Thermal conductivity of graphene nanoplatelets filled composites fabricated by solvent-free processing for the excellent filler dispersion and a theoretical approach for the composites containing the geometrized fillers

The thermal conductivity of polymer composites containing nanofillers such as GNP (graphene nanoplatelet) and carbon black (CB) was investigated using experimental and theoretical approaches. We developed a fabrication method that allows different shapes and sizes of nanofillers to be highly dispersed in polymer resin. When the bulk and in-plane thermal conductivities of the fabricated composites were measured, they were found to increase rapidly as the GNP filler content increased. The in-plane thermal conductivity of composites with 20 wt.% GNP filler was found to reach a maximum value of 1.98 W/m K. The measured thermal conductivities were compared with the calculated values based on a micromechanics model where the waviness of nanofillers could be taken into account. The waviness of the incorporated GNP filler is an important physical factor that determines the thermal conductivity of composites and must be taken into consideration in theoretical calculations.     

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.     

The influence of compression molding techniques on thermal conductivity of UHMWPE/BN and UHMWPE/(BN + MWCNT) hybrid composites with segregated structure

Various ultra-high-molecular-weight polyethylene (UHMWPE)/boron nitride (BN) and UHMWPE/(BN + multi-wall carbon nanotube (MWCNT)) composites with segregated structure were prepared by using the compression molding process. The dispersion of fillers under different compression molding were observed by optical microscopy and scanning electron microscopy. The results showed that integrated thermal conductive networks were formed after cold-pressing sintering. However, these networks would be destroyed by middle-high pressure/high temperature treatment. Although the treatment of high pressure/high temperature can effectively improve the crystallinity and crystal size of UHMWPE, the thermal conductivity of composite dramatically decreased due to the replacement of filler-filler by filler-polymer-filler interface. The 1D-MWCNT is liable to entangle with 2D-BNs and formed MWCNT-BN networks even at high pressure/high temperature, leading to a nearly constant thermal conductivity (reached 1.794 W/m·K with the addition of 50% (BNs + MWCNT) hybrid fillers). Besides, the dispersion of the fillers have a great influence on thermal stability of the composites.     

Heterogeneously structured conductive carbon fiber composites by using multi-scale silver particles

This paper reports a new approach to enhance the through-thickness thermal conductivity of laminated carbon fabric reinforced composites by using nanoscale and microscale silver particles in combination to create heterogeneously structured continuous through-thickness thermal conducting paths. High conductivity of 6.62 W/(m K) with a 5.1 v% silver volume fraction can be achieved by incorporating these nanoscale and microscale silver particles in EWC-300X/Epon862 composite. Silver flakes were distributed within the inter-tow area, while nanoscale silver particles penetrated into the fiber tows. The combination of different sizes of silver fillers is able to effectively form continuous through-thickness conduction paths penetrating fiber tows and bridging the large inter-tow resin rich areas. Positive hybrid effects to thermal conductivity were found in IM7/EWC300X/sliver particle hybrid composites. In addition, microscale fillers in resin rich areas showed less impact on tensile performance than nanoscale particles applied directly on fiber surface.     

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.     

Thermal conductivity of Cu/diamond composites prepared by a new pretreatment of diamond powder

Cu/diamond composites were fabricated by spark plasma sintering (SPS) after the surface pretreatment of the diamond powders, in which the diamond particles were mixed with copper powder and tungsten powder (carbide forming element W). The effects of the pretreatment temperature and the diamond particle size on the thermal conductivity of diamond/copper composites were investigated. It was found that when 300 μm diamond particles and Cu–5 wt.% W were mixed and preheated at 1313 K, the composites has a relatively higher density and its thermal conductivity approaches 672 W (m K)⁻¹.     

