Enhancing the thermal conductivity of polyacrylonitrile- and pitch-based carbon fibers by grafting carbon nanotubes on them

The thermal conductivities of ultrahigh tensile strength polyacrylonitrile (PAN)-based (T1000GB) and ultrahigh modulus pitch-based (K13D) carbon fibers with carbon nanotubes (CNTs) grown on them using chemical vapor deposition were measured using a thermal diffusivity meter. The thermal conductivities of the resulting hybrid materials were calculated to be 18.6 ± 1.7 and 965.6 ± 30.0 W/m K for T1000GB and K13D, respectively, while the respective original conductivities were 12.6 ± 1.0 and 745.5 ± 16.0 W/m K. The results clearly show that the CNTs grafting improves the thermal conductivities of both types of fiber.     

Effect of functionalized carbon nanotubes on the thermal conductivity of epoxy composites

Direct functionalized carbon nanotubes (CNTs) were utilized to form the heat flow network for epoxy composites through covalent integration. A method of preparing a fully heat flow network between benzenetricarboxylic acid grafted multi-walled carbon nanotubes (BTC-MWCNTs) and epoxy matrix is described. A Friedel-Crafts modification was used to functionalize MWCNTs effectively and without damaging the MWCNT surface. Raman spectra, X-ray photoelectron spectra and thermogravimetric analysis reveal the characteristics of functionalized MWCNTs. The scanning electron microscope images of the fracture surfaces of the epoxy matrix showed BTC-MWCNTs exhibited higher solubility and compatibility than pristine-MWCNTs. The MWCNTs/epoxy composites were prepared by mixing BTC-MWCNTs and epoxy resin in tetrahydrofuran, followed by a cross-linking reaction with a curing agent. The BTC was grafted onto the MWCNTs, creating a rigid covalent bond between MWCNTs and epoxy resin and forming an effective network for heat flow. The effect of functionalized MWCNTs on the formation of the heat flow network and thermal conductivity was also investigated. The thermal conductivity of composites exhibits a significant improvement from 0.13 to 0.96 W/m K (an increase of 684%) with the addition of a small quantity (1-5 vol%) of BTC-MWCNTs.     

Anisotropic thermal conductivity of polypropylene composites filled with carbon fibers and multiwall carbon nanotubes

Polypropylene‐based composites filled with carbon fibers and multiwall carbon nanotubes were produced by coagulation precipitation technique. Composite articles were produced by conventional injection molding technique. It was shown that the addition of carbon nanotubes (10% of total amount of carbon fibers) results in significantly increased anisotropic thermal conductivity of the composite due to formation of thermal conductive bridges between carbon fibers, which are oriented during molding. The addition of CNTs has a significant effect with more than a 50–70% increase of both the axial and transverse thermal conductivity of the composite. Produced composites were used for injection molding of polymeric radiators for LED lamps, showing sufficient heat dissipation efficiency allowing using them for industrial application in the field. POLYM. COMPOS., 36:1951–1957, 2015. © 2014 Society of Plastics Engineer     

Influence of carbon nanotubes on thermal and electrical conductivity of zirconia-based composite

Carbon nanotubes (CNTs) are widely used in ceramic-matrix composites (CMC) as a filler. An individual carbon nanotube exhibits extremely high thermal conductivity, however, the influence of CNTs on the thermal conductivity of CMCs is moderate. In contrast, even a small quantity of CNTs significantly increases the electrical conductivity of CMCs. The present paper studies this contradictory influence for ZrO₂-CNTs composites with 3, 5, 10 and 20 vol% multi-wall carbon nanotubes (MWCNTs). Their thermal and electrical conductivity was studied by the laser flash method and electrochemical impedance spectroscopy. The analysis reveals that the moderate influence of MWCNTs on the thermal conductivity of composites originates from the similar thermal conductivity of MWCNTs in a bundle and zirconia. On the other hand, the substantial difference in the electrical conductivity of MWCNTs and zirconia leads to an exponential increase in the electrical conductivity of the ZrO₂-CNTs composite even with small additions of nanotubes.     

