Thermophysical properties of multi-wall carbon nanotube bundles at elevated temperatures up to 830 K

Thermal transport measurements in multi-wall carbon nanotube (MWCNT) bundles at elevated temperatures up to 830 K are reported using a novel generalized electrothermal technique. Compared with individual CNTs, the thermal conductivity (k) of MWCNT bundles is two to three orders of magnitude lower, suggesting the thermal transport in MWCNT bundles is dominated by the tube-to-tube thermal contact resistance. The effective density for the two MWCNT bundles, which is difficult to measure using other techniques, is determined at 116 kg/m³ and 234 kg/m³. The thermal diffusivity slightly decreases with temperature while k exhibits a small increase with temperature up to 500 K and then decreases. For the first time, the behavior of specific heat for MWCNTs above room temperature is determined. The specific heat is close to graphite at 300–400 K but is lower than that for graphite above 400 K, indicating that the behavior of phonons in MWCNT bundles is dominated by boundary scattering rather than by the three-phonon Umklapp process. The analysis of the radiation heat loss suggests that it needs to be considered when measuring the thermophysical properties of micro/nano wires of high aspect ratios at elevated temperatures, especially for individual MWCNTs due to their extremely small diameters.     

Nano- and microstructural effects on thermal properties of poly (l-lactide)/multi-wall carbon nanotube composites

In this work the thermal properties of poly (l-lactide)/multi-wall carbon nanotube (PLLA/MWCNT) composites have been investigated. Thermal conductivity was determined after measuring specific heat capacity (C_p), thermal diffusivity (D) and bulk density (ρ) of composites. Thermal conductivity rises up to 0.345 W/m K at 5 wt.% after reaching a minimum value of about 0.12 W/m K at 0.75 wt.%. In order to understand the heat-conduction process, experimentally obtained thermal conductivities were fitted to an existing theoretical model. The much lower thermal conductivity of composites compared with the value estimated from the intrinsic thermal conductivity of the nanotubes and their volume fraction could be explained in terms of the obtained large thermal resistance (R_k) of 1.8 ± 0.3 × 10^?8 m² K/W at nanotube–matrix interface. The CNT dispersion in the composites was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Although the thermal resistance dramatically reduces the estimated bulk thermal conductivity of composites, the existence of an interconnected conductive nanotube network for thermal diffusion in PLLA/MWCNT composites demonstrates that the addition of carbon nanotubes represents an efficient strategy in order to successfully enhance the thermal conductivity of insulator polymers.     

An Evaluation of the Thermophysical Properties of Stoichiometric CeO2 in Comparison to UO2 and PuO2

The thermal conductivity of stoichiometric CeO₂ was determined through measurement of thermal expansion from 313 to 1723 K, thermal diffusivity from 298 to 1473 K, and specific heat capacity from 313 to 1373 K. The thermal conductivity was then calculated as the product of the density, thermal diffusivity, and specific heat capacity. The thermal conductivity was found to obey an (A + BT)^?1 relationship with A = 6.776×10^?2 m·K·W^?1 and B = 2.793 × 10^?4 m·W^?1. Extrapolations of applied models were made to provide suggested data for the specific heat capacity, thermal diffusivity, and thermal conductivity data up to 1723 K. Results of thermal expansion and heat capacity measurements agreed well with the limited low‐temperature data available in the literature. The thermal conductivity values provided in the current study are significantly higher than the only high‐temperature data located for CeO₂. This is attributed to the tendency of CeO₂ to rapidly reduce at elevated temperatures given the available partial pressure of O₂ in air at ambient pressure. The CeO₂ data are compared to literature values for UO₂ and PuO₂ to evaluate its suitability as a surrogate in nuclear fuel systems where thermal transport is a primary criterion for performance     

Synergistic improvement of thermal conductivity of thermoplastic composites with mixed boron nitride and multi-walled carbon nanotube fillers

The thermal conductivity of composites with a polyphenylene sulfide (PPS) matrix and a mixture of boron nitride (BN) power and multi-wall carbon nanotube (MWCNT) fillers was investigated. Synergistic improvement in thermal conductivity of the composite was observed due to the generation of three-dimensional thermal transfer pathways between the BN and MWCNT. The improvement strongly depended on surface treatment of the MWCNTs, such as hydrogen peroxide and acid treatments. The thermal conductivity of the composite was affected by the interaction and interfacial thermal resistance between the PPS matrix and the MWCNTs. The maximum thermal conductivity achieved was 1.74 W/m K for a composite that was pelletizable, injection moldable, and thermally conductive with low electrical conductivity and good mechanical properties.     

