Enhanced thermal conductivity and retained electrical insulation for polyimide composites with SiC nanowires grown on graphene hybrid fillers

Polyimide (PI) composites containing one-dimensional SiC nanowires grown on two-dimensional graphene sheets (1D–2D SiC_NWs-GSs) hybrid fillers were successfully prepared. The PI/SiC_NWs-GSs composites synchronously exhibited high thermal conductivity and retained electrical insulation. Moreover, the heat conducting properties of PI/SiC_NWs-GSs films present well reproducibility within the temperature range from 25 to 175 °C. The maximum value of thermal conductivity of PI composite is 0.577 W/mK with 7 wt% fillers loading, increased by 138% in comparison with that of the neat PI. The 1D SiC nanowires grown on the GSs surface prevent the GSs contacting with each other in the PI matrix to retain electrical insulation of PI composites. In addition, the storage modulus and Young’s modulus of PI composites are remarkably improved in comparison with that of the neat PI.     

Tribological performance of carbon nanotube–graphene oxide hybrid/epoxy composites

An investigation is conducted on the effect of the hybrid of multi-wall carbon nanotubes (MWCNTs) and graphene oxide (GO) nanosheets on the tribological performance of epoxy composites at low GO weight fractions of 0.05–0.5 phr. The MWCNT amount is kept constant at 0.5 phr, which is typical for CNT/epoxy composites with enhanced mechanical properties. Friction and wear tests against smooth steel show that the introduction of 0.5 phr MWCNTs into the epoxy matrix increases the friction coefficient and decreases the specific wear rate. When testing the tribological performance of MWCNT/GO hybrids, it is shown that at a high GO amount of 0.5 phr, the friction coefficient is decreased below that of the neat matrix whereas the wear rate is increased above that of the neat matrix. At an optimal hybrid formulation, i.e., 0.5 phr MWCNTs and 0.1 phr GO, a further increase in the friction coefficient and a further reduction in the specific wear rate are observed. The specific wear rate is reduced by about 40% down to a factor of 11 relative to the neat epoxy when the GO content is 0.1 phr.     

Graphene woven fabric-reinforced polyimide films with enhanced and anisotropic thermal conductivity

Due to the growing needs of thermal management in modern electronics, polyimide-based (PI) composites are increasingly demanded in thermal interface materials (TIMs). Graphene woven fabrics (GWFs) with a mesh structure have been prepared by chemical vapor deposition and used as thermally conductive filler. With the incorporation of 10-layer GWFs laminates (approximate 12 wt%), the in-plane thermal conductivity of GWFs/PI composite films achieves 3.73 W/mK, with a thermal conductivity enhancement of 1418% compared to neat PI. However, the out-of-plane thermal conductivity of the composites is only 0.41 W/mK. The in-plane thermal conductivity exceeds its out-of plane counterpart by over 9 times, indicating a highly anisotropic thermal conduction of GWFs/PI composites. The thermal anisotropy and the enhanced in-plane thermal conductivity can be attributed to the layer-by-layer stacked GWFs network in PI matrix. Thus, the GWFs-reinforced polyimide films are promising for use as an efficient heat spreader for electronic cooling applications.     

Highly conductive graphene oxide/polyaniline hybrid polymer nanocomposites with simultaneously improved mechanical properties

Graphene oxide (GO) was added to a polymer composites system consisting of surfactant-wrapped/doped polyaniline (PANI) and divinylbenzene (DVB). The nanocomposites were fabricated by a simple blending, ultrasonic dispersion and curing process. The new composites show higher conductivity (0.02–9.8 S/cm) than the other reported polymer system filled with PANI (10⁻⁹–10⁻¹ S/cm). With only 0.45 wt% loading of GO, at least 29% enhancement in electric conductivity and 29.8% increase in bending modulus of the composites were gained. Besides, thermal stability of the composites was also improved. UV–Vis spectroscopy, X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) revealed that addition of GO improves the dispersion of PANI in the polymer composite, which is the key to realize high conductivity.     