Anchoring carbon nanotubes to boron nitride microrods for enhancing the thermal conductivity of polystyrene

The development of high-performance thermally conductive fillers is crucial for the thermal management of polymer-based composites. Herein, a facile precursor pyrolysis strategy was adopted to fabricate boron nitride@multiwalled carbon nanotubes (BN@MWCNTs) fillers, wherein uniformly distributed MWCNTs were firmly anchored on BN microrods. Benefiting from the unique structure, the BN@MWCNTs act as fillers in the design of polystyrene (PS)/BN@MWCNTs composites via in situ polymerization. As a result, a 7.74-fold higher thermal conductivity (TC) (9.55 W/m·K) was achieved for the 10 wt% BN@MWCNTs, as compared to native PS/BN/MWCNTs prepared by the conventional melt-mixing method. More importantly, the PS/BN@MWCNTs composites exhibited satisfactory electrical insulation owing to the isolation effect of BN. Overall, this work provides a promising frontier for the design of polymer-based thermally conducting materials for applications in thermal management.     

An experimental study on thermal conductivity and viscosity of nanofluids containing carbon nanotubes

Recently, there has been considerable interest in the use of nanofluids for enhancing thermal performance. It has been shown that carbon nanotubes (CNTs) are capable of enhancing the thermal performance of conventional working liquids. Although much work has been devoted on the impact of CNT concentrations on the thermo-physical properties of nanofluids, the effects of preparation methods on the stability, thermal conductivity and viscosity of CNT suspensions are not well understood. This study is focused on providing experimental data on the effects of ultrasonication, temperature and surfactant on the thermo-physical properties of multi-walled carbon nanotube (MWCNT) nanofluids. Three types of surfactants were used in the experiments, namely, gum arabic (GA), sodium dodecylbenzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS). The thermal conductivity and viscosity of the nanofluid suspensions were measured at various temperatures. The results showed that the use of GA in the nanofluid leads to superior thermal conductivity compared to the use of SDBS and SDS. With distilled water as the base liquid, the samples were prepared with 0.5 wt.% MWCNTs and 0.25% GA and sonicated at various times. The results showed that the sonication time influences the thermal conductivity, viscosity and dispersion of nanofluids. The thermal conductivity of nanofluids was typically enhanced with an increase in temperature and sonication time. In the present study, the maximum thermal conductivity enhancement was found to be 22.31% (the ratio of 1.22) at temperature of 45°C and sonication time of 40 min. The viscosity of nanofluids exhibited non-Newtonian shear-thinning behaviour. It was found that the viscosity of MWCNT nanofluids increases to a maximum value at a sonication time of 7 min and subsequently decreases with a further increase in sonication time. The presented data clearly indicated that the viscosity and thermal conductivity of nanofluids are influenced by the sonication time. Image analysis was carried out using TEM in order to observe the dispersion characteristics of all samples. The findings revealed that the CNT agglomerates breakup with increasing sonication time. At high sonication times, all agglomerates disappear and the CNTs are fragmented and their mean length decreases.     

Enhanced thermal conductivity in Si3N4 ceramic by addition of a small amount of carbon

In order to fabricate Si₃N₄ ceramic with enhanced thermal conductivity, 93 mol%α-Si₃N₄-2 mol%Yb₂O₃-5 mol%MgO powder mixture was doped with 5 mol% carbon, and sintered firstly at 1500 °C for 8 h and subsequently at 1900 °C for 12 h under 1 MPa nitrogen pressure. During the first-step sintering, the carbothermal reduction process significantly reduced the oxygen content and increased the N/O ratio of intergranular secondary phase, resulting in the precipitation of Yb₂Si₄O₇N₂ crystalline phase, higher β-Si₃N₄ content and larger rod-like β-Si₃N₄ grains in the semi-finished Si₃N₄ sample. After the second-step sintering, the final dense Si₃N₄ product acquired coarser elongated grains, lower lattice oxygen content, tighter Si₃N₄-Si₃N₄ interfaces and more devitrified intergranular phase due to the further carbothermal reduction of oxynitride secondary phase. Consequently, the addition of carbon enabled Si₃N₄ ceramic to gain a significant increase of ∼25.5% in thermal conductivity from 102 to 128 W∙m⁻¹ K⁻¹.     

