyl ester (VE) resins with a bimodal distribution of molecular weights were prepared via methacrylation of epoxy monomers. Bimodal VE resins and neat polymers had viscosities and mechanical properties similar to that of commercial resins. E-glass composites were prepared and also found to have similar mechanical and thermo-mechanical properties relative to composites fabricated using commercial resins. However, the fracture toughness of the bimodal resins was superior to that of the commercial resins partially as a result of increased molecular relaxations that were manifested in a broader glass transition. Overall, bimodal resins allow for the use of low styrene content (33 wt%), while maintaining excellent thermal, mechanical, and fracture properties for the neat resins and composites.     

The mechanics of graphene nanocomposites: A review

The preparation and characterisation of the different forms of graphene are reviewed first of all. The different techniques that have been employed to prepare graphene such as mechanical and solution exfoliation, and chemical vapour deposition are discussed briefly. Methods of production of graphene oxide by the chemical oxidation of graphite are then described. The structure and mechanical properties of both graphene and graphene oxide are reviewed and it is shown that although graphene possesses superior mechanical properties, they both have high levels of stiffness and strength. It is demonstrated how Raman spectroscopy can be used to characterise the different forms of graphene and also follow the deformation of exfoliated graphene, with different numbers of layers, in model composite systems. It is shown that continuum mechanics can be employed to analyse the behaviour of these model composites and used to predict the minimum flake dimensions and optimum number of layers for good reinforcement. The preparation of bulk nanocomposites based upon graphene and graphene oxide is described finally and the properties of these materials reviewed. It is shown that good reinforcement is only found at relatively low levels of graphene loading and that, due to difficulties with obtaining good dispersions, challenges still remain in obtaining good mechanical properties for high volume fractions of reinforcement.     

Morphology, mechanical and thermal properties of graphene-reinforced poly(butylene succinate) nanocomposites

Graphene nanosheets (GNSs) reinforced poly(butylene succinate) (PBS) nanocomposites are facilely obtained by a solution-based processing method. Graphene nanosheets, which are derived from chemically reduced graphite oxide (GO), are characterized by AFM, TEM, XRD and Raman spectra. The state of dispersion of the GNSs in the PBS matrix is examined by SEM observations that reveals homogeneous distribution of GNSs in PBS matrix. A 21% increase in tensile strength and a 24% improvement of storage modulus are achieved by addition of 2.0 wt% of GNS. The electrical conductivity and thermal stability of the graphene-based nanocomposite are also improved. DSC measurement indicates that the presence of graphene sheets does not have a remarkable impact on the crystallinity of the nanocomposites. Therefore, the high performances of the nanocomposites are mainly attributed to the uniform dispersion of GNSs in the polymer matrix and strong interfacial interactions between both components.     

Effects of extrusion and heat treatment on the microstructure and tensile properties of in situ TiBw/Ti6Al4V composite with a network architecture

In situ TiB whisker reinforced Ti6Al4V (TiBw/Ti64) composites with a network architecture were extruded and heat treated in order to further improve their mechanical properties. The microstructure results show that the equiaxed network architecture was extruded to column network architecture and TiB whisker to alignment distribution. The transformed β phase is formed and the residual stress generated during extrusion obviously decreases after water quenching and aging processes. The tensile test results show that the strength, elastic modulus and ductility of the composites can be significantly improved by the subsequent extrusion, and then, the strength can be further improved by water quenching and aging processes after hot extrusion deformation. The elastic modulus of the as-sintered composites with a novel network microstructure follows the upper bound of Hashin-Shtrikman (H-S) theory before extrusion, while that of the as-extruded composites with a column network microstructure agrees well with the prediction from Halpin-Tsai equation.     

New biocomposites based on thermoplastic starch and bacterial cellulose

Bacterial cellulose, produced by Acetobacter Xylinum, was used as reinforcement in composite materials with a starch thermoplastic matrix. The composites were prepared in a single step with cornstarch by adding glycerol/water as the plasticizer and bacterial cellulose (1% and 5% w/w) as the reinforcing agent. Vegetable cellulose was also tested as reinforcement for comparison purposes. These materials were characterized by different techniques, namely TGA, XRD, DMA, tensile tests, SEM and water sorption assays. All composites showed good dispersion of the fibers and a strong adhesion between the fibers and the matrix. The composites prepared with bacterial cellulose displayed better mechanical properties than those with vegetable cellulose fibers. The Young modulus increased by 30 and 17 fold (with 5% fibers), while the elongation at break was reduced from 144% to 24% and 48% with increasing fiber content, respectively for composites with bacterial and vegetable cellulose.     

Micromechanical deformations in PP/lignocellulosic filler composites: Effect of matrix properties

Polypropylene composites were prepared from three different PP matrices, a homopolymer, a random and a heterophase copolymer, and corn cob to study the effect of matrix characteristics on deformation and failure. The components were homogenized in an internal mixer and compression molded to 1 mm thick plates. Mechanical properties were characterized by tensile testing, while micromechanical deformations by acoustic emission measurements and fractography. The results proved that the dominating micromechanical deformation process may change with matrix properties. Yield stress determined from the stress vs. strain traces may cover widely differing processes. Debonding is the dominating process when the adhesion of the components is poor, while matrix yielding and/or filler fracture dominate when adhesion is improved by the introduction of a functionalized polymer. The dominating deformation mechanism is determined by component properties and adhesion. Interfacial adhesion, matrix yield stress and the inherent strength of the reinforcement can be limiting factors in the improvement of composite strength. The properties of polymer composites reinforced with lignocellulosic fillers are determined by micromechanical deformation processes, but they are independent of the mechanism of these processes.