Interfacial microstructure and its effect on thermal conductivity of SiCp/Cu composites

Thermal conductivity of SiCp/Cu composites was usually far below the expectation, which is usually attributed to the low real thermal conductivity of matrix. In the present work, highly pure Cu matrix composites reinforced with acid washed SiC particles were prepared by the pressure infiltration method. The interfacial microstructure of SiCp/Cu composites was characterized by layered interfacial products, including un-reacted SiC particles, a Cu–Si layer, a polycrystalline C layer and Cu–Si matrix. However, no Cu₃Si was found in the present work, which is evidence for the hypothesis that the formation of Cu₃Si phase in SiC/Cu system might be related to the alloying elements in Cu matrix and residual Si in SiC particles. The thermal conductivity of SiCp/Cu composites was slightly increased with the particle size from 69.9 to 78.6 W/(m K). Due to high density defects, the real thermal conductivity of Cu matrix calculated by H–J model was only about 70 W/(m K). The significant decrease in thermal conductivity of Cu matrix is an important factor for the low thermal conductivity of SiCp/Cu composites. However, even considered the significant decrease of thermal conductivity of Cu matrix, theoretical values of SiCp/Cu composites calculated by H–J model were still higher than the experimental results. Therefore, an ideal particle was introduced in the present work to evaluate the effect of interfacial thermal resistance. The reverse-deduced effective thermal conductivities of ideal particles according to H–J model was about 80 W/(m K). Therefore, severe interfacial reaction in SiCp/Cu composites also leads to the low thermal conductivity of SiCp/Cu composites.     

The effect of interfacial state on the thermal conductivity of functionalized Al2O3 filled glass fibers reinforced polymer composites

Rapidly increasing packaging density of electronic devices puts forward higher requirements for thermal conductivity of glass fibers reinforced polymer (GFRP) composites, which are commonly used as substrates in printed circuit board. Interface between fillers and polymer matrix has long been playing an important role in affecting thermal conductivity. In this paper, the effect of interfacial state on the thermal conductivity of functionalized Al₂O₃ filled GFRP composites was evaluated. The results indicated that amino groups-Al₂O₃ was demonstrated to be effective filler to fabricate thermally conductive GFPR composite (1.07 W/m K), compared with epoxy group and graphene oxide functionalized Al₂O₃. It was determined that the strong adhesion at the interface and homogeneous dispersion of filler particles were the key factors. Moreover, the effect of interfacial state on dielectric and thermomechanical properties of GFRP composites was also discussed. This research provides an efficient way to develop high-performance GFRP composites with high thermal conductivity for integrated circuit packaging applications.     

The thermal conductivity of Al(OH)3 covered MWCNT/epoxy terminated dimethyl polysiloxane composite based on analytical Al(OH)3 covered MWCNT

Aluminum-hydroxide-covered multi-walled carbon nanotubes (A–MWCNT) were fabricated as a thermally conductive material. The thermal conductivity of A–MWCNT was estimated based on Casimir theory. The effective thermal conductivity of A–MWCNT was estimated at about ∼26 W/mK. The thermal conductivity of A–MWCNT/epoxy-terminated polydimethylsiloxane (ETDS) composite was examined as a function of A–MWCNT loading, and the results showed the maximum value at 1.5 wt% of A–MWCNT loading, above which it decreased slightly. The effective medium approximation (EMA) developed by Maxwell–Garnett (M–G) was used to analyze the thermal conducting behavior of the composite. The experimental results showed negative deviation from the expected thermal conductivity, k_e, beyond 1.5 wt% of A–MWCNT loading, because the composites containing A–MWCNT were strongly affected by interfacial resistance. The interfacial resistance value calculated from M–G approximation increased when filler loading was higher than 1.5 wt% because of the folded and partially agglomerated A–MWCNT along with insufficient interfacial interactions.     

Thermal conductivity of epoxy composites with a binary-particle system of aluminum oxide and aluminum nitride fillers

Aluminum oxide and aluminum nitride with different sizes were used alone or in combination to prepare thermally conductive polymer composites. The composites were categorized into two systems, one including composites filled with large-sized aluminum nitride and small-sized aluminum oxide particles, and the other including composites filled with large-sized aluminum oxide and small-sized aluminum nitride. The use of these hybrid fillers was found to be effective for increasing the thermal conductivity of the composite, which was probably due to the enhanced connectivity offered by the structuring filler. At a total filler content of 58.4 vol.%, the maximum values of both thermal conductivities in the two systems were 3.402 W/mK and 2.842 W/mK, respectively, when the volume ratio of large particles to small particles was 7:3. This result was represented when the composite was filled with the maximum packing density and the minimum surface area at the same volume content. As such, the proposed thermal model predicted thermal conductivity in good agreement with experimental values.     

