Thermal transport phenomena and limitations in heterogeneous polymer composites containing carbon nanotubes and inorganic nanoparticles

An Off-Lattice Monte Carlo model was developed to investigate effective thermal conductivities (K_eff) and thermal transport limitations of polymer composites containing carbon nanotubes (CNTs) and inorganic nanoparticles. The simulation results agree with experimental data for poly(ether ether ketone) (PEEK) with inclusions of CNTs and tungsten disulfide (WS₂) nanoparticles. The developed model can predict the thermal conductivities of multiphase composite systems more accurately than previous models by taking into account interfacial thermal resistance (R_bd) between the nanofillers and the polymer matrix, and the nanofiller orientation and morphology. The effects of (i) R_bd of CNT–PEEK and WS₂–PEEK (0.0232–115.8 × 10⁻⁸ m²K/W), (ii) CNT concentration (0.1–0.5 wt%), (iii) CNT morphology (aspect ratio of 50–450, and diameter of 2–8 nm), and (iv) CNT orientation (parallel, random and perpendicular to the heat flux) on K_eff of a multi-phase composite are quantified. The simulation results show that K_eff of multiphase composites increases when the CNT concentration increases, and when the R_bd of CNT–PEEK and WS₂–PEEK interfaces decrease. The thermal conductivity of composites with CNTs parallel to the heat flux can be enhanced ∼2.7 times relative to that of composites with randomly-dispersed CNTs. CNTs with larger aspect ratio and smaller diameter can significantly improve the thermal conductivity of a multiphase polymer composite.     

Synthesis,microstructure and electrical conductivity of carbon nanotube–alumina nanocomposites

Carbon nanotube–alumina (CNT–Al₂O₃) nanocomposites have been synthesized by direct growth of carbon nanotubes on alumina by chemical vapor deposition (CVD) and the as-grown nanocomposites were densified by spark plasma sintering (SPS). Surface morphology analysis shows that the CNTs and CNT bundles are very well distributed between the matrix grains creating a web of CNTs as a consequence of their in situ synthesis. Even after the SPS treatment, the CNTs in the composite material are still intact. Experimental result shows that the electrical conductivity of the composites increases with the CNT content and falls in the range of the conductivity of semiconductors. The nanocomposite with highest CNT content has electrical conductivity of 3336 S/m at near room temperature, which is about 13 orders of magnitude increase over that of pure alumina.     

Physical properties of carbon nanotube sheets drawn from nanotube arrays

We report mechanical, thermal, and electrical properties of novel sheet materials composed of multiwalled carbon nanotubes, drawn from a CNT array. At low loading there is some slippage of CNTs but at higher loading tensile strength σ₀ = 7.9 MPa and Young’s modulus E = 310 MPa. The room-temperature thermal conductivity of the CNT sheet was 2.5 ± 0.5 W m^?1 K^?1, giving a thermal conductivity to density ratio of κ/ρ = 65 W m^?1 K^?1 g^?1 cm³. The heat capacity shows 1D behavior for T > 40 K, and 2D or 3D behavior at lower temperatures. The room-temperature specific heat was 0.83 J g^?1 K^?1. The iV curves above 10 K have Ohmic behavior while the iV curve at T = 2 K is non-Ohmic, and a model to explain both ranges is presented. Negative magnetoresistance was found, increasing in magnitude with decreasing temperature (?15% at T = 2 K and B = 9 T). The tensile strength, Young’s modulus and electrical conductivity of the CNT sheet are low, in comparison with other CNT materials, likely due to defects. Thermal conductivity is dominantly phononic but interfacial resistance between MWCNTs prevents the thermal conductivity from being higher.     

Enhancing buckypaper conductivity through co-deposition with copper nanowires

Buckypapers, the thin sheets made from an aggregate of carbon nanotubes (CNTs), have demonstrated promising electrical and thermal conductivities. However, the high in-plane to perpendicular anisotropy makes its application as thermal interface materials difficult. In order to increase the perpendicular electrical and thermal conductivities, copper nanowires (Cu NWs) were introduced into buckypapers. The Cu NWs stuck into the empty spaces between CNTs, connected them perpendicularly, and even induced a certain perpendicular CNT alignment. The electrical conductivity increased continuously with increasing the Cu content, while the smallest anisotropy was observed at the 50 wt.% Cu filling because an in-plane Cu network formed and improved much more the in-plane conductivity above this filling. On the contrary, as CNTs are more thermally conducting than Cu, the loading of Cu NWs over 50 wt.% decreased the thermal conductivity. Our measurement showed a high perpendicular conductivity of 10.1 W/m K at the 50 wt.% loading, more than quadruple and double as compared with the ones for a pure buckypaper and the one filled with 67–75 wt.% Cu NWs.     

