Study on thermal properties of graphene foam/graphene sheets filled polymer composites

The polymer composites composed of graphene foam (GF), graphene sheets (GSs) and pliable polydimethylsiloxane (PDMS) were fabricated and their thermal properties were investigated. Due to the unique interconnected structure of GF, the thermal conductivity of GF/PDMS composite reaches 0.56 W m⁻¹ K⁻¹, which is about 300% that of pure PDMS, and 20% higher than that of GS/PDMS composite with the same graphene loading of 0.7 wt%. Its coefficient of thermal expansion is (80–137) × 10⁻⁶/K within 25–150 °C, much lower than those of GS/PDMS composite and pure PDMS. In addition, it also shows superior thermal and dimensional stability. All above results demonstrate that the GF/PDMS composite is a good candidate for thermal interface materials, which could be applied in the thermal management of electronic devices, etc.     

Enhanced thermal-conductive and anti-dripping properties of polyamide composites by 3D graphene structures at low filler content

In this work, 3D graphene structures constructed by graphene foam (GF) were introduced into polyamide-6 (PA6) matrix for the purpose of enhancing the thermal-conductive and anti-dripping properties of PA6 composites. The GF were prepared by one-step hydrothermal method. The PA6 composites were synthesized by in-situ thermal polycondensation method to realize PA6 chains covalently grafted onto the graphene sheets. The 3D interconnected graphene structure favored the formation of the consecutive thermal conductive paths or networks even at relatively low graphene loadings. As a result, the thermal conductivity was improved by 300% to 0.847 W·m⁻¹·K⁻¹ of PA6 composites at 2.0 wt% graphene loading from 0.210 W·m⁻¹·K⁻¹ of pure PA6 matrix. The presence of self-supported 3D structure alone with the covalently-grafted PA6 chains endowed the PA6 composites good anti-dripping properties.     

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.     

Enhanced conductivity behavior of polydimethylsiloxane (PDMS) hybrid composites containing exfoliated graphite nanoplatelets and carbon nanotubes

Polydimethylsiloxane (PDMS) hybrid composites consisting of exfoliated graphite nanoplatelets (xGnPs) and multiwalled carbon nanotubes functionalized with hydroxyl groups (MWCNTs-OH) were fabricated, and the effects of the xGnP/MWCNT-OH ratio on the thermal, electrical, and mechanical properties of polydimethylsiloxane (PDMS) hybrid composites were investigated. With the total filler content fixed at 4 wt%, a hybrid composite consisting of 75% × GnP/25% MWCNT-OH showed the highest thermal conductivity (0.392 W/m K) and electrical conductivity (1.24 × 10⁻³ S/m), which significantly exceeded the values shown by either of the respective single filler composites. The increased thermal and electrical conductivity found when both fillers are used in combination is attributed to the synergistic effect between the fillers that forms an interconnected hybrid network. In contrast, the various different combinations of the fillers only showed a modest effect on the mechanical behavior, thermal stability, and thermal expansion of the PDMS composite.     

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.     

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.     

Improved cryogenic interlaminar shear strength of glass fabric/epoxy composites by graphene oxide

The cryogenic interlaminar shear strength (ILSS) at cryogenic temperature (77 K) of glass fabric (GF)/epoxy composites is investigated as a function of the graphene oxide (GO) weight fraction from 0.05 to 0.50 wt% relative to epoxy. For the purpose of comparison, the ILSS of the GF/epoxy composites is also examined at room temperature (RT, 298 K). The results show that the cryogenic ILSS is greatly improved by about 32.1% and the RT ILSS is enhanced by about 32.7% by the GO addition at an appropriate content of 0.3 wt% relative to epoxy. In addition, the ILSS of the composite at 77 K is much higher than that at RT due to the relatively strong interfacial GF/epoxy adhesion at 77 K compared to the RT case.     

Thermal conductivity of Cu–Zr/diamond composites produced by high temperature–high pressure method

Copper matrix composites reinforced with about 90 vol.% of diamond particles, with the addition of zirconium to copper matrix, were prepared by a high temperature–high pressure method. The Zr content was varied from 0 to 2.0 wt.% to investigate the effect on interfacial microstructure and thermal conductivity of the Cu–Zr/diamond composites. The highest thermal conductivity of 677 W m⁻¹ K⁻¹ was achieved for the composite with 1.0 wt.% Zr addition, which is 64% higher than that of the composite without Zr addition. This improvement is attributed to the formation of ZrC at the interface between copper and diamond. The variation of thermal conductivity of the composites was correlated to the evolution of interfacial microstructure with increasing Zr content.     