Improving thermal conductivity while retaining high electrical resistivity of epoxy composites by incorporating silica-coated multi-walled carbon nanotubes

Silica-coated multi-walled carbon nanotubes (MWCNT@SiO₂) were synthesized by a sol–gel method and then incorporated into an epoxy matrix. The less stiff silica intermediate shell on the MWCNTs not only alleviates the modulus mismatch between the stiff MWCNTs and the soft epoxy, but also improves the interaction between them. The thermal conductivities of the epoxy/MWCNT@SiO₂ composites increase by 51% and 67% at low filler loadings of 0.5 wt.% and 1 wt.%, respectively. At the same time, the silica shell retains the high electrical resistivity of these composites.     

用激光导热仪测定炭黑填充橡胶的导热系数

用激光导热仪测定了5种填充不同量炭黑N 220的胶料在30～140℃时的导热系数,分析了导热系数随温度和炭黑填充量变化的关系,发现胶料的导热系数均随着温度的升高呈线性增大趋势,随炭黑填充量的增加也逐渐增大.将导热系数与温度和炭黑填充量进行了关联,得到了线性回归方程式,进而确立了适合于计算不同温度和不同炭黑N 220填充量胶料导热系数的关联方程A=0.133 77 2.008 74×10-4t 0.001 64 X.将用该方程计算的结果与实验值进行比较,60个数据点的平均相对误差仪为0.93%.     

焙烧炭砖孔结构和热导率与硅粉加入量的关系

以电煅无烟煤(5～3、3～1、≤1及≤0.088 mm,w(固定碳)=95.17%,w(挥发分)=0.37%,w(灰分)=4.14%)、鳞片石墨(≤0.147和≤0.074 mm,w(固定碳)=96.5%)、棕刚玉粉(≤0.074 mm,w(Al2O3>)=93.5%,w(TiO2)=2.3%)和硅粉(≤0.043 mm,w(Si)=96.37%)为原料,固定骨料与细粉的质量比为60∶40,细粉中硅粉和电煅无烟煤细粉总量固定为14%(质量分数),改变硅粉加入量(质量分数)分别为3%、5%、8%、10%、14%,以液态热塑性酚醛树脂为结合剂,乌洛托品作固化剂制成炭砖,于1 400℃3 h埋炭焙烧,借助于X射线衍射仪、压汞仪、激光导热仪、扫描电子显微镜和能谱分析仪等测试手段,研究了不同硅粉加入量的焙烧炭砖的孔结构及热导率.结果表明:因炭砖焙烧过程单质硅原位反应形成β-SiC、Si2N2O和石英等陶瓷相,填充、阻隔或封闭了气孔,故硅粉加入量控制着试样内部的气孔分布、平均孔径和孔径<1 μm气孔的孔容积率;受材料组成和孔结构变化影响,炭砖的热导率也发生相应变化;随硅粉加入量增加,试样中孔径分布范围由宽变窄,平均孔径逐渐减小,<1 μm孔的容积率增加,气孔呈微孔化趋势;当试样中硅粉加入量超过8%时,气孔的平均孔径<0.3 μm,<1 μm孔容积率超过70%,试样的热导率急剧下降.     