The hierarchical structure and properties of multifunctional carbon nanotube fibre composites

The axial mechanical, electrical and thermal properties of carbon nanotubes (CNTs) can be exploited macroscopically by assembling them parallel to each other into a fibre during their synthesis by chemical vapour deposition. Multifunctional composites with high volume fraction of CNT fibres are then made by direct polymer infiltration of an array of aligned fibres. The fibres have a very high surface area, causing the polymer to infiltrate them and resulting in a hierarchical composite structure. The electrical and thermal conductivities of CNT/epoxy composites are shown to be superior to those of equivalent specimens with T300 carbon fibre (CF) which is widely used in industry. From measurements of longitudinal coefficient of thermal expansion (CTE) of the composites we show that the CTE of CNT fibres is approximately ?1.6 × 10^?6 K^?1, similar to in-plane graphite. The combination of electrical, thermal and mechanical properties of CNT fibre composites demonstrates their potential for multifunctionality.     

Thermoelectric properties of carbon nanotube reinforced cement-based composites fabricated by compression shear

Carbon nanotubes (CNTs) with weight percent of 5.0%, 10.0% and 15.0% were added into the cement matrix to fabricate CNT reinforced cement-based composites (CNTs/CC) by mixing and dry compression shear methods. Seebeck coefficient, electrical conductivity and thermal conductivity of the as-received CNTs/CC were measured and analyzed in detail. The CNTs/CC exhibits the thermoelectric behavior of p-type semiconductor. CNTs were dispersed uniformly in cement matrix by compression shear stress, which promoted a relatively high electrical conductivity (0.818 S/cm) and Seebeck coefficient (57.98 μV/°C) of CNTs/CC. Combining with their lower thermal conductivity ranged from 0.734 to 0.947 W m^?1 K^?1, the CNTs/CC shows the highest thermoelectric figure of merit (ZT) has reached 9.33 × 10^?5, Which is benefit to the applications in large-scale energy harvesting in the buildings and pavements with low cost in the future cities.     

Overcoming the quality–quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion–extraction process

Dispersion-printing processes are essential for the fabrication of various devices using carbon nanotubes (CNTs). Insufficient dispersion results in CNT aggregates, while excessive dispersion results in the shortening of individual CNTs. To overcome this tradeoff, we propose here a repetitive dispersion–extraction process for CNTs. Long-duration ultrasonication (for 100 min) produced an aqueous dispersion of CNTs with sodium dodecylbenzene sulfonate with a high yield of 64%, but with short CNT lengths (a few μm), and poor conductivity in the printed films (∼450 S cm⁻¹). Short-duration ultrasonication (for 3 min) yielded a CNT dispersion with a very small yield of 2.4%, but with long CNTs (up to 20–40 μm), and improved conductivity in the printed films (2200 S cm⁻¹). The remaining sediment was used for the next cycle after the addition of the surfactant solution. 90% of the CNT aggregates were converted into conductive CNT films within 13 cycles (i.e., within 39 min), demonstrating the improved conductivity and reduced energy/time requirements for ultrasonication. CNT lines with conductivities of 1400–2300 S cm⁻¹ without doping and sub-100 μm width, and uniform CNT films with 80% optical transmittance and 50 Ω/sq sheet resistance with nitric acid doping were obtained on polyethylene terephthalate films.     

Electrical and thermal properties of SiC-Zr2CN composites sintered with Y2O3-Sc2O3 additives

SiC-Zr₂CN composites were fabricated from β-SiC and ZrN powders with 2 vol% equimolar Y₂O₃-Sc₂O₃ additives via conventional hot pressing at 2000 °C for 3 h in a nitrogen atmosphere. The electrical and thermal properties of the SiC-Zr₂CN composites were investigated as a function of initial ZrN content. Relative densities above 98% were obtained for all samples. The electrical conductivity of Zr₂CN composites increased continuously from 3.8 × 10³ (Ωm)⁻¹ to 2.3 × 10⁵ (Ωm)⁻¹ with increasing ZrN content from 0 to 35 vol%. In contrast, the thermal conductivity of the composites decreased from 200 W/mK to 81 W/mK with increasing ZrN content from 0 to 35 vol%. Typical electrical and thermal conductivity values of the SiC-Zr₂CN composites fabricated from a SiC-10 vol% ZrN mixture were 2.6 × 10⁴ (Ωm)⁻¹ and 168 W/m K, respectively.     