Thermal conductivity of a graphene oxide–carbon nanotube hybrid/epoxy composite

Thermally conductive graphene oxide (GO)–multi-wall carbon nanotube (MWCNT)/epoxy composite materials were fabricated by epoxy wetting. The polar functionality on the GO surface allowed the permeation of the epoxy resin due to a secondary interaction between them, which allowed the fabrication of a composite containing a high concentration of this hybrid filler. The thermal transport properties of the composites were maximized at 50 wt.% of filler due to fixed pore volume fraction in filtrated GO cake. When the total amount of filler was fixed 50 wt.% while changing the amount of MWCNTs, a maximum thermal conductivity was obtained with the addition of about 0.36 wt.% of MWCNTs in the filler. Measured thermal conductivity was higher than the predicted value based on the by Maxwell–Garnett (M–G) approximation and decreased for MWCNT concentrations above 0.4%. The increased thermal conductivity was due to the formation of 3-D heat conduction paths by the addition of MWCNTs. Too high a MWCNT concentration led to increased phonon scattering, which in turn led to decreased thermal conductivity. The measured storage modulus was higher than that of the solvent mixed composite because of the insufficient interface between the large amount of filler and the epoxy.     

Crystallization of poly(ε-caprolactone)/MWCNT composites: A combined SAXS/WAXS,electrical and thermal conductivity study

In situ crystallization of poly(ε-caprolactone) (PCL) filled with different contents (0.2–5 wt%) of multiwalled carbon nanotubes (MWCNTs) was investigated in X-ray (SAXS/WAXS) synchrotron experiments simultaneously with thermal and electric conductivity measurements. The combined study provides information on nucleation ability of MWCNT, crystallization and melting kinetics, degree of crystallinity as well as the evolution of thermal diffusivity and electrical conductivity of PCL/MWCNT composites during isothermal and non-isothermal crystallization.     

Thermal properties and transition studies of multi-wall carbon nanotube/nylon-6 composites

Transition behavior and thermal properties of a multi-wall carbon nanotube (MWCNT)/nylon-6 composite (P-composite) made by in situ polymerization and subsequently structurally modified by high-pressure–high-temperature treatment have been established. The thermal conductivity (κ) of nylon-6 improved ∼27% by the addition of 2.1 wt.% MWCNT filler simultaneously as the heat capacity per unit volume decreased ∼22% compared with that of nylon-6 at 1 atm and 298 K. Moreover, the MWCNT filler raises the glass transition temperature (T_g) of nylon-6, but the pressure dependence of T_g remains unchanged. A model for κ indicates that the interfacial thermal resistance between the MWCNT filler and the nylon-6 matrix decreases 20% up to 1 GPa and most significantly above 0.8 GPa. P-composite was structurally modified by a sluggish cold-crystallization transition at 1.0 GPa, 530 K, which further increased κ by as much as ∼37% as the crystallinity of nylon-6 improved from 31% to 58% with a preferred crystal orientation and increased crystal size.     

Thermal performance of vertically-aligned multi-walled carbon nanotube array grown on platinum film

Vertically-aligned carbon nanotube array is expected to inherit high thermal conductivity and mechanical compliance of individual carbon nanotube and serve as thermal interface material. In this paper, vertically-aligned multi-walled carbon nanotube arrays have been directly grown on Pt film and the thermal performance has been studied by using laser flash technique. The determined thermal diffusivity decreases from 0.187 to 0.135 cm² s⁻¹ and the thermal conductivity increases from 1.8 to 3.1 W m⁻¹ K⁻¹ as temperature increases from 243.2 to 453.2 K. The fracture surface of the array peeled off the Pt film was characterized by scanning electron microscopy. It has been illustrated that the tearing surface is not smooth but fluffy with torn carbon nanotubes, indicating strong interfacial bonding and consequent small interface resistance between carbon nanotube array and Pt film. According to Raman spectra and transmission electron microscopy image, the possible mechanisms responsible for the thermal transport degradation are low packing density, twist, and the presence of impurities, amorphous carbon, defects and flaws. The influence of intertube van der Waals interactions has been studied by comparing the phonon dispersion relations and is expected to be not significant.     

