多壁碳纳米管-聚氨酯/聚丙烯复合材料导电网络结构的演变与性能调控

为研究多壁碳纳米管(MWCNTs)和热塑性弹性对MWCNTs-聚氨酯/聚丙烯(MWCNTs-TPU/PP)复合材料结晶性能、导电性能、拉伸性能及外场响应行为,通过溶液-熔融法制备了MWCNTs-TPU/PP复合材料。MWCNTs的引入能够提高MWCNTs-TPU/PP复合材料的导电性能和结晶性能,导电逾渗值质量分数约为1.9wt%,开始结晶温度从117.5℃提高到131.2℃。通过电阻仪和温控装置的联用在线表征了在不同热处理温度下导电网络的构建和破坏过程,随着热处理温度从110℃提高到175℃,MWCNTs-TPU/PP复合材料的导电性能和结晶度得到改善;TPU的引入能够显著降低MWCNTs-TPU/PP复合材料对温度的反应时间从约10 min缩短到约3 min,温度响应行为得到显著改善。通过拉伸数据分析表明,MWCNTs含量的增加能够提高MWCNTs-TPU/PP复合材料的拉伸强度和断裂伸长率,MWCNTs添加量为2.5wt%时,复合材料的拉伸强度从~35 MPa提高到~47 MPa;应变-电阻数据表明,TPU的引入能够改善MWCNTs-TPU/PP复合材料在循环拉伸过程中应变的可回复性和导电网络结构的稳定性。      

Effect of homogeneous Al(OH)3 covered MWCNT addition on the thermal conductivity of Al2O3/epoxy-terminated poly(dimethylsiloxane) composites

Aluminum hydroxide covered multiwalled carbon nanotubes (A-MWCNTs) were synthesized as a conducting additive to alumina-epoxy-terminated poly(dimethylsiloxane). The measured diffusivity and calculated conductivity exhibited dissimilar behavior between several Al₂O₃ concentrations as a function of A-MWCNT loading, which correlated with the interface density and interconnectivity of the structures. The fabricated heterostructured A-MWCNT did not have a significant effect on the thermal conductivity of the composite because of phonon scattering at the interface. A small amount of A-MWCNT was feasible for establishment of a heat conductive percolating network with the greatest enhancement of thermal conductivity and diffusivity at an A-MWCNT loading of 1.0 and 2.0 wt%. Continuously increasing thermal transport properties were observed with the 49.1 vol.% Al₂O₃ loading which derived from a lower interface density nanowire and polymer matrix with enhanced interconnectivity.     

Electrical conductivity enhancement of polymer/multiwalled carbon nanotube (MWCNT) composites by thermally-induced defunctionalization of MWCNTs

We report a thermally-induced increase of electrical conductivity of polymer/multiwalled carbon nanotube (MWCNT) composites using Diels-Alder-adduct-modified MWCNTs as additives. Thermal treatments of the composites induce the defunctionalization of the modified MWCNTs through retro-DA reaction, consequently to recover the electrical conductivity of MWCNTs and to increase the conductivity of PVDF/MWCNT composites. For the composites possessing 0.5 wt % of MWCNTs, thermal treatment increases the electrical conductivity from 2 × 10(-12) S cm(-1) to 4 × 10(-8) S cm(-1) and significantly reduces the value of percolation threshold. Meanwhile, the thermal treatment does not alter the mechanical properties of the composites.     

Fabrication and thermal conductivity of copper matrix composites reinforced with Mo2C or TiC coated graphite fibers

Graphite fiber reinforced Cu-based composites have good thermal conductivity, low coefficient of thermal expansion for heat sink applications. In these composites, the quality of interfacial bonding between the copper matrix and the graphite fibers has significant influence on the thermal properties of composites. In this study, two different carbide coatings (Mo₂C or TiC) were synthesized on graphite fiber to promote the interfacial bonding in composites. Fibers/Cu composites had been produced by spark plasma sintering process. The results showed that the densification, interfacial bonding and thermal conductivity of coated composites were improved distinctly compared to that of uncoated ones. The enhanced composites present 16–44% increase of thermal conductivity in X–Y plane. An original theoretical model was proposed to estimate the interface thermal resistance. The result showed that the interfacial thermal resistance was largely reduced by one order of magnitude with the introduction of carbide interlayer.     