Growing polystyrene chains from the surface of graphene layers via RAFT polymerization and the influence on their thermal properties

The polystyrene (PS) macromolecular chains were grafted on the surface of graphene layers by reversible addition-fragmentation chain transfer (RAFT) polymerization. In this procedure, a RAFT agent, 4-Cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, was used to functionalize the thermal reduced graphene oxide (TRGO) to obtain the precursor (TRGO-RAFT). It can be calculated that the grafting density of PS/graphene (PRG) composites was about 0.18 chains per 100 carbons. Successful in-plain attachment of RAFT agent to TRGO and PS chain to TRGO-RAFT was shown an influence on the thermal property of the PRG composites. The thermal conductivity (λ) improved from 0.150 W m⁻¹ K⁻¹ of neat PS to 0.250 W m⁻¹ K⁻¹ of PRG composites with 10 wt% graphene sheets loading. The thermal property of PRG composites increased due to the homogeneous dispersion and ordered arrangement of graphene sheets in PS matrix and the formation of PRG composites.     

Effects of poly(oxyethylene)-block structure in polyetheramines on the modified carbon nanotube/poly(lactic acid) composites

The hybrids of multi-walled carbon nanotube and poly(lactic acid) (MWCNT/PLA) were prepared by a melt-blending method. In order to enhance the compatibility between the PLA and MWCNTs, the surface of the MWCNTs was covalently modified by Jeffamine® polyetheramines by functionalizing MWCNTs with carboxylic groups. Different molecular weights and hydrophilicity of the polyethermaines were grafted onto MWCNTs with the assistance of a dehydrating agent. The results showed that low-molecular-weight Jeffamine® polyetheramine modified MWCNTs can effectively improve the thermal properties of PLA composites. On the other hand, high-molecular-weight and poly(oxyethylene)-segmented polyetheramine could render the modified MWCNTs of well dispersion in PLA, and consequently affecting the improvements of mechanical properties and conductivity of composite materials. With the addition of 3.0 wt% MWCNTs, the increment of E′ of the composite at 40 °C was 79%. For conductivity, the surface resistivity decreased from 1.27 × 10¹² Ω/sq for neat PLA to 8.30 × 10⁻³ Ω/sq for the composites.     

Controlled retting of hemp fibres: Effect of hydrothermal pre-treatment and enzymatic retting on the mechanical properties of unidirectional hemp/epoxy composites

The objective of this work was to investigate the use of hydrothermal pre-treatment and enzymatic retting to remove non-cellulosic compounds and thus improve the mechanical properties of hemp fibre/epoxy composites. Hydrothermal pre-treatment at 100 kPa and 121 °C combined with enzymatic retting produced fibres with the highest ultimate tensile strength (UTS) of 780 MPa. Compared to untreated fibres, this combined treatment exhibited a positive effect on the mechanical properties of hemp fibre/epoxy composites, resulting in high quality composites with low porosity factor (α_pf) of 0.08. Traditional field retting produced composites with the poorest mechanical properties and the highest α_pf of 0.16. Hydrothermal pretreatment at 100 kPa and subsequent enzymatic retting resulted in hemp fibre composites with the highest UTS of 325 MPa, and stiffness of 38 GPa with 50% fibre volume content, which was 31% and 41% higher, respectively, compared to field retted fibres.     

Heat treated wood–nylon 6 composites

Heat treatment is a relatively benign modification method that is growing as an industrial process to improve hygroscopicity, dimensional stability and biological resistance of lignocellulosic fillers. There also has been increased interest in the use of lignocellulosic fillers in numerous automotive applications. This study investigated the influence of untreated and heat treated wood fillers on the mechanical and rheological properties of wood filled nylon 6 composites for possible under-the-hood applications in the automobile industry where conditions are too severe for commodity plastics to withstand. In this study, exposure of wood to high temperatures (212 °C for 8 h) improved the thermal stability and crystallinity of wood. Heat treated pine and maple filled nylon 6 composites (at 20 wt.% loading) had higher tensile strengths among all formulations and increased tensile strength by 109% and 106% compared to neat nylon 6, respectively. Flexural modulus of elasticity (FMOE) of the neat nylon 6 was 2.34 GPa. The FMOE increased by 101% and 82% with the addition of 30 wt.% heat treated pine and 20 wt.% heat treated maple, where it reached maximum values of 4.71 GPa and 4.27 GPa, respectively. The rheological properties of the composites correlated with the crystallinity of wood fillers after the heat treatment. Wood fillers with high crystallinity after heat treatment contributed to a higher storage modulus, complex viscosity and steady shear viscosity and low loss factor in the composites. This result suggests that heat treatment substantially affects the mechanical and rheological properties of wood filled nylon 6 composites. The mechanical properties and thermogravimetric analysis indicated that the heat treated wood did not show significant thermal degradation under 250 °C, suggesting that the wood-filled nylon composites could be especially relevant in thermally challenging areas such as the manufacture of under-the-hood automobile components.     