Electromagnetic wave absorption properties of graphene modified with carbon nanotube/poly(dimethyl siloxane) composites

By using a catalytic growth procedure, carbon nanotubes (CNTs) are in situ formed on reduced graphene oxide (RGO) sheet at 600 °C. CNTs growing on RGO planes through covalent C–C bond possess lower interfacial contact electrical resistance. As a hybrid structure, the CNTs/graphene (CNT/G) are well dispersed into poly (dimethyl siloxane). The hybrid combining electrically lossy CNTs and RGO, which disperses in electrically insulating matrix, constructs an electromagnetic wave (EM) absorbing material with ternary hierarchical architecture. The interfacial polarization in heterogeneous interface plays an important role in absorbing EM power. When the filler loading is 5 wt.% and thickness of absorber is 2.75 mm, the minimum value of reflection coefficient and the corresponding frequency are −55 dB and 10.1 GHz, and the effective absorption bandwidth reaches 3.5 GHz. Therefore, combining the CNTs and graphene sheet into three-dimensional structures produces CNT/G hybrids that can be considered as an effective route to design light weight and high-performance EM absorbing material, while the effective EM absorption frequency can be designed.     

Preparation-microstructure-property relationships in double-walled carbon nanotubes/alumina composites

Double-walled carbon nanotube/alumina composite powders with low carbon contents (2–3 wt.%) are prepared using three different methods and densified by spark plasma sintering. The mechanical properties and electrical conductivity are investigated and correlated with the microstructure of the dense materials. Samples prepared by in situ synthesis of carbon nanotubes (CNTs) in impregnated submicronic alumina are highly homogeneous and present the higher electrical conductivity (2.2–3.5 S cm⁻¹) but carbon films at grain boundaries induce a poor cohesion of the materials. Composites prepared by mixing using moderate sonication of as-prepared double-walled CNTs and lyophilisation, with little damage to the CNTs, have a fracture strength higher (+30%) and a fracture toughness similar (5.6 vs 5.4   MPa m^1/2) to alumina with a similar submicronic grain size. This is correlated with crack-bridging by CNTs on a large scale, despite a lack of homogeneity of the CNT distribution.     

Reducing thermal contact resistance using a bilayer aligned CNT thermal interface material

A thermal interface material (TIM) was fabricated by synthesizing aligned carbon nanotubes (CNT) on both sides of a thin copper foil. The Hot Disk^® method was applied to measure the thermal conductivity of these CNT-TIMs. Results showed that a thicker copper foil substrate or CNT layer led to a lower overall thermal resistance. The laser flash method was used to study the performance of the bilayer aligned CNT-TIMs using two copper plates as heat source and sink. An enhancement in thermal conductivity of more than 290% could be obtained under an applied contact pressure of 0.01 MPa, as compared with two copper plates in direct contact. By filling in the space between the CNTs in the CNT layer with a conventional thermal conductive elastomer, Sylgard 160, the thermal resistance of the TIM was reduced to 8.78 mm² K/W, a value that is better than similar devices in the literature.     

Effect of carbon nanotubes with different lengths on mechanical and electrical properties of silica-filled styrene butadiene rubber compounds

Carbon nanotubes (CNTs) having three different lengths of 5, 30, and 100 μm were added to silica-filled styrene butadiene rubber (SBR) compounds in order to investigate the effect of the CNT addition on the dynamic and electrical properties. The amounts of CNTs were 1, 2, 4, and 7 phr, while the amount of silica was set high at 80 phr to clearly demonstrate the performance of the CNTs as fillers. The effect of CNTs on the silica-filled SBR compounds on the tensile properties is not significant, but the addition of longer CNTs with high loading severely deteriorated the dynamic properties, but considerably enhanced electrical conductivity. The medium loading of CNTs in silica-filled SBR compounds is suitable for the improvement of the electrical conductivity without severely sacrificing the dynamic properties.     

