Effect of processing technique on the transport and mechanical properties of graphite nanoplatelet/rubbery epoxy composites for thermal interface applications

Graphite nanoplatelet (GNP)/rubbery epoxy composites were fabricated by mechanical mixer (MM) and dual asymmetric centrifuge speed mixer (SM). The properties of the GNP/rubbery epoxy were compared with GNP/glassy epoxy composites. The thermal conductivity of GNP/rubbery epoxy composite (25 wt.% GNP, particle size 15 μm) reached 2.35 W m⁻¹ K⁻¹ compared to 0.1795 W m⁻¹ K⁻¹ for rubbery epoxy. Compared with GNP/rubbery epoxy composite, at 20 wt.%, GNP/glassy epoxy composite has a slightly lower thermal conductivity but an electrical conductivity that is 3 orders of magnitude higher. The viscosity of rubbery epoxy is 4 times lower than that of glassy epoxy and thus allows higher loading. The thermal and electrical conductivities of composites produced by MM are slightly higher than those produced by SM due to greater shearing of GNPs in MM, which results in better dispersed GNPs. Compression and hardness testing showed that GNPs increase the compressive strength of rubbery epoxy ∼2 times without significantly affecting the compressive strain and hardness. The GNP/glassy epoxy composites are 40 times stiffer than the GNP/rubbery epoxy composites. GNP/rubbery epoxy composites with their high thermal conductivity, low electrical conductivity, low viscosity before curing and high conformability are promising thermal interface materials.     

Yttria-stabilized zirconia-based composites with adaptive thermal conductivity

Thermal conductivity trends in a “chameleon coating” thin film were characterized with a time-domain thermoreflectance (TDTR) technique. A yttria-stabilized zirconia (YSZ)-based nanocomposite material containing ∼21 vol.% silver (Ag) was employed for this study. The thermal conductivity (k) of the as-deposited composite film was measured with TDTR and found to have a value of 7.4 ± 1.4 W m⁻¹ K⁻¹. The film was then annealed at 500 °C for 1 h to stimulate Ag flow from within the composite to the surface via diffusion. The Ag that coalesced on the surface during annealing was removed to expose the underlying porous YSZ matrix, and the sample was reexamined with the TDTR technique. The thermal conductivity of the porous nanocomposite YSZ material was then measured to be 1.6 ± 0.2 W m⁻¹ K⁻¹, which is significantly lower than a fully dense control sample of pure nanocrystalline YSZ (2.0 ± 0.1 W m⁻¹ K⁻¹). The annealed film displayed a 20% reduction in thermal conductivity as compared to the control sample and a 4–5-fold reduction in thermal conductivity as compared to the as-deposited material. The experiments demonstrate temperature triggering of a composite material, resulting in self-modifying thermal conductivity and diffusion-controlled porosity. These aspects can be used to enhance or restrict thermal transport (i.e., a thermal switch). The applicability of the TDTR technique to measurements of thin, nanoporous film materials is also demonstrated.     

Thermal conductivity of liquid crystalline epoxy/BN filler composites having ordered network structure

BN filler was added to a liquid crystalline (LC) epoxy resin to obtain a high thermal conductive material. The LC epoxy/BN composites, which were cured at different temperatures, formed an isotropic or LC polydomain phase structure. The relationship between the network orientation containing mesogenic groups and the dispersibility of the BN filler was discussed. As a result, the thermal conductivity of the LC polydomain system was drastically enhanced even at a relatively low volume fraction of BN (30 vol%), regardless of the fact that both the LC and isotropic phase systems consisted of the same resin and filler content combination. This result is due to the formation of thermal conductive paths by the BN filler by exclusion of the BN filler from the LC domain formed during the curing process in the composite having the LC polydomain matrix.     

The low temperature thermoelectric properties of CuxTiSe2−ySy

The low temperature thermoelectric properties of TiSe₂, co-doped with Cu and S, are reported. Partial S substitution for Se changes the magnitude of the indirect bandgap, while the Cu-doping independently controls the n-type carrier concentration. The Seebeck coefficients are negative, in the range of −50 to −200 μV K⁻¹, and the resistivities are 0.1-10 mΩ cm. The thermal conductivity for the sample with the largest thermoelectric power factor was found to be relatively low, 3-4 W m⁻¹ K⁻¹, and decreases with decreasing temperature. The thermoelectric efficiencies for the best materials found in this system, typified by Cu_0.02TiSe_1.7S_0.3, were largest at 0.07 at 300 K and decreased to 0.01 at 75 K.     