Improving the thermal and mechanical properties of polysulfone by incorporation of graphene oxide

Nanocomposites of polysulfone (PSF)-graphene oxide (GO) were prepared by classical phase inversion method. The structural and surface features and the mechanical and thermal performances of the prepared materials were investigated in detail. TEM and X-ray diffraction analysis indicated a good compatibility and excellent dispersability with PSF matrix for the low GO content (0.25, 0.5 and 1 wt.%) composites. It was observed that GO dispersion was reasonably homogeneous for the composite with 2 wt.% GO. The mechanical properties of the prepared materials were found to be greatly enhanced by the addition of GO for some compositions. The thermogravimetrical investigation demonstrated considerable improvements in thermal stability for the composite with low GO content. This novel material offers a feasible candidate for practical membrane application.     

A facile assembly of polyimide/graphene core–shell structured nanocomposites with both high electrical and thermal conductivities

Polyimide/reduced graphene oxide (PI/r-GO) core–shell structured microspheres were fabricated by in-situ reduction of graphene oxide (GO), which was coated on the surface of PI microspheres via hydrogen bonding and π–π stacking interaction. The highly ordered 3D core–shell structure of PI/r-GO microspheres with graphene shell thickness of 3 nm was well characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM) and Raman spectra. The glass transition temperature (T_g) of PI/r-GO microspheres was slightly increased because of the interaction of r-GO and PI matrix while the temperature at 5% weight loss (T_5%) of PI/r-GO microspheres was decreased due to the side effect of reductant hydrazine hydrate. The PI/r-GO nanocomposites exhibited highly electrical conductivity with percolation threshold of 0.15 vol% and ultimate conductivity of 1.4 × 10⁻² S/m. Besides, the thermal conductivity of PI/r-GO nanocomposites with 2% weight content of r-GO could reach up to 0.26 W/m K.     

High-temperature dielectric and electromagnetic interference shielding properties of SiCf/SiC composites using Ti3SiC2 as inert filler

Ti₃SiC₂ filler has been introduced into SiC_f/SiC composites by precursor infiltration and pyrolysis (PIP) process to optimize the dielectric properties for electromagnetic interference (EMI) shielding applications in the temperatures of 25–600 °C at 8.2–12.4 GHz. Results indicate that the flexural strength of SiC_f/SiC composites is improved from 217 MPa to 295 MPa after incorporating the filler. Both the complex permittivity and tan δ of the composites show obvious temperature-dependent behavior and increase with the increasing temperatures. The absorption, reflection and total shielding effectiveness of the composites with Ti₃SiC₂ filler are enhanced from 13 dB, 7 dB and 20 dB to 24 dB, 21 dB and 45 dB respectively with the temperatures increase from 25 °C to 600 °C. The mechanisms for the corresponding enhancements are also proposed. The superior absorption shielding effectiveness is the dominant EMI shielding mechanism. The optimized EMI shielding properties suggest their potentials for the future shielding applications at temperatures from 25 °C to 600 °C.     

Enhanced thermal conductivity and dielectric properties of Al/β-SiCw/PVDF composites

Polymeric composites with high thermal conductivity, high dielectric permittivity but low dissipation factor have wide important applications in electronic and electrical industry. In this study, three phases composites consisting of poly(vinylidene fluoride) (PVDF), Al nanoparticles and β-silicon carbide whiskers (β-SiC_w) were prepared. The thermal conductivity, morphological and dielectric properties of the composites were investigated. The results indicate that the addition of 12 vol% β-SiC_w not only improves the thermal conductivity of Al/PVDF from 1.57 to 2.1 W/m K, but also remarkably increases the dielectric constant from 46 to 330 at 100 Hz, whereas the dielectric loss of the composites still remain at relatively low levels similar to that of Al/PVDF at a wider frequency range from 10⁻¹ Hz to 10⁷ Hz. With further increasing the β-SiC_w loading to 20 vol%, the thermal conductivity and dielectric constant of the composites continue to increase, whereas both the dielectric loss and conductivity also rise rapidly.     