Catalytic effect of iron oxide on carbon/carbon composites during graphitization

Coal tar pitch matrix was modified by addition of iron oxide in different proportions i.,e. 0, 1, 3 and 5% by weight. The matrix was used to develop carbon fibre reinforced composites heat treated to 1000 and 2500 °C, respectively. The catalytic effect of iron oxide was ascertained by measuring the physical properties viz. the inter layer spacing, thermal conductivity and flexural strength of the composites. Low concentrations of the catalyst resulted in improvement in the thermal conductivity of composites from 68 × 10⁻² W/m K for 0% to 127 × 10⁻² W/m K for 1% iron oxide concentration. The flexural strength of graphitized composites, however, showed a remarkable increase from 325 MPa for 0% to 450 MPa for 5% iron oxide concentrations. The increase in flexural strength was probably due to the development of large numbers of grain boundaries whereas the increase in the thermal conductivity was most likely due to larger crystallite size i.e. decreases in the interlayer spacing (d₀₀₂) of the graphitized composites.     

Thermal conductivity of MWCNT/epoxy composites: The effects of length,alignment and functionalization

Carbon nanotubes (CNTs) show great promise to improve composite electrical and thermal conductivity due to their exceptional high intrinsic conductance performance. In this research, long multi-walled carbon nanotubes (long-MWCNTs) and its thin sheet of entangled nanotubes were used to make composites to achieve higher electrical and thermal conductivity. Compared to short-MWCNT sheet/epoxy composites, at room temperature, long-MWCNT samples showed improved thermal conductivity up to 55 W/mK. The temperature dependence of thermal conductivity was in agreement with κ ∝ Tⁿ (n = 1.9–2.3) below 150 K and saturated around room temperature due to Umklapp scattering. Samples with the improved CNT degree of alignment by mechanically stretching can enhance the room temperature thermal conductivity to over 100 W/mK. However, functionalization of CNTs to improve the interfacial bonding resulted in damaging the CNT walls and decreasing the electrical and thermal conductivity of the composites.     

Parametric study of intrinsic thermal transport in vertically aligned multi-walled carbon nanotubes using a laser flash technique

The thermal diffusivity of vertically aligned carbon nanotube (VACNT, multi-walled) films synthesized by thermal chemical vapor deposition was measured by a laser flash technique, and shown to be ～30 mm² s^?1 along the tube-alignment direction. The calculated thermal conductivities of the VACNT films and the individual CNTs were ～27 and ～540 W m^?1 K^?1, respectively. The technique was verified to be reliable although a proper sampling procedure is critical. A systematic parametric study of the effects of defects, buckling, tip-to-tip contacts, packing density, and tube–tube interaction on the thermal diffusivity was carried out. Defects and buckling decreased the thermal diffusivity dramatically. An increased packing density was beneficial in increasing the collective thermal conductivity of the VACNT film; however, the increased tube–tube interaction in dense VACNT films decreased the effective thermal conductivity of the individual CNTs in the films. The tip-to-tip contact resistance was shown to be ～1 × 10^?7 m² K W^?1. The study will shed light on the potential application of VACNTs as thermal interface materials in microelectronic packaging.     

Effects of baffle inclination angle on flow and heat transfer of a heat exchanger with helical baffles

Numerical simulations were carried out to study the impacts of various baffle inclination angles on fluid flow and heat transfer of heat exchangers with helical baffles. The simulations were conducted for one period of seven baffle inclination angles by using periodic boundaries. Predicted flow patterns from simulation results indicate that continual helical baffles can reduce or even eliminate dead regions in the shell side of shell-and-tube heat exchangers. The average Nusselt number increases with the increase of the baffle inclination angle α when α < 30°. Whereas, the average Nusselt number decreases with the increase of the baffle inclination angle when α > 30°. The pressure drop varies drastically with baffle inclination angle and shell-side Reynolds number. The variation of the pressure drop is relatively large for small inclination angle. However, for α > 40°, the effect of α on pressure drop is very small. Compared to the segmental heat exchangers, the heat exchangers with continual helical baffles have higher heat transfer coefficients to the same pressure drop. Within the Reynolds number studied for the shell side, the optimal baffle inclination angle is about 45°, with which the integrated heat transfer and pressure drop performance is the best. The detailed knowledge on the heat transfer and flow distribution in this investigation provides the basis for further optimization of shell-and-tube heat exchangers.     