Nanocomposites based on MWCNT and styrene–butadiene–styrene block copolymers: Effect of the preparation method on dispersion and polymer–filler interactions

Composites of Kraton-D® 1102 BT (a styrene–butadiene–styrene block copolymer) and multi-walled carbon nanotubes (MWCNTs) were prepared by melt mixing. The composites were characterized by electrical conductivity measurements (Coleman’s method), mechanical properties (DMA and stress–strain tests), thermal stability (thermogravimetry) and morphology of dispersion (SEM). Finally, the resulting composites were compared with those made by the solution casting method. The results showed a strong influence of the preparation methodology on the final properties of the composites due to changes in morphology. Composites prepared by casting showed a higher electrical conductivity than extruded ones; the composites with 6 wt.% of MWCNT prepared by extrusion presented conductivity of the same order of magnitude as the composite with 1 wt.% of MWCNT prepared by casting – 10⁻³ to 10⁻⁴ S cm⁻¹. However, the extruded samples presented better mechanical properties than the casting ones.     

Enhanced thermal conductivity of epoxy nanocomposites filled with hybrid filler system of triethylenetetramine-functionalized multi-walled carbon nanotube/silane-modified nano-sized silicon carbide

Multi-walled carbon nanotubes (MWCNTs) were first treated by a 3:1 (v/v) mixture of concentrated H₂SO₄/HNO₃, and then triethylenetetramine (TETA) grafting was carried out. Nano-sized silicon carbide particles (SiC_np) were modified by the silane coupling agent. Epoxy nanocomposites filled with hybrid filler system containing TETA-functionalized MWCNTs and silane-modified SiC_np were prepared. The investigation on the thermal conductivity of epoxy nanocomposites filled with single filler system and hybrid filler system was performed. Chemical surface treatment is conducive to the enhancement of thermal conductivity of epoxy composites. The thermal conductivity of epoxy composites with hybrid filler system is higher than that of epoxy composites with any single filler system (functionalized MWCNTs or modified SiC_np), which is due to the effective combination of MWCNT-to-MWCNT and SiC_np-to-SiC_np conductive networks. Hybrid filler system could provide synergistic effect and cost reduction simultaneously.     

Construction of 3D Skeleton for Polymer Composites Achieving a High Thermal Conductivity

Owing to the growing heat removal issue in modern electronic devices, electrically insulating polymer composites with high thermal conductivity have drawn much attention during the past decade. However, the conventional method to improve through‐plane thermal conductivity of these polymer composites usually yields an undesired value (below 3.0 Wm^?1 K^?1). Here, construction of a 3D phonon skeleton is reported composed of stacked boron nitride (BN) platelets reinforced with reduced graphene oxide (rGO) for epoxy composites by the combination of ice‐templated and infiltrating methods. At a low filler loading of 13.16 vol%, the resulting 3D BN‐rGO/epoxy composites exhibit an ultrahigh through‐plane thermal conductivity of 5.05 Wm^?1 K^?1 as the best thermal‐conduction performance reported so far for BN sheet‐based composites. Theoretical models qualitatively demonstrate that this enhancement results from the formation of phonon‐matching 3D BN‐rGO networks, leading to high rates of phonon transport. The strong potential application for thermal management has been demonstrated by the surface temperature variations of the composites with time during heating and cooling.     

Three-dimensional thermal conductive behavior of graphite materials sintered from ribbon mesophase pitch-based fibers

Block graphite prepared from ribbon mesophase pitch-based fibers, which are arranged unidirectionally, exhibits three-dimensional anisotropic thermal conductive behavior. The thermal conductivity (TC) of the graphite along the direction parallel to the fiber axis is 30-40× that of the other two directions. And with increasing graphitization temperature, the TC of the graphite material treated at 3273 K in the direction parallel to the fiber axis increases and reaches 837 W m⁻¹ K⁻¹, while that in other direction decreases to 11 W m⁻¹ K⁻¹ because of regular arrangement of graphite crystallites.     