Radiolytic synthesis of conducting polypyrrole/carbon nanotube composites

Conducting polypyrrole (PPy)/multi-wall carbon nanotube (MWNT) composites have been synthesized by the in situ gamma radiation-induced chemical polymerization method at room temperature. The resulting cable-like morphology of the composite (PPy–MWNT) structures was characterized by elemental analysis, Fourier transform infrared, field-emission scanning electron microscope, thermal gravimetric analysis, X-ray photoelectron spectroscopy, and transmission electron microscope. The standard four-point probe method was utilized for measuring the conductivity of the samples. We observed no significant chemical reaction between the polymer and carbon nanotube, which only showed that polypyrrole chains are tightly coated on to MWNT. The physical properties of the composites (PPy–MWNT) were measured and showed that the MWNT were modified by conducting polypyrrole with various properties enhanced.     

Determination of the thermal boundary resistance in the transport approach

We present a new theoretical determination of the thermal boundary resistance at a metal-liquid helium interface. The phonon temperature drops and heat flux densities at the interface are deduced from the numerical solution of the phonon Boltzmann equation inside the metal, with only electron-phonon scattering considered. A calculation of the thermal boundary resistance is performed and a comparison with the Khalatnikov theory is made ; the results differ considerably, the transport approach giving a far smaller resistance, though the phonon boundary conditions in our work are also determined by the classical acoustic theory.Laboratoire associé au Centre National de la Recherche Scientifique.     

Structure and properties of highly oriented polyoxymethylene/multi-walled carbon nanotube composites produced by hot stretching

Highly-oriented polyoxymethylene (POM)/multi-walled carbon nanotube (MWCNT) composites were fabricated through solid hot stretching technology. With the draw ratio as high as 900%, the oriented composites exhibited much improved thermal conductivity and mechanical properties along the stretching direction compared with that of the isotropic samples before drawing. The thermal conductivity of the composite with 11.6 vol.% MWCNTs can reach as high as 1.2 W/m K after drawing. Microstructure observation demonstrated that the POM matrix had an ordered fibrillar bundle structure and MWCNTs in the composite tended to align parallel to the stretching direction. Wide-angle X-ray diffraction results showed that the crystal axis of the POM matrix was preferentially oriented perpendicular to the draw direction, while MWCNTs were preferentially oriented parallel to the draw direction. The strong interaction between the POM matrix and the MWCNTs hindered the orientation movement of molecules of POM, but induced the orientation movement of MWCNTs.     

Thermal conductivity of polymer composites based on the length of multi-walled carbon nanotubes

The anisotropic development of thermal conductivity in polymer composites was evaluated by measuring the isotropic, in-plane and through-plane thermal conductivities of composites containing length-adjusted short and long multi-walled CNTs (MWCNTs). The thermal conductivities of the composites were relatively low irrespective of the MWCNT length due to their high contact resistance and high interfacial resistance to polymer resins, considering the high thermal conductivity of MWCNTs. The isotropic and in-plane thermal conductivities of long-MWCNT-based composites were higher than those of short-MWCNT-based ones and the trend can accurately be calculated using the modified Mori-Tanaka theory. The in-plane thermal conductivity of composites with 2 wt% long MWCNTs was increased to 1.27 W/m·K. The length of MWCNTs in polymer composites is an important physical factor in determining the anisotropic thermal conductivity and must be considered for theoretical simulations. The thermal conductivity of MWCNT polymer composites can be effectively controlled in the processing direction by adjusting the length of the MWCNT filler.     

Highly enhanced thermal conductivity of thermoplastic nanocomposites with a low mass fraction of MWCNTs by a facilitated latex approach

The construction of a three-dimensional (3D) compactly interconnected carbon nanotube (CNT) network could offer a substantial increase in the thermal conductivity of the polymeric nanocomposite. In order to achieve desirable 3D conductive architectures in the polymeric matrix, a facilitated latex technique was employed to coat multi-walled CNT (MWCNT) onto micro-sized polymeric powders. The microstructure and rheological characterization study were conducted to evaluate the internal distribution of MWCNTs within the polymeric matrices. The crystallinity of the polymer, the kinetics of crystallization, and the influence of surface functionalization on thermal conductivity were also investigated. The selected steroid-based surfactant (sodium cholate) could improve the interfacial coupling of CNT-CNT and CNT-polymer to reduce the interfacial thermal resistances. Meanwhile, the 3D architecture of MWCNTs could provide a phonon transport pathway and accelerate the recrystallization process of semi-crystalline polymers. MWCNTs and the surfactant had a synergic effect on the enhancement of thermal conductivity of the nanocomposites.     