Electrical conductivity of well-exfoliated single-walled carbon nanotubes

Aqueous suspensions of single-walled carbon nanotubes (SWCNTs) with controlled degree of exfoliation were used to prepare conductive thin films. Controlled exfoliation was achieved by physical separation of SWCNT bundles using our previously established nanoplatelet-dispersion method. Thin film networks of individual SWCNTs produced with this approach exhibit universal conduction behavior indicative of an isotropic network of random resistors with nearly monodisperse bond conductance distribution. Networks made of partially exfoliated SWCNTs experience a significant shift in percolation threshold because of effective local alignment of individual SWCNTs into bundles. Bundling increases the conductivity of the SWCNTs at higher concentration because of low contact resistance electron transport between metallic SWCNTs. The most significant impact of bundling is the development of non-universal electrical scaling. These findings suggest that while individually exfoliated SWCNTs should be of substantial importance for electrical devices requiring small increases in electrical conductivity at low concentration, adequate control of bundling may enable or enhance performance for applications requiring higher conductivity.     

Ambient effects on the electrical conductivity of carbon nanotubes

We show that the electrical conductivity of single walled carbon nanotubes (SWCNT) networks is affected by oxygen and air humidity under ambient conditions by more than a magnitude. Later, we intentionally modified the electrical conductivity by functionalization with iodine and investigated the changes in the band structure by optical absorption spectroscopy.Measuring in parallel the tubes electrical conductivity and optical absorption spectra, we found that conduction mechanism in SWCNT is comparable to that of intrinsically conducting polymers. We identified, in analogy to conducting polymers, in the infrared spectra a new absorption band which is responsible for the increased conductivity, leading to a closing gap in semiconducting SWCNT.We could show that by different functionalizations of the same SWCNT starting material the properties like conductivity can be dramatically changed, leading to different imaginable applications. We investigated here, an ultraviolet sensor with weakly modified SWCNT.     

Functionalization of multiwalled carbon nanotubes by reversible addition fragmentation chain-transfer polymerization

In this study, a new way was used to chemically synthesize polymer-connected MWNT nanocomposites. Reversible addition fragmentation chain-transfer (RAFT) agent was successfully grafted onto the surface of multiwalled carbon nanotubes (MWNTs). Polystyrene (PS) chains were successfully grafted from the surface of MWNTs via RAFT process by using RAFT agent immobilized on MWNTs. FTIR, XPS and TGA were used to determine chemical structure and the grafted PS quantities of the resulting products. TEM images of the samples provide direct evidence for the formation of a core-shell nanostructure, i.e. the MWNT coated with polymer layer and the solubility be improved.     

Oxidation of multiwalled carbon nanotubes by nitric acid

The oxidation of MWCNTs in nitric acid was monitored using sample weight, Raman spectrum, solubility, morphology and alignment. The influence of the acid concentration, temperature and oxidation duration on the monitored parameters was assessed. A new method, based on optical microscopy is proposed for the determination of MWCNT solubility in concentrated aqueous-suspensions. The investigations revealed that the solubility is determined not only by the functional groups on the MWCNT, but also by the functionalized amorphous carbon generated during the digestion of the nanotubes. High solubility (20–40 mg/ml) is obtained only after prolonged exposure (24–48 h) in concentrated acid (60%). But in these conditions 60–90% of the MWCNTs are lost. Furthermore the MWCNTs are strongly fragmented and covered by amorphous carbon after 48 h of oxidation. It was found that the solubility correlates well with the area ratio of the G and D bands from the Raman spectrum. SEM examination of the MWCNT films showed extended alignment after 24 h of oxidation.     