Microstructures and improved wear resistance of 3D needled C/SiC composites with graphite filler

Three-dimensional (3D) needled carbon/carbon (C/C) composites with a lowest porosity of 15.6% were achieved after 1 cycle of impregnation by phenolic resin slurry containing graphite filler, hot-pressing curing and pyrolysis. Carbon/silicon carbide (C/SiC) composites were obtained by liquid silicon infiltrating C/C composites. The aim was to incorporate cost effectiveness and excellent performance of C/SiC braking material. Using filler content not exceeding 30 wt% in the slurry promised undamaged C/C segments in C/SiC composites. The linear wear rate of C/SiC using 30 wt% filler was 0.33 μm side⁻¹ cycle⁻¹ and displayed a fourfold decrease; its weight wear rate was 2.46 mg side⁻¹ cycle⁻¹ and minus 171%, compared with the previously reported values of C/SiC without filler, at a braking velocity of 28 m/s. Its friction coefficients and friction stability coefficients appeared relative insensitive to changes in braking velocities and displayed higher values at high braking velocities compared with the previous values.     

A novel gel polymer electrolyte based on polyacrylonitrile (PAN) and its application in a solar cell

A PAN-based gel polymer electrolyte with possible iodide ion conductivity was prepared by incorporating a mixture of Pr₄N⁺I⁻, iodine, EC and PC in PAN. Out of various compositions prepared and characterised, the sample with composition PAN (13%):EC (31%):PC (45%):Pr₄N⁺I⁻ (7%):I₂ (4%) by weight ratio, exhibited the maximum room temperature (25°C) conductivity of 2.95×10⁻³ S cm⁻¹. The predominantly ionic nature of the electrolyte was established by using the dc polarisation technique. The temperature dependence of ionic conductivity follows the VTF behaviour, indicating the amorphous nature of the electrolyte. Dye-sensitised photoelectrochemical solar cells prepared using this electrolyte exhibited an open circuit voltage (V_oc) of 0.69 V, a short circuit current (I_sc) of 3.73 mA cm⁻² for an incident light intensity of 600 W m⁻² yielding an overall quantum efficiency of 2.99%.     

The thermal conductivity of embedded nano-aluminum nitride-doped multi-walled carbon nanotubes in epoxy composites containing micro-aluminum nitride particles

Amino-functionalized nano-aluminum nitride (nano-AlN) particles were doped onto the surfaces of chlorinated multi-walled carbon nanotubes (MWCNTs) to act as fillers in thermally conducting composites. These synthesized materials were embedded in epoxy resin. Then, the untreated micro-aluminum nitride (micro-AlN) particles were added to this resin, whereby the composites filled with nano-AlN-doped MWCNTs (0, 0.5, 1, 1.5, 2 wt%) and micro-AlN (25.2, 44.1, 57.4 vol%) were fabricated. As a result, the thermal diffusivity and conductivity of all composites continuously improved with increasing nano-AlN-doped MWCNT content and micro-AlN filler loading. The thermal conductivity reached its maximum, which was 31.27 times that of the epoxy alone, when 2 wt% nano-AlN-doped MWCNTs and 57.4 vol% micro-AlN were added to the epoxy resin. This result is due to the high aspect ratio of the MWCNTs and the surface polarity of the doped nano-AlN and micro-AlN particles, resulting in the improved thermal properties of the epoxy composite.     

Vacuum insulation panels—From research to market

Vacuum insulation panels (VIPs) have a thermal resistance about a factor of 10 higher than that of equally thick conventional polystyrene boards. Similar to thermos flasks these systems make use of ‘vacuum’ to suppress the heat transfer via gaseous conduction. While thermos flasks are to be pumped down to a high vacuum, filling material integrated in the flat VIP elements, which bears the atmospheric pressure load, reduces the requirements on the vacuum and thus on the tightness of the vacuum casing. Optimal in this respect is a kernel of fumed silica. This kernel is evacuated to below 1 mbar and sealed in a high-barrier laminate, which consists of several layers of Al-coated polyethylene (PE) and polyethylene terephthalate (PET). The laminate is optimized for low air and moisture leakage rates and thus for a long service life. The evacuated silica kernel has a thermal conductivity of about 0.004 W m⁻¹ K⁻¹ at room temperature, mainly resulting from solid thermal conduction along the tenuous silica backbone. As the kernel is nanoporous, the gaseous thermal conductivity becomes noticeable only for pressures above 10 mbar. At about 200 mbar the thermal conductivity measures about 0.008 W m⁻¹ K⁻¹. Such a gas pressure could occur after several decades of usage in a middle European climate. With VIP, slim yet highly insulating façade constructions can be realized. A centre U-value of 0.2 W m⁻² K⁻¹ can be achieved for a VIP thickness of only 2 cm, if optimized kernels and barrier laminates as well as stringent quality control are employed. A successful “self-trial” using VIPs within a façade of the ZAE-building in Würzburg in 1999 was the starting point for new applications of evacuated insulations in the building sector.     