Thermal conductivity of ge and ge-si core-shell nanowires in the phonon confinement regime

Heterostructure core-shell semiconductor nanowires (NWs) have attracted tremendous interest recently due to their remarkable properties and potential applications as building blocks for nanodevices. Among their unique traits, thermal properties would play a significant role in thermal management of future heterostructure NW-based nanoelectronics, nanophotonics, and energy conversion devices, yet have been explored much less than others. Similar to their electronic counterparts, phonon spectrum and thermal transport properties could be modified by confinement effects and the acoustic mismatch at the core-shell interface in small diameter NWs (<20 nm). However, fundamental thermal measurement on thin core shell NWs has been challenging due to their small size and their expected low thermal conductivity (κ). Herein, we have developed an experimental technique with drastically improved sensitivity capable of measuring thermal conductance values down to ～10 pW/K. Thermal conductivities of Ge and Ge-Si core-shell NWs with diameters less than 20 nm have been measured. Comparing the experimental data with Boltzmann transport models reveals that thermal conductivities of the sub-20 nm diameter NWs are further suppressed by the phonon confinement effect beyond the diffusive boundary scattering limit. Interestingly, core-shell NWs exhibit different temperature dependence in κ and show a lower κ from 300 to 388 K compared to Ge NWs, indicating the important effect of the core-shell interface on phonon transport, consistent with recent molecular dynamics studies. Our results could open up applications of Ge-Si core shell NWs for nanostructured thermoelectrics, as well as a new realm of tuning thermal conductivity by "phononic engineering".     

Factors affecting the magnitudes and anisotropies of the thermal and electrical conductivities of poly(l-lactic) acid composites with carbon fibers of various sizes

Investigation of the thermal and electrical conductivities of poly(l-lactic acid) composites containing carbon fibers (CFs) of various sizes has revealed that the thermal conductivity depends largely on the length of the CFs in the composites and that the electrical conductivity depends largely on the aspect ratio of the CFs. These different dependencies are due to the effect of the number of interfaces between the CFs in a percolation network formed in the composites, where electron transport is enhanced but phonon thermal conduction is limited by phonon scattering at the interfaces between the CFs. The anisotropy of each conductivity is also influenced by the length of the CFs, which could determine the alignment of the CFs in the molded composites.     

Effects of carbon nanotubes and carbon fiber reinforcements on thermal conductivity and ablation properties of carbon/phenolic composites

The ablation properties and thermal conductivity of carbon nanotube (CNT) and carbon fiber (CF)/phenolic composites were evaluated for different filler types and structures. It was found that the mechanical and thermal properties of phenolic-polymer matrix composites were improved significantly by the addition of carbon materials as reinforcement. The concentrations of CF and CNT reinforcing materials used in this study were 30 vol% and 0.5 wt%, respectively. The thermal conductivity and thermal diffusion of the different composites were observed during ablation testing, using an oxygen–kerosene (1:1) flame torch. The thermal conductivity of CF mat/phenolic composites was higher than that of random CF/phenolic composites. Both CF mat and CNT/phenolic composites exhibited much better thermal conductivity and ablation properties than did neat phenolic resin. The more conductive carbon materials significantly enhanced the heat conduction and dissipation from the flame location, thereby minimizing local thermal damage.     