Synergistic effect of hybrid graphene nanoplatelet and multi-walled carbon nanotube fillers on the thermal conductivity of polymer composites and theoretical modeling of the synergistic effect

We found that the thermal conductivity of polymer composites was synergistically improved by the simultaneous incorporation of graphene nanoplatelet (GNP) and multi-walled carbon nanotube (MWCNT) fillers into the polycarbonate matrix. The bulk thermal conductivity of composites with 20 wt% GNP filler was found to reach a maximum value of 1.13 W/m K and this thermal conductivity was synergistically enhanced to reach a maximum value of 1.39 W/m K as the relative proportion of MWCNT content was increased but the relative proportion of GNP content was decreased. The synergistic effect was theoretically estimated based on a modified micromechanics model where the different shapes of the nanofillers in the composite system could be taken into account. The waviness of the incorporated GNP and MWCNT fillers was found to be one of the most important physical factors determining the thermal conductivity of the composites and must be taken into consideration in theoretical calculations.     

The thermal and mechanical properties of graphite foam/epoxy resin composites

A series of epoxy resin (EP) filled graphite foam (GF) composites were prepared to explore a new material with good heat transfer property. The effects of the mass fraction of EP and the network structure of GFs on the thermal diffusivity and the compression strength of the composites were investigated. The thermal diffusivity of the GF/EP composite with EP mass fraction of 91.45% was raised to 6.541 mm²/s, which was 45.7 times higher than the pure EP. The thermal conductivity reached to 14.67 W/(m K), which was 43.1 times higher than the pure EP. The compression strength of the GF/EP increased 55% above the value of pure EP. In addition, the thermal diffusivity of GF/EP increased with the decrease of the mass fraction of EP. A model was formulated to calculate the pressure needed for a mass fraction of EP.     

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.     

Thermally reduced graphene oxide acting as a trap for multiwall carbon nanotubes in bi-filler epoxy composites

The effect of thermally reduced graphene oxide (TRGO) on the electrical percolation threshold of multi wall carbon nanotube (MWCNT)/epoxy cured composites is studied along with their combined rheological/electrical behavior in their suspension state. In contrast to MWCNT and carbon black (CB) based epoxy composites, there is no prominent percolation threshold for the bi-filler (TRGO–MWCNT/epoxy) composite. Furthermore, the electrical conductivity of the bi-filler composite is two orders of magnitude lower (∼1 × 10⁻⁵ S/m) than the pristine MWCNT/epoxy composites (∼1 × 10⁻³ S/m). This result is primarily due to the strong interaction between TRGO and MWCNTs. Optical micrographs of the suspension and scanning electron micrographs of the cured composites indicate trapping of MWCNTs onto TRGO sheets. A morphological model describing this interaction is presented.     

Enhanced microwave absorption properties of flake-shaped FePCB metallic glass/graphene composites

A novel kind of composite absorber, i.e. FePCB/graphene composite, with excellent microwave absorption properties was successfully fabricated by a simple and scalable ball milling method. After being milled, the FePCB particles displayed flaky morphology with large aspect ratio. The complex permittivity and permeability of the flaky FePCB distinctly increased compared with those before milling. Furthermore, with the introduction of graphene, the flaky FePCB/graphene composite exhibited excellent microwave absorption performance with strong absorption and wide absorption band. In particular, for FePCB/graphene composite with an absorber thickness of 2 mm, the reflection loss (RL) reached a minimum of −45.3 dB at 12.6 GHz and the effective absorption bandwidth (RL < −10 dB) covered 5.4 GHz. The enhanced microwave absorption performance of the FePCB/graphene composite was attributed to the high magnetic loss and improved impedance matching which were closely related to the flake-shaped FePCB particles and the introduction of graphene sheets.     