Highly conducting poly(methyl methacrylate)/carbon nanotubes composites: Investigation on their thermal, dynamic-mechanical, electrical and dielectric properties

Nanocomposites of poly(methyl methacrylate) (PMMA) containing various multi-walled carbon nanotubes (MWCNT) contents were prepared using melt mixing. Several techniques were employed to study the influence of the MWCNT addition on the thermal, mechanical, electrical and dielectric properties of the PMMA matrix. The electrical percolation threshold (p_c) was found to be 0.5 vol.% by performing AC and DC conductivity measurements. Significantly high conductivity levels (σ_dc) were achieved: σ_dc exceeds 10⁻² S/cm already at 1.1 vol.%, the criterion for EMI shielding (σ_dc > 10⁻¹ S/cm) is fulfilled at 2.9 vol.%, and the highest loaded sample (5.2 vol.%) gave a maximum value of 0.5 S/cm. Dielectric relaxation spectroscopy measurements in broad frequency (10⁻¹−10⁶ Hz) and temperature ranges (−150 to 170 °C) indicated weak polymer-filler interactions, in consistency with differential scanning calorimetry and dynamic-mechanical analysis findings. Weak polymer-filler interactions and absence of crystallinity facilitate the achievement of high conductivity levels in the nanocomposites.     

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.     

Multi-scale electrical response of silicon nitride/multi-walled carbon nanotubes composites

Dense silicon nitride (Si₃N₄) composites with various amounts (0-8.6 vol%) of multi-walled carbon nanotubes (MWCNTs) are electrically characterised by combining macroscopic dc-ac and nanoscale conductive scanning force microscopy (C-SFM) measurements. In this way, a coherent picture of the dominant charge transport mechanisms in Si₃N₄/MWCNTs composites is presented. A raise of more than 10 orders of magnitude in the electrical dc conductivity compared to the blank specimen is measured for MWCNTs contents above 0.9 vol%. Semiconductor and metallic-like behaviours are observed depending on both the temperature and the MWCNTs content. Macroscopic measurements are further supported at the nanoscale by means of C-SFM. The metallic-type conduction is associated to charge transporting along the nanotube shells, whereas the semiconductor behaviour is linked to hopping conduction across nanotube-nanotube contacts and across intrinsic defect clusters within the nanotubes.     

Rapid synthesis of homogeneous MnO2/multi-wall carbon nanotubes nanostructure and its electrochemical capacitive behavior

A homogeneous composite of MnO₂/multi-wall carbon nanotubes (MnO₂/MWCNTs) was rapidly and efficiently synthesized by a redox reaction of MnO₄⁻ and Mn²⁺ on the MWCNTs under ultrasonic irradiation. The structure and morphology of the obtained MnO₂ and MnO₂/MWCNTs composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Electrochemical investigation indicated that the maximum specific capacitance of the MnO₂/MWCNTs composite, measured by galvanostatic charge-discharge test, was 315 F g^− 1, compared to the pristine MnO₂ (192 F g^− 1) and MWCNTs electrode (25 F g^− 1), showing the synergistic effect of MWCNTs and MnO₂. The homogeneous hybrid nanostructure and the good conductivity of MWCNTs were considered to be responsible for its preferable electrochemical performances.     

The formation of magnetite nanoparticles on the sidewalls of multi-walled carbon nanotubes

Linear polyethyleneimine (PEI) was used as a non-covalent functionalizing agent to modify multi-walled carbon nanotubes (MWCNTs). Fe₃O₄ nanoparticles were then formed along the sidewalls of the as-modified MWCNTs through a simple solvothermal method. X-ray diffraction, Fourier transform infrared spectrometry, transmission electron microscopy, and vibrating sample magnetometry were used to characterize the MWCNT/Fe₃O₄ nanocomposites. Results indicated that Fe₃O₄ nanoparticles with diameters ranging from 50 to 200 nm were attached to the surface of the MWCNTs by electrostatic interaction. PEI was found to improve the electrical conductivity of the MWCNT/Fe₃O₄ nanocomposites. The magnetic saturation value of these magnetic nanocomposites was 61.8 emu g⁻¹. These magnetic MWCNT/Fe₃O₄ nanocomposites are expected to have wide applications in bionanoscience and technology.     