Carbon nanotubes/cyanate ester composites with low percolation threshold,high dielectric constant and outstanding thermal property

A novel kind of multi-walled carbon nanotubes (MWCNTs)/cyanate ester (CE) composites with low percolation threshold, high dielectric constant and excellent thermal property was developed. In order to investigate the effect of the surface nature of MWCNTs on the morphology and properties of the composites, MWCNTs and surface treated carbon nanotubes (MWCNTs–OH) were used to prepare two sorts of composites, coded as M/CE and M–OH/CE, respectively. Results show that increasing the content of MWCNTs or MWCNTs–OH, the dielectric constant of both kinds of composites initially increases until reaches the maximum value, and then decreases. In addition, when the percolation occurs, dielectric constant and loss of both kinds of composites decrease quickly with the increase of the tested frequency. The addition of MWCNTs into CE decreases the glass transition temperature and thermal stability, while the incorporation of MWCNTs–OH significantly improves the thermal stability of CE resin.     

Probing Anisotropic Thermal Conductivity of Transition Metal Dichalcogenides MX2 (M = Mo,W and X = S,Se) using Time‐Domain Thermoreflectance

Transition metal dichalcogenides (TMDs) are a group of layered 2D semiconductors that have shown many intriguing electrical and optical properties. However, the thermal transport properties in TMDs are not well understood due to the challenges in characterizing anisotropic thermal conductivity. Here, a variable‐spot‐size time‐domain thermoreflectance approach is developed to simultaneously measure both the in‐plane and the through‐plane thermal conductivity of four kinds of layered TMDs (MoS₂, WS₂, MoSe₂, and WSe₂) over a wide temperature range, 80–300 K. Interestingly, it is found that both the through‐plane thermal conductivity and the Al/TMD interface conductance depend on the modulation frequency of the pump beam for all these four compounds. The frequency‐dependent thermal properties are attributed to the nonequilibrium thermal resistance between the different groups of phonons in the substrate. A two‐channel thermal model is used to analyze the nonequilibrium phonon transport and to derive the intrinsic thermal conductivity at the thermal equilibrium limit. The measurements of the thermal conductivities of bulk TMDs serve as an important benchmark for understanding the thermal conductivity of single‐ and few‐layer TMDs.     

Enhanced crack detection sensitivity of carbon fiber composites by carbon nanotubes directly grown on carbon fibers

The ability of highly conductive hybrid carbon–fiber/carbon nanotube loaded epoxy composites to sense matrix cracking damage in situ is demonstrated. Multi-walled carbon-nanotubes (MWCNTs) are grown perpendicular to and on the surface of a woven carbon–fiber fabric using a chemical vapor deposition process. An increase in sensitivity of resistance change under interlaminar fracture is shown through a series of double cantilever beam (DCB) tests on samples prepared with MWCNTs grown on both sides of carbon–fiber fabric lamina placed at the top and bottom surfaces of an 8-layer test panel whereas samples with MWCNTs inside the samples did not show much increase in sensitivity of resistance change compared with the baseline samples without MWCNTs. The results suggest that the addition of surface positioned hierarchical carbon-nanotube lamina on composite structures has the potential for autonomic sensing of internal matrix damage.     

PAN-based carbon fibers/PMMA composites: thermal, dielectric, and DC electrical properties

The study deals with thermal, dielectric, and DC electrical properties of polyacrylonitrile (PAN)-based carbon fibers/poly(methyl methacrylate) composites. The polymer composites contain 0, 5, 10, 20 and 30 wt.% PAN-based carbon fibers. The thermal conductivity was studied as a function of filler content and temperature. It was found that the thermal conductivity is enhanced by addition of carbon fibers concentration and temperature. The dielectric properties were determined using impedance measurements. The results showed that the dielectric constant and dielectric loss are decreased with frequency, and increased with both temperature and fibers content. The DC electrical conductivity, temperature coefficient of resistance, and activation energy were studied as a function of fibers concentration in the temperature ranges 30–110?°C. It was found that the composites exhibit negative temperature coefficient of resistivity and enhancement of electrical conductivity with increasing temperature and carbon fibers concentration. The observed increase in the DC conductivity was explained according to the approach of conductive paths and connections between the carbon fibers.     