Chemical functionalization of graphene oxide for improving mechanical and thermal properties of polyurethane composites

Graphene oxide (GO) was chemically functionalized to prepare polyurethane (PU) composites with improved mechanical and thermal properties. In order to achieve a well exfoliated and stable GO suspension in an organic solvent (dimethylformamide, DMF), 4, 4′-methylenebis(phenyl isocyanate) and polycaprolactone diol, which were the two monomers for synthesizing PU, were selectively used to functionalize GO. The obtained functionalized GO (FGO) could form homogeneous dispersions in DMF solvent and the PU matrix, as well as provide a good compatibility with the PU matrix. The most efficient improvement of mechanical properties was achieved when 0.4 wt.% FGO was added into the PU matrix, showing increases in the tensile stress, elongation at break and toughness by 34.2%, 27.6%, and 64.5%, respectively, compared with those of PU. Regarding the thermal stability, PU filled with 1 wt.% FGO showed the largest extent of improvement with T_2% and T_50% (the temperatures at which 2% and 50% weight-loss happened) 16 °C and 21 °C higher than those of PU, respectively. The significant improvement in both mechanical properties and thermal stability of FGO/PU composites should be attributed to the homogeneous dispersion of FGO in the PU matrix and strong interfacial interaction between them.     

Retention of mechanical performance of polymer matrix composites above the glass transition temperature by vascular cooling

An actively cooled vascular polymer matrix composite containing 3.0% channel volume fraction retains greater than 90% flexural stiffness when exposed continuously to 325 °C environmental temperature. Non-cooled controls suffered complete structural failure through thermal degradation under the same conditions. Glass–epoxy composites (T_g = 152 °C) manufactured by vacuum assisted resin transfer molding contain microchannel networks of two different architectures optimized for thermal and mechanical performance. Microchannels are fabricated by vaporization of poly(lactide) fibers treated with tin(II) oxalate catalyst that are incorporated into the fiber preform prior to resin infiltration. Flexural modulus, material temperature, and heat removal rates are measured during four-point bending testing as a function of environmental temperature and coolant flow rate. Simulations validate experimental measurements and provide insight into the thermal behavior. Vascular specimens with only 1.5% channel volume fraction centered at the neutral bending axis also retained over 80% flexural stiffness at 325 °C environmental temperature.     

Multi-step microwave reduction of graphite oxide and its use in the formation of electrically conductive graphene/epoxy composites

The multi-step MW reduction technique was developed in this study to obtain reduced graphene oxides; EG, RGO-1, and RGO-2 with MW irradiation time of 1, 2, and 3 min, respectively. Results of TGA, IR, and elemental analysis demonstrated that the degree of reduction of GO increased with increasing the MW irradiation time. Overall, 3 min of MW irradiation of GO in 3 steps was sufficient to obtain highly reduced GO (C/O ratio 10.38 by elemental analysis). The electrical percolation threshold of composites was observed as 1 wt% and 0.3 wt% for RGO-1 and RGO-2, respectively. Even at 0.5 wt% loading of RGO-2 in epoxy, the T_g value of the composite increased by 10 °C, indicating a strong interfacial interaction between graphene and epoxy resin.     

Polydopamine coating layer on graphene for suppressing loss tangent and enhancing dielectric constant of poly(vinylidene fluoride)/graphene composites

Graphene with polydopamine (PDA) coating layer which displays promoted dispersibility in organic solvent was prepared through self-polymerization of dopamine onto graphene oxide (GO) and subsequent chemical reduction. The PDA coated reduced GO (RDGO) is homogeneously incorporated into poly(vinylidene fluoride) (PVDF) matrix, which exhibit a percolation threshold at 0.643 wt%. The dielectric constant of PVDF with 0.70 wt% RDGO increases to 176, about 17 times of neat PVDF. Importantly, the loss tangent is suppressed to 0.337 due to reduction of the concentration and mobility of ionizable carboxylic groups by PDA. The enhancement of dielectric constant probably rises from duplex interfacial polarization induced by graphene–semiconductor interface, and semiconductor–insulator interface. The composites displays advantages in excellent dielectric properties and good flexibility and processability guaranteed by low loading of RDGO, which is suitable for the development of dielectric materials for energy storage.     

Manufacture and characterisation of thermoplastic composites made from PLA/hemp co-wrapped hybrid yarn prepregs

PLA/hemp co-wrapped hybrid yarns were produced by wrapping PLA filaments around a core composed of a 400 twists/m and 25 tex hemp yarn (Cannabis sativa L) and 18 tex PLA filaments. The hemp content varied between 10 and 45 mass%, and the PLA wrapping density around the core was 150 and 250 turns/m. Composites were fabricated by compression moulding of 0/90 bidirectional prepregs, and characterised regarding porosity, mechanical strength and thermal properties by dynamic mechanical thermal analysis (DMTA) and differential scanning calorimetry (DSC). Mechanical tests showed that the tensile and flexural strengths of the composites markedly increased with the fibre content, reaching 59.3 and 124.2 MPa when reinforced with 45 mass% fibre, which is approximately 2 and 3.3 times higher compared to neat PLA. Impact strength of the composites decreased initially up to 10 mass% fibre; while higher fibre loading (up to 45 mass%) caused an increase in impact strength up to 26.3 kJ/m², an improvement of about 2 times higher compared to neat PLA. The composites made from the hybrid yarn with a wrapping density of 250 turns/m showed improvements in mechanical properties, due to the lower porosity. The fractured surfaces were investigated by scanning electron microscopy to study the fibre/matrix interface.     