Effect of polymer modifier chain length on thermal conductive property of polyamide 6/graphene nanocomposites

The influence of polymer modifier chain length on the thermal conductivity of polyamide 6/graphene (GA) nanocomposites, including through-plane (λ_z) and in-plane (λ_x) directions were investigated. Here, three chain lengths of double amino-terminated polyethylene glycol (NH₂–PEG–NH₂) were used to covalently functionalize graphene with graphene content of 5.0 wt%. Results showed that λ_z was enhanced with the chain length of NH₂–PEG–NH₂ increased, but λ_x reached a maximum value at a certain chain length of NH₂–PEG–NH₂. The maximum λ_z and λ_x of GA are 0.406 W m⁻¹ K⁻¹ and 9.710 W m⁻¹ K⁻¹, respectively. This study serves as a foundation for further research on the thermal conductive property of graphene nanocomposites using different chain lengths of polymer modifier to improve the λ_z and λ_x of the thermal conductive materials.     

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 conductive ethylene vinyl acetate composites filled with reduced graphene oxide and polyaniline

A conductive network composed of reduced graphene oxide (RGO) planes and polyaniline (PANI) chains was designed and fabricated by in situ polymerization of aniline monomer on the RGO planes. It was further used for fabrication of conductive composites with a polymer matrix–ethylene vinyl acetate (EVA). The composites achieve improved conductivity at a low filler loading although the host polymer–EVA–is of insulator. For instance, compared to the pure EVA polymer, the conductivity of the composite filled with 4.0 wt.% RGO and 8.0 wt.% PANI increases from 1.2 × 10^?14 S cm^?1 to 1.07 × 10^?1 S cm^?1. In addition, thermal stability of the composites is also enhanced by the filler loading.     

Three-dimensional carbon nanotube based polymer composites for thermal management

In this study, the porous multiwall carbon nanotube (MWCNT) foams possessing three-dimensional (3D) scaffold structures have been introduced into polydimethylsiloxane (PDMS) for enhancing the overall thermal conductivity (TC). This unique interconnected structure of freeze-dried MWCNT foams can provide thermally conductive pathways leading to higher TC. The TC of 3D MWCNT and PDMS composites can reach 0.82 W/m K, which is about 455% that of pure PDMS, and 300% higher than that of composites prepared from traditional blending process. The obtained polymer composites not only exhibit superior mechanical properties but also dimensional stability. To evaluate the performance of thermal management, the LED modulus incorporated with the 3D MWCNT/PDMS composite as heat sink is also fabricated. The composites display much faster and higher temperature rise than the pristine PDMS matrix, suggestive of its better thermal dissipation. These results imply that the as-developed 3D-MWCNT/PDMS composite can be a good candidate in thermal interface for thermal management of electronic devices.     

Synergistic effect of boron nitride flakes and tetrapod-shaped ZnO whiskers on the thermal conductivity of electrically insulating phenol formaldehyde composites

Tetrapod-shaped zinc oxide (T-ZnO) whiskers and boron nitride (BN) flakes were employed to improve the thermal conductivity of phenolic formaldehyde resin (PF). A striking synergistic effect on thermal conductivity of PF was achieved. The in-plane thermal conductivity of the PF composite is as high as 1.96 W m⁻¹ K⁻¹ with 30 wt.% BN and 30 wt.% T-ZnO, which is 6.8 times higher than that of neat PF, while its electrical insulation is maintained. With 30 wt.% BN and 30 wt.% T-ZnO, the flexural strength of the composite is 312.9% higher than that of neat PF, and 56.2% higher that of the PF composite with 60 wt.% BN. The elongation at break is also improved by 51.8% in comparison with that of the composite with 60 wt.% BN. Such a synergistic effect results from the bridging of T-ZnO whiskers between BN flakes facilitating the formation of effective thermal conductance network within PF matrix.     

Polysaccharidic binders for the conception of an insulating agro-composite

The objective of this study is the formulation of a natural polysaccharidic binder for the conception of an insulating bio-based composite made with sunflower stalk particles. The formulation was performed using chitosan cross-linked with Genipin and mixed with alginate, guar gum and starch. A fractional factorial experimental design within 32 essays was established to find the formulation leading to composites with the best combination between good mechanical properties and limited amount of chitosan in the binder. Composites with a thermal conductivity (κ) of 0.07 W m⁻¹ K⁻¹ and a maximum tensile stress (σ_max) of 0.2 MPa were obtained with a total binder ratio of 5.5% (w/w). The results of this study show that the insulating bio-based composites evaluated have competitive mechanical and thermal performances compared with other eco-friendly insulating materials available on the market.     

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.