Effects of the electrical conductivity and orientation of silicon substrate on the synthesis of multi-walled carbon nanotubes by thermal chemical vapor deposition

We studied the effects of the electrical conductivity and orientation of silicon substrate on both catalytic Fe thin film and the structure and morphology of multi-walled carbon nanotube (MWNT) grown by low-pressure chemical vapor deposition. Both p-type Si(100) and Si(111) substrates with three different doping concentrations (high, low, undoped) were used to evaluate the formation of catalytic nanoparticles and the growth of MWNTs. The morphology of catalytic nanoparticles such as size and density was characterized by field-emission scanning electron microscopy, Cs-corrected energy-filtered transmission electron microscopy, and X-ray photoelectron spectroscopy. Structural characteristics of MWNTs grown on different combinations of silicon substrate orientation and electrical conductivities (σ) were also systematically analyzed. Based on the experimental results, growth modes of MWNTs could be controlled by choosing an appropriate combination of σ and orientation of Si substrates.     

Increasing the semiconducting fraction in ensembles of single-walled carbon nanotubes

The carbon source and growth conditions for single-walled carbon nanotube (SWCNT) growth in hot-wall chemical vapor deposition affect the chirality of the SWCNT ensemble produced. Raman spectroscopy elucidates the trends of the SWCNT semiconducting percentage grown under different conditions. Field-effect transistors using few SWCNTs per transistor were fabricated to allow for a semiconducting SWCNT enumeration and to confirm these trends. The semiconducting SWCNT percent in isopropanol-based devices peaked at 800 °C with 85% semiconducting. 2-Butanol-based and methane-based devices were 70% and 32% semiconducting, respectively.     

Electrical conductivity and thermal stability of polypropylene containing well-dispersed multi-walled carbon nanotubes disentangled with exfoliated nanoplatelets

The morphology, crystallization behavior, electrical conductivity, and thermal stability of polypropylene (PP) modified with disentangled multi-walled carbon nanotubes (MWCNTs) is reported. Slightly oxidized MWCNT clusters were disentangled in solution by mild sonication in the presence of exfoliated α-zirconium phosphate nanoplatelets. The disentangled MWCNTs were isolated using acid-induced coagulation to precipitate the nanoplatelets, and were subsequently reacted with octadecylamine. The recovered functionalized MWCNTs (F-MWCNTs) are disentangled and easily dispersed in a commercial PP matrix, and serve as more efficient nucleating agents than the untreated MWCNTs. The PP/F-MWCNT composites exhibit an extremely low percolation-like transition in electrical conductivity, which is attributed to the preservation of a random dispersion of disentangled F-MWCNTs upon cooling from the melt. The thermal stability of PP in air is also substantially enhanced at loadings below the percolation threshold due to the tremendous interfacial area between the polymer chains and the free radical scavenging F-MWCNTs. The present approach provides an efficient and potentially scalable route for commercial production of conductive semi-crystalline thermoplastics. The method may be adapted to uniformly disperse MWCNTs in other polymer matrices by appropriate selection of surface functionality.     

Study of the synergistic effect of boron nitride and carbon nanotubes in the improvement of thermal conductivity of epoxy composites

The enhancement of the thermal conductivity, keeping the electrical insulation, of epoxy thermosets through the addition of pristine and oxidized carbon nanotubes (CNTs) and microplatelets of boron nitride (BN) was studied. Two different epoxy resins were selected: a cycloaliphatic (ECC) epoxy resin and a glycidylic (DGEBA) epoxy resin. The characteristics of the composites prepared were evaluated and compared in terms of thermal, thermomechanical, rheological and electrical properties. Two different dispersion methods were used in the addition of pristine and oxidized CNTs depending on the type of epoxy resin used. Slight changes in the kinetics of the curing reaction were observed in the presence of the fillers. The addition of pristine CNTs led to a greater enhancement of the mechanical properties of the ECC composite whereas the oxidized CNTs presented a greater effect in the DGEBA matrix. The addition of CNTs alone led to a marked decrease of the electrical resistivity of the composites. Nevertheless, in the presence of BN, which is an electrically insulating material, it was possible to increase the proportion of pristine CNTs to 0.25 wt% in the formulation without deterioration of the electrical resistivity. A small but significant synergic effect was determined when both fillers were added together. Improvements of about 750% and 400% in thermal conductivity were obtained in comparison to the