Carbon nanotube/carbon nanofiber growth from industrial by-product gases on low- and high-alloy steels

The growth of carbon nanotubes (CNTs) on sheet metal surfaces (including low- and high-alloyed steel and Ni-plated steel) has been explored using a mixture of CO, CO₂, and H₂ as the precursor feedstock in a thermal chemical vapor deposition process. The influence of various experimental parameters such as the reactor temperature, reaction time, and precursor composition on the yield, purity, and dimensions of the CNTs has been elucidated. Addition of CO₂ during CNT growth leads to higher carbon deposition rates, especially for low- and high-alloyed steel. The diameters of the obtained CNTs range from 12 to 300 nm at carbon deposition rates of ～0.3 mg cm^?2 min^?1. The CNTs are observed to be uniformly distributed and adhered firmly to the substrates. The experimental conditions for CNT growth on sheet metal surfaces are very similar to concentrations and temperatures of a typical effluent stream of the steel industry. This process thus holds potential to harness waste gases to fabricate CNT-based coatings that impart added functionality to sheet metals, while further reducing the carbon footprint of steel plants.     

On the manufacturing and electrical and mechanical properties of ultra-high wt.% fraction aligned MWCNT and randomly oriented CNT epoxy composites

The effect of CNT orientation on electrical and mechanical properties is presented on the example of an ultra-high filler loaded multi-walled carbon nanotube (68 wt.% MWCNTs) epoxy-based nanocomposite. A novel manufacturing method based on hot-press infiltration through a semi-permeable membrane allows to obtain both, nanocomposites with aligned and randomly oriented CNTs (APNCs and RPNCs) over a broad filler loading range of ≈10–68 wt.%. APNCs are based on low-defected, mm-long aligned MWCNT arrays grown in chemical vapour deposition (CVD) process. Electrical conductivity and mechanical properties were measured parallel and perpendicular to the direction of CNTs. RPNCs are based on both, aligned mm-long MWCNTs and randomly oriented commercial μm-long and entangled MWCNTs (Baytube C150P, and exemplarily Arkema Graphistrength C100). The piezoresistive strain sensing capability of these high-wt.% APNCs and RPNCs had been investigated towards the influence of CNT orientations. For the highest CNT fraction of 68 wt.% of unidirectional aligned CNTs a Young’s modulus of E_|| ≈ 36 GPa and maximum electrical conductivity of σ_|| ≈ 37·10⁴ S/m were achieved.     

Thermal fatigue and hypothermal atomic oxygen exposure behavior of carbon nanotube wire

In low earth orbit (LEO), components of space systems are exposed to damaging hypothermal atomic oxygen and thermal fatigue. Carbon nanotube (CNT) wires are candidate materials for different applications in space systems. Thirty-yarn CNT wire’s behavior was evaluated when exposed to hypothermal atomic oxygen and thermal fatigue. CNT wire specimens were exposed to a nominal fluence of hypothermal atomic oxygen of 2 × 10²⁰ atoms/cm². The erosion rate due to hypothermal collision between atomic oxygen and CNT wires was calculated to be 2.64 × 10⁻²⁵ cm³/atom, which is comparable to highly ordered pyrolytic graphite. The tensile strength of CNT wire was not affected by this exposure, and a minor reduction of electrical conductivity (2.5%) was found. Scanning electron microscopy (SEM) and Energy Dispersive X-ray spectroscopy analysis showed erosion of surface layer with depleted carbon and increased oxygen. Thermal fatigue excursion of 5000 cycles from 70 to −50 °C at a rate of 55 °C/min showed no loss in tensile strength; however a large decrease in conductivity (18%) was seen. SEM analysis showed that the thermal fatigue created buckling of yarn and fracture of individual CNTs bundles. These reduced the effective area and electrical conductivity of CNT wire.     

Electrical conductivity of carbon nanotubes grown inside a mesoporous anodic aluminium oxide membrane

Well-aligned, open-ended carbon nanotubes (CNTs), free of catalyst and other carbon products, were synthesized inside the pores of an anodic aluminium oxide (AO) template without using any metallic catalyst. The CNTs and the CNT/AO composites were characterized by scanning and transmission electron microscopy, thermogravimetric analysis, Raman spectroscopy and X-ray diffraction. Particular care was devoted to the reactor design, synthesis conditions, the catalytic role of the templating alumina surface and the preservation of the alumina structure. The transport properties (sorption, diffusion and permeability) to water vapor were evaluated for both the alumina template and the CNT/AO composite membrane. The measured effective electrical volume conductivity of the CNT/AO composite was found ranging from a few up to 10 kS/m, in line with the recent literature. The estimated averaged values of the CNTs-wall conductivity was around 50 kS/m.     