Enhancement of thermal and electrical conductivities of cyanoacrylate by addition of carbon based nanofillers

Nanocomposites with addition of graphite nanoparticles, multi-walled carbon nanotubes (MWCNTs), and graphene in cyanoacrylate from 0.1 to 0.5 or 0.6 vol% were fabricated. The influences of morphology towards thermal and electrical conductivities of cyanoacrylate nanocomposites were studied. Microstructure based on field emission scanning electron microscopy and transmission electron microscopy images indicated that nanofillers have unique morphologies which affect the thermal and electrical conductivities of nanocomposites. The maximum thermal conductivity values were measured at 0.3195 and 0.3500 W/mK for 0.4 vol% of MWCNTs/cyanoacrylate and 0.5 vol% of graphene/cyanoacrylate nanocomposite, respectively. These values were improved as high as 204 and 233% as compared with the thermal conductivity of neat cyanoacrylate. Nanocomposites with 0.2 vol% MWCNTs/cyanoacrylate fulfilled the requirement for ESD protection material with surface resistivity of 6.52?×?10⁶ Ω/sq and volume resistivity of 6.97?×?10⁹ Ω m. On the other hand, 0.5 vol% MWCNTs/cyanoacrylate nanocomposite can be used as electrical conductive adhesive. Compared with graphene and graphite nanofillers, MWCNTs is the best filler to be used in cyanoacrylate for improvement in thermal and electrical conductivity enhancement at low filler loading.     

Preparation and properties of hollow glass microsphere-filled epoxy-matrix composites

Hollow glass microsphere (HGM)–filled epoxy composites, with filler content ranging from 0 to 51.3 vol.%, were prepared in order to modify the dielectric properties of the epoxy. The results showed that the dielectric constant (D_k) and dielectric loss (D_f) of the composites decreased simultaneously with increasing HGM content, which was critical for the provision of superior high-frequency device performance. Other properties of the composite, such as the coefficient of thermal expansion (CTE) and the glass transition temperature (T_g), were also improved. The improvement in these properties was related to strong interaction between the HGM and epoxy, which was indicated by the formation of an interphase between the HGM and epoxy-matrix. It was unsatisfactory in this study that the thermal conductivity of the composites also decreased with HGM content. In order to obtain relatively high thermal conductivity and a low dielectric constant simultaneously, this paper suggests further adding other filler.     

Thermal stability of the Mobil Five type metallosilicate molecular sieves—An in situ high temperature X-ray diffraction study

We have carried out in situ high temperature X-ray diffraction (HTXRD) studies of silicalite-1 (S-1) and metallosilicate molecular sieves containing iron, titanium and zirconium having Mobil Five (MFI) structure (iron silicalite-1 (FeS-1), titanium silicalite-1 (TS-1) and zirconium silicalite-1 (ZrS-1), respectively) in order to study the thermal stability of these materials. Isomorphous substitution of Si⁴⁺ by metal atoms is confirmed by the expansion of unit cell volume by X-ray diffraction (XRD) and the presence of Si-O-M stretching band at ∼960 cm⁻¹ by Fourier transform infrared (FTIR) spectroscopy. Appearance of cristobalite phase is seen at 1023 and 1173 K in S-1 and FeS-1 samples. While the samples S-1 and FeS-1 decompose completely to cristobalite at 1173 and 1323 K, respectively, the other two samples are thermally stable upto 1623 K. This transformation is irreversible. Although all materials show a negative lattice thermal expansion, their lattice thermal expansion coefficients vary. The thermal expansion behavior in all samples is anisotropic with relative strength of contraction along ‘a’ axes is more than along ‘b’ and ‘c’ axes in S-1, TS-1, ZrS-1 and vice versa in FeS-1. Lattice thermal expansion coefficients (α_v) in the temperature range 298-1023 K were −6.75 × 10⁻⁶ K⁻¹ for S-1, −12.91 × 10⁻⁶ K⁻¹ for FeS-1, −16.02 × 10⁻⁶ K⁻¹ for TS-1 and −17.92 × 10⁻⁶ K⁻¹ for ZrS-1. The highest lattice thermal expansion coefficients (α_v) obtained were −11.53 × 10⁻⁶ K⁻¹ for FeS-1 in temperature range 298-1173 K, −20.86 × 10⁻⁶ K⁻¹ for TS-1 and −25.54 × 10⁻⁶ K⁻¹ for ZrS-1, respectively, in the temperature range 298-1623 K. Tetravalent cation substitution for Si⁴⁺ in the lattice leads to a high thermal stability as compared to substitution by trivalent cations.