Simultaneously enhanced thermal conductivity and dielectric properties of borosilicate glass-based LTCC with AlN and h-BN additions

Microwave devices with reduced dielectric loss and electronic components with increased integration density necessitate the higher performance of electronic packaging materials. The h-BN/AlN/CaCO₃-MgO-B₂O₃-SiO₂-Li₂CO₃ glass composites were prepared via tape-casting and then sintered by pressureless and hot-pressing, respectively. The thermal conductivity of pressureless sintered composite was increased to 6.55 W/(m·K) by incorporating 3 wt% h-BN, and the thermal expansion of 4.47 ppm/K was achieved along with low dielectric constant of 5.76 and dielectric loss of 7.02 × 10⁻⁴ at 24 GHz. In contrast, the hot-pressing sintered composite containing 4 wt% h-BN exhibited higher thermal conductivity of 10.3 W/(m·K) and lower dielectric loss of 4.77 × 10⁻⁴. The microstructure characterization indicated the construction of heat conduction networks, and XRD analysis illustrated the formation of crystallization in the glass. Such low-temperature co-fired ceramic (LTCC) with high thermal conductivity and low dielectric loss would be a promising candidate for electronic packaging and 5G communication applications.     

Polymer composites with enhanced thermal conductivity via oriented boron nitride and alumina hybrid fillers assisted by 3-D printing

Herein, oriented boron nitride (BN)/alumina (Al₂O₃)/polydimethylsiloxane (PDMS) composites were obtained by filler orientation due to the shear-inducing effect via 3-D printing. The oriented BN platelets acted as a rapid highway for heat transfer in the matrix and resulted in a significant increase in the thermal conductivity along the orientation direction. Extra addition of spherical Al₂O₃ enhanced the fillers networks and resulted in the dramatic growth of slurry viscosity. This, together with filler orientation induced the synergism and provided large increases in the thermal conductivity. A high orientation degree of 90.65% and in-plane thermal conductivity of 3.64 W/(m∙K) were realized in the composites with oriented 35 wt% BN and 30 wt% Al₂O₃ hybrid fillers. We attributed the influence of filler orientation and hybrid fillers on the thermal conductivity to the decrease of thermal interface resistance of composites and proposed possible theoretical models for the thermal conductivity enhancement mechanisms.     

Fabrication and properties of highly transparent Tm3Al5O12 (TmAG) ceramics

Highly transparent Tm₃Al₅O₁₂ (TmAG) ceramics were fabricated by solid-state reaction and vacuum sintering. Densification, microstructure evolution, mechanical, thermal, and optical properties of the TmAG ceramics were investigated. Fully dense TmAG ceramic with average grain size of 15 μm was obtained by sintering at 1780 °C for 20 h. The in-line transmittance was 80.5% at 2000 nm. The absorption coefficients at 682 nm and 785 nm were 8.03 cm⁻¹ and 8.33 cm⁻¹, respectively. The Vickers hardness, the Young modulus, the bending strength, and the fracture toughness values were 15.14 GPa, 343 GPa, 230 MPa, and 2.35 MPa m^1/2, respectively. The thermal conductivity at room temperature was 3.3 W/m K and the average linear thermal expansion coefficient from 20 °C to 1000 °C was 8.915 × 10⁻⁶ K.     

Energy harvesting and temperature sensing thermoelectric devices based on the carbon template method

A series of self-supporting carbon nanomaterial films with different morphologies were employed as conductive templates for n-junction after polyethyleneimine (PEI) doping by taking advantages of the entanglement between carbon nanotubes. With the assistance of dimethyl sulfoxide (DMSO)-treated poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) films as p-junction, flexible and light-weight thermoelectric generators (TEGs) were assembled. The effect of the morphology of the carbon nanomaterial, including multi-walled carbon nanotube (MWCNT), whisker carbon nanotube (WSCNT), and graphene on the electrical conductivity, mechanical properties and morphology of n-junction was investigated, on basis of which thermoelectric properties of TEG were evaluated. The properties of the three carbon-based self-supporting films show significant differences. The MWCNT/PEI film exhibits a tensile strength of up to 36.23 ± 0.57 MPa due to the high entanglement network density of MWCNT. The entanglement of WSCNT/MWCNT/PEI provides an ideal conductive template for PEI to prepare n-junction material. TEGs with PEDOT:PSS-DMSO and WSCNT/MWCNT/PEI as p- and n-junctions show high power generation performance and cyclability. The output power density is up to 4.6 nW/cm² at ΔT = 42.0 K, matched to a suitable load. With its fast response and slow recovery, this TEG is expected to be used for human health monitoring and energy storage.     