Size-scale effects of silica on bis-GMA/TEGDMA based nanohybrid dental restorative composites

The present study focuses on the effect of size-scale combination of silica on the mechanical and dynamic mechanical properties of acrylate based (50% Bis-GMA and 50% TEGDMA by weight) composites with an aim to overcome the conventional problem of high-volume fraction filling of acrylate based composites, typically used in restorative dentistry. Two classes of light-cured composites based on the size-scale combination of silica (7 nm + 2 μm; 14 nm + 2 μm) as the filler were prepared. FTIR spectroscopy revealed functionality and interactions whereas morphological investigations concerning the state of distribution and dispersion of nano- and micro-silica has been carried out by SEM–EDX Si-dot mapping. The dynamic mechanical properties, compressive, flexural and diametral tensile strengths were characterized. Micromechanical analysis of viscoelastic storage moduli following Kerner composite model has revealed an enhancement in the reinforcement efficiency of the nanohybrid composites based on the filler size-scale combination of 14 nm + 2 μm with 10 wt.% nanofiller loading. The compressive strength of the micro-filled composite (with 2 μm silica only) was found to remain comparable to that of the nanohybrid with 5 wt.% of 7 nm silica and 10 wt.% of 14 nm silica filled composites. Diametral tensile strength has been observed to be influenced by the size-scale combination and extent of nanofiller loading. The effective volume fractions in the composites validating the experimentally determined DTS were calculated following Nicolais–Narkis model. Our study demonstrates the conceptual feasibility of exploring the optimization of size-scale combinations of filler for enhancement in reinforcement efficiency by manipulating the volume fraction of filler induced immobilized polymer chains by resorting to the principle of micromechanics.     

Effects of high-temperature annealing on the microstructure and properties of C/SiC–ZrB2 composites

C/SiC–ZrB₂ composites prepared via precursor infiltration and pyrolysis (PIP) were treated at high temperatures ranging from 1200 °C to 1800 °C. The mass loss rate of the composites increased with increasing annealing temperature and the flexural properties of the composites increased initially and then decreased reversely. Out of the four samples, the flexural strength and the modulus of the specimen treated at 1400 °C are maximal at 216.9 MPa and 35.5 GPa, suggesting the optimal annealing temperature for mechanical properties is 1400 °C. The fiber microstructure evolution during high-temperature annealing would not cause the decrease of fiber strength, and moderate annealing temperature enhanced the thermal stress whereas weakened the interface bonding, thus boosting the mechanical properties. However, once the annealing temperature exceeded 1600 °C, element diffusion and carbothermal reduction between ZrO₂ impurity and carbon fibers led to fiber erosion and a strong interface, jeopardizing the mechanical properties of the composites. The mass loss rate and linear recession rate of composites treated at 1800 °C are merely 0.0141 g/s and 0.0161 mm/s, respectively.     

Functional shape memory composite nanofibers with graphene oxide filler

In the present study, we prepared a series of graphene oxide (GO) filled shape memory polyurethane (SMPU) nanofibers and systematically investigated the morphological, thermal and mechanical properties, surface wettability, and the shape memory effect (SME) followed by the proposed programming model. The results show that GO can be well dispersed within the SMPU matrix, and the introduction of GO significantly improves the mechanical strength, surface wettability, and thermal stability of the SMPU. Compared with pristine SMPU nanofibrous mats, the prepared SMPU/GO nanofibrous mats have better SME and lower thermal shrinkage. When the loading amount of GO increased to 4.0 wt%, the thermal shrinkage ratio (R_ts) of composite nanofibrous mats could be as low as 4.7 ± 0.3%, while the average fixation ratio (R_f) and recovery ratio (R_r) could be as high as 92.1% and 96.5%, respectively. The study indicates that GO is a desirable reinforcing filler for preparing shape memory nanofibers with improved properties.