Synthesis,morphology and physical properties of multi-walled carbon nanotube/biphenyl liquid crystalline epoxy composites

We have developed multi-walled carbon nanotube/liquid crystalline epoxy composites and studied the effects of incorporation carbon nanotubes (CNTs) on the morphology, thermal and mechanical properties of the composites. The CNTs are functionalized by liquid crystalline (LC) 4,4′-bis(2,3-epoxypropoxy) biphenyl (BP) epoxy resin for the ease of dispersion and the formation of long range ordered structure. The epoxy functionalized CNT (ef-CNT) were dispersed in the LC BP epoxy resin that can be thermal cured with an equivalent of 4,4′-diamino-diphenylsulfone to form composite. The curing process was monitored by polarized optical microscopy. The results indicate the LC resin was aligned along the CNTs to form fiber with dendritic structure initially then further on to obtain micro-sized spherical crystalline along with fibrous crystalline. With homogeneous dispersion and strong interaction between nanotubes and matrix, the composite containing 2.00 wt.% ef-CNT exhibits excellent thermal and mechanical properties. When the amount of ef-CNT exceeds 2.00 wt.%, vitrification stage of curing is fast reached, which lowers the degree of conversion. As compared with the neat resin, the composite containing 2.00 wt.% ef-CNT increases the glass transition temperature by 70.0 °C, the decomposition temperature by 13.8 °C, the storage modulus by 40.9%, and the microhardness by 63.3%.     

Heat conduction mechanisms in hot pressed ZrB2 and ZrB2–SiC composites

Thermal diffusivity and conductivity of hot pressed ZrB₂ with different amounts of B₄C (0–5 wt%) and ZrB₂–SiC composites (10–30 vol% SiC) were investigated experimentally over a wide range of temperature (25–1500 °C). Both thermal diffusivity and thermal conductivity were found to decrease with increase in temperature for all the hot pressed ZrB₂ and ZrB₂–SiC composites. At around 200 °C, thermal conductivity of ZrB₂–SiC composites was found to be composition independent. Thermal conductivity of ZrB₂–SiC composites was also correlated with theoretical predictions of the Maxwell–Eucken relation. The dominated mechanisms of heat transport for all hot pressed ZrB₂ and ZrB₂–SiC composites at room temperature were confirmed by Wiedemann–Franz analysis by using measured electrical conductivity of these materials at room temperature. It was found that electronic thermal conductivity dominated for all monolithic ZrB₂ whereas the phonon contribution to thermal conductivity increased with SiC contents for ZrB₂–SiC composites.     

A large increase in the thermal conductivity of carbon nanotube/polymer composites produced by percolation phenomena

We have studied the thermal conductivity of carbon nanotube/polymer composites as a function of the CNT volume fraction using a steady-state measurement technique. The results show a large increase in the thermal conductivity at a small loading of carbon nanotube volume fraction (ca. 1.4 vol.%). The remarkably high increase in the thermal conductivity is described well by thermal transport through networks of carbon nanotubes in the polymer matrix, following a critical power law indicating percolating behavior, which shows the thermal percolation in the vicinity of the electrical percolation threshold concentration.     

Mechanical and functional properties of Al2O3–ZrO2–MWCNTs nanocomposites

Multi-walled carbon nanotubes (MWCNTs) are often reported as additives improving mechanical and functional properties of ceramic composites. However, despite tremendous efforts in the field in the past 20 years, the results are still inconclusive. This paper studies room temperature properties of the composites with polycrystalline alumina matrix reinforced with 0.5–2 vol.% MWCNTs (composites AC) and zirconia toughened alumina with 5 vol.% of yttria partially stabilised zirconia (3Y-PSZ) containing 0.5–2 vol.% of MWCNTs (composites AZC). Dense composites were prepared through wet mixing of the respective powders with functionalised MWCNTs, followed by freeze granulation, and hot-pressing of granulated powders. Room temperature bending strength, Young's modulus, indentation fracture toughness, thermal and electrical conductivity of the composites were studied, and related to their composition and microstructure. Slight increase of Young's modulus, indentation fracture toughness, bending strength, and thermal conductivity was observed at the MWCNTs contents ≤1 vol.%. At higher MWCNTs contents the properties were impaired by agglomeration of the MWCNTs. The DC electrical conductivity increased with increasing volume fraction of the MWCNTs.