A comparative study on the electrical,thermal and mechanical properties of ethylene–octene copolymer based composites with carbon fillers

Conducting polymer composites (CPC) were prepared with an ethylene–octene copolymer (EOC) matrix and with either carbon fibers (CFs) or multiwall carbon nanotubes (MWCNTs) as fillers. Their electrical and thermal conductivities, mechanical properties and thermal stabilities were evaluated and compared. CF/EOC composites showed percolation behavior at a lower filler level (5 wt.%) than the MWCNT/EOC composites (10 wt.%) did. Alternating current (AC) conductivity and real part of permittivity (dielectric constant) of these composites were found to be frequency-dependent. Dimensions and electrical conductivities of individual fillers have a great influence on the conductivities of the composites. CF/EOC composites possessed higher conductivity than the MWCNT-composites at all concentrations, due to the higher length and diameter of the CF filler. Both electrical and thermal conductivities were observed to increase with increasing filler level. Tensile moduli and thermal stabilities of both (CF/EOC and MWCNT/EOC) composites increase with rising filler content. Improvements in conductivities and mechanical properties were achieved without any significant increase in the hardness of the composites; therefore, they can be potentially used in pressure/strain sensors. Thermoelectric behavior of the composites was also studied. Accordingly, CF and MWCNT fillers are versatile and playing also other roles in their composites than just being conducting fillers.     

Synergetic effect of thermal conductive properties of epoxy composites containing functionalized multi-walled carbon nanotubes and aluminum nitride

This study investigates the thermal conductivity of epoxy composites containing two hybrid fillers which are multi-walled carbon nanotubes (MWCNTs) and aluminum nitride (AlN). To form a covalent bonds between the fillers and the epoxy resin, poly(glycidyl methacrylate) (PGMA) were grafted onto the surface of nano-sized MWCNTs via free radical polymerization and micro-sized AlN was modified by zirconate coupling agent. Results show that functionalized fillers improve thermal conductivity of epoxy composites, due to the good dispersion and interfacial adhesion, which is confirmed by scanning electron microscope. Furthermore, the hybrid fillers provide synergetic effect on heat conductive networks. The thermal conductivity of epoxy composites containing 25 vol.% modified AlN and 1 vol.% functionalized MWCNTs is 1.21 W/mK, comparable to that of epoxy composites containing 50 vol.% untreated AlN (1.25 W/mK), which can reduce the half quantity of AlN filler used.     

Properties of graphene nanopowder and multi-walled carbon nanotube-filled epoxy thin-film nanocomposites for electronic applications: The effect of sonication time and filler loading

Graphene nanopowder (GNP) and multi-walled carbon nanotube (MWCNT)-filled epoxy thin-film composites were fabricated using ultrasonication and the spin coating technique. The effect of sonication time (10, 20 and 30 min) and GNP loading (0.05–1 vol%) on the tensile and electrical properties of GNP/epoxy thin-film composites was investigated. The addition of GNP decreased the material’s tensile strength and modulus. However, among the tested samples, the GNP/epoxy composites produced using 20 min of sonication time had a slightly higher tensile strength and modulus, with a lower electrical percolation threshold volume fraction. The effect of sonication time was supported by morphological analysis, which showed an improvement in GNP dispersion with increased sonication time. However, GNP deformation was observed after a long sonication time. The GNP/epoxy composites at different filler loadings showed higher electrical properties but slightly lower tensile properties compared with the MWCNT/epoxy composites fabricated using 20 min of sonication time.     

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.     

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.     