Effects of poly(oxyethylene)-block structure in polyetheramines on the modified carbon nanotube/poly(lactic acid) composites

The hybrids of multi-walled carbon nanotube and poly(lactic acid) (MWCNT/PLA) were prepared by a melt-blending method. In order to enhance the compatibility between the PLA and MWCNTs, the surface of the MWCNTs was covalently modified by Jeffamine® polyetheramines by functionalizing MWCNTs with carboxylic groups. Different molecular weights and hydrophilicity of the polyethermaines were grafted onto MWCNTs with the assistance of a dehydrating agent. The results showed that low-molecular-weight Jeffamine® polyetheramine modified MWCNTs can effectively improve the thermal properties of PLA composites. On the other hand, high-molecular-weight and poly(oxyethylene)-segmented polyetheramine could render the modified MWCNTs of well dispersion in PLA, and consequently affecting the improvements of mechanical properties and conductivity of composite materials. With the addition of 3.0 wt% MWCNTs, the increment of E′ of the composite at 40 °C was 79%. For conductivity, the surface resistivity decreased from 1.27 × 10¹² Ω/sq for neat PLA to 8.30 × 10⁻³ Ω/sq for the composites.     

Enhancement of thermal and mechanical properties of flexible graphene oxide/carbon nanotube hybrid films though direct covalent bonding

The thermal conductivity and mechanical properties of graphene oxide/multiwalled carbon nanotube (GO/MWCNT) hybrid films with and without covalent bonding were examined. Chlorinated GO and amino-functionalized MWCNT were bonded covalently to fabricate chemically bonded GO/MWCNT hybrid films. Mixtures of surface-modified GO and MWCNT were filtered and then subjected to hot-pressing to fabricate stacked films. Examination of these chemically bonded hybrid films revealed higher thermal conductivity than in physically bonded hybrid films, because of the synergetic interaction of functional groups in GO and MWCNT in the films. However, the addition of excess MWCNT to the films led to an increased phonon scattering density and a decreased thermal conductivity. The hybrid films fabricated by the optimized process endured about 20000 bending cycles without rupturing or losing their thermal conductivity. The mechanical properties showed enhanced performance after increased MWCNT loading at elevated temperature due to the reinforcement effect of the MWCNT between GO layers.     

Measurement of the Intrinsic Thermal Conductivity of a Multiwalled Carbon Nanotube and Its Contact Thermal Resistance with the Substrate

The intrinsic thermal conductivity of an individual carbon nanotube and its contact thermal resistance with the heat source/sink can be extracted simultaneously through multiple measurements with different lengths of the tube between the heat source and the heat sink. Experimental results on a 66‐nm‐diameter multiwalled carbon nanotube show that above 100 K, contact thermal resistance can contribute up to 50% of the total measured thermal resistance; therefore, the intrinsic thermal conductivity of the nanotube can be significantly higher than the effective thermal conductivity derived from a single measurement without eliminating the contact thermal resistance. At 300 K, the contact thermal resistance between the tube and the substrate for a unit area is 2.2 × 10^?8 m² K W^?1, which is on the lower end among several published data. Results also indicate that for nanotubes of relatively high thermal conductance, electron‐beam‐induced gold deposition at the tube–substrate contacts may not reduce the contact thermal resistance to a negligible level. These results provide insights into the long‐lasting issue of the contact thermal resistance in nanotube/nanowire thermal conductity measurements and have important implications for further understanding thermal transport through carbon nanotubes and using carbon nanotube arrays as thermal interface materials.     

Enhancement of tensile and thermal properties of epoxy nanocomposites through chemical hybridization of carbon nanotubes and alumina

This paper presents the properties of epoxy nanocomposites, prepared using a synthesized hybrid carbon nanotube–alumina (CNT–Al₂O₃) filler, via chemical vapour deposition and a physically mixed CNT–Al₂O₃ filler, at various filler loadings (i.e., 1–5%). The tensile and thermal properties of both nanocomposites were investigated at different weight percentages of filler loading. The CNT–Al₂O₃ hybrid epoxy composites showed higher tensile and thermal properties than the CNT–Al₂O₃ physically mixed epoxy composites. This increase was associated with the homogenous dispersion of CNT–Al₂O₃ particle filler; as observed under a field emission scanning electron microscope. It was demonstrated that the CNT–Al₂O₃ hybrid epoxy composites are capable of increasing tensile strength by up to 30%, giving a tensile modulus of 39%, thermal conductivity of 20%, and a glass transition temperature value of 25%, when compared to a neat epoxy composite.