Multi-walled carbon nanotubes (MWCNTs) and room temperature ionic liquids (RTILs) carbon paste Er(III) sensor based on a new derivative of dansyl chloride

Solution studies showed the strong interaction of [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (NSP) with Er(III) ions. NSP was used as a sensing material during construction of carbon paste Er(III) sensors. The electrodes were modified with 1-n-butyl-3-methylimidazolium tetrafluoroborate, [bmim]BF₄, as room temperature ionic liquid (RTIL) and multi-walled carbon nanotube (MWCNT). Potentiometric sensors constructed with [bmim]BF₄ and MWCNTs show better sensitivity, selectivity, response time, and response stability compared to Er(III) carbon paste sensors. The best performance for the modified sensor was obtained with an electrode composition of 20% [bmim]BF₄, 20% NSP, 45% graphite powder and 15% MWCNT. This particular sensor formulation exhibits a Nernstian response (19.8 ± 0.3 mV decade⁻¹) toward Er(III) ions in the range of 1.0 × 10⁻⁷ to 1.0 × 10⁻¹ mol L⁻¹ with a detection limit of 5.0 × 10⁻⁸ mol L⁻¹. The proposed modified Er(III) sensor can be used over the pH range from 3.5 to 9.0.     

Spontaneous polymerization of 2-ethynylpyridine with acylated multi-walled carbon nanotubes in supercritical carbon dioxide and their optical and electrochemical performance

A facile and green approach was proposed for the synthesis of multi-walled carbon nanotubes (MWCNTs) covalently functionalized with poly (2-ethynylpyridine) (MWCNT/P2EP) in supercritical carbon dioxide as a reaction medium. The oxidized MWCNTs were refluxed with thionyl chloride to yield COCl terminated MWCNTs, which were subsequently used as an initiator for the spontaneous polymerization of 2-ethynylpyridine to produce the MWCNT/P2EP hybrid. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction confirmed the formation of amorphous MWCNT/P2EP with a large surface area of 38 m² g⁻¹ and high nitrogen content (up to 8%). Microscopic results revealed that the MWCNTs were well embedded in the polymer matrix and the P2EP chains were wrapped around the carbon nanotube wall. The strong covalent coupling at the interface of the MWCNT/P2EP resulted in high electrical conductivity and enhanced thermal stability. Furthermore, the optical and electrochemical properties were investigated. The hybrid exhibited a photoluminescence peak at 510 nm corresponding to the photon energy of 2.44 eV.     

Simultaneously Improved Thermal Conductivity and Dielectric Properties of NBR Composites by Constructing 3D Hybrid Filler Networks

This work aims to address the heat accumulation issue in electronic components during high-frequency operation through the preparation of novel thermally conductive composites. First, polydopamine (PDA) and in-situ growth of silver (Ag) nanoparticles are applied for the surface modification of graphene oxide (GO) and carbon nanotube (CNT) to prepare pGO@Ag and pCNT@Ag hybrid filler, respectively. Then, nitrile butadiene rubber (NBR) is chosen as the polymeric matrix and simultaneously incorporated with both pGO@Ag and pCNT@Ag to prepare polymeric composites with excellent thermal conductivity (TC) and dielectric constant (ɛ_r). Due to the construction of 3D heat conduction networks by utilizing 2D pGO@Ag and 1D pCNT@Ag, the fabricated NBR composites achieved the maximum TC of 1.0112 W/(mK), which is 636% higher than that of neat NBR (0.1373 W (mK)⁻¹). At the filler loading of 9 vol%, the TC of pGO@Ag/pCNT@Ag/NBR composite is 152% that of GO/CNT/NBR composite (0.6660 W (mK)⁻¹). Moreover, due to electron polarization effect of GO and CNT and micro-capacitor effect of Ag nanoparticles, a large ɛ_r of 147.12 is attained at 10 Hz for NBR composites. Overall, the development of dielectric polymer materials with high TC is beneficial for enhancing the service life and safety stability of the electronic components.     

Anisotropic carbon nanotube papers fabricated from multiwalled carbon nanotube webs

We fabricated large-scale anisotropic carbon nanotube (CNT) paper sheets by stacking long-lasting multiwalled CNT (MWCNT) webs without using binder materials. The MWCNTs are highly aligned in the webs and they retain their alignment in the fabricated paper. Although MWCNTs are just connected by van der Waals force, tensile strength is as strong as 75.6 MPa. In addition, resistivity and thermal conductivity is as good as 2.5 × 10⁻³ Ω cm and 70 W/m K, respectively. The present high anisotropy ratios of 7.3 in resistivity and of 8.1 in thermal conductivity are due to the high alignment of the ultra-long MWCNTs which have lengths of millimeters. High-speed web drawing with a draw speed of over 10 m/s enables very rapid fabrication. The material properties of CNT structures can be measured by conventional methods for macroscopic samples rather than methods designed for nanomaterials. CNT web technology will enable CNTs to be used in new applications.