Comparison of carbon nanofiller-based polymer composite adhesives and pastes for thermal interface applications

Graphite nanoplatelets (GNP), carbon black (CB) and carbon nanotubes are extensively researched to produce thermal interface materials (TIMs). This work reports comparison of interfacial thermal conductance (ITC) of carbon nanofiller-based polymer composite adhesives and pastes. The results show that total thermal contact resistance (TTCR) of GNP/rubbery epoxy composite was the same as that of an equivalent glassy epoxy composite. Although CB-based rubbery epoxy and silicone composites can be applied as thin bondlines, their TTCRs were significantly higher than GNP/rubbery epoxy. GNP incorporation into CB/rubbery epoxy composite improves the ITC of the CB/rubbery epoxy composites but the performance of CB/GNP/rubbery epoxy was inferior to GNP/rubbery epoxy. The thermal paste of GNP/polyetheramine had TTCR of 4.8 × 10^− 6 m²·K/W which is comparable to commercial TIM-paste. The paste produced with silicone had relatively poor ITC versus that prepared with polyetheramine. The paste having smaller particle sized GNPs offers lower TTCR than that prepared with large sized GNPs. The GNP/rubbery epoxy adhesives produced from precursor pastes gave the lowest TTCRs in comparison with the other adhesives. This study suggests that GNPs offer potential for enhancing ITC of TIMs and that ITC of adhesives depends on fillers' thermal conductivity and their interfacial contact with substrates.     

Highly thermally conductive POSS-g-SiCp/UHMWPE composites with excellent dielectric properties and thermal stabilities

Polyhedral oligomeric silsesquioxane grafting thermally conductive silicon carbide particle (POSS-g-SiCp) fillers, are performed to fabricate highly thermally conductive ultra high molecular weight polyethylene (UHMWPE) composites combining with optimal dielectric properties and excellent thermal stabilities, via mechanical ball milling followed by hot-pressing method. The POSS-g-SiCp/UHMWPE composite with 40 wt% POSS-g-SiCp exhibits relative higher thermal conductivity, lower dielectric constant and more excellent thermal stability, the corresponding thermally conductive coefficient of 1.135 W/mK, the dielectric constant of 3.22, and the 5 wt% thermal weight loss temperature of 423 °C, which holds potential for packaging and thermal management in microelectronic devices. Agari’s semi-empirical model fitting reveals POSS-g-SiCp fillers have strong ability to form continuous thermally conductive networks.     

Morphology and thermal conductivity of polyacrylate composites containing aluminum/multi-walled carbon nanotubes

Polyacrylate composites with various fillers such as multi-walled carbon nanotube (CNT), aluminum flake (Al-flake), aluminum powders and Al–CNT were prepared by a ball milling. The thermal decomposition temperature increased by as much as 64 °C for polyacrylate/Al-flake 70 wt% composite compared to polyacrylate. The thermal conductivity of polyacrylate/Al–CNT composites increased from 0.50 to 1.67 W/m K as the Al–CNT content increases from 50 to 80 wt%. The thermal conductivity of the composite sheet increases with the sheet thickness. At the given filler concentration (90 wt%), the composite filled with aluminum powder of 13 μm has a higher thermal conductivity than the one filled 3 μm powder, and the composite filled with mixture of two powders showed a synergistic effect on the thermal conductivity. The morphology indicates that the dispersion of CNT in the polyacrylate/Al-flake + CNT composite is not perfect, and agglomeration of CNTs was observed.     

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.     

Preparation of low-density polyethylene/low-temperature expandable graphite composites with high thermal conductivity by an in situ expansion melt blending process

A facile strategy with the advantages of low cost and ease of mass production was presented to prepare low-density polyethylene (LDPE)/low-temperature expandable graphite (LTEG) composites with relatively high thermal conductivity by an in situ expansion melt blending process. LTEGs were expanded and delaminated into graphite multi-layers and graphite nanoplatelets during processing which synergistically created more thermo-conducting paths in the composites and hence led to great improvements in thermal conductivity. Thermal conductivity of the composite with 60 wt% of LTEG loading was increased by 23 times as compared to the pure LDPE, increasing from 0.47 to 11.28 W/mK. The incorporation of LTEG decreased the melting temperature and the degree of crystallinity of LDPE. Percolation threshold of both the electrical conductivity and rheological measurements was observed at about 8 vol% of LTEG loading. Moreover, the LDPE/LTEG composites showed better thermal stability compared to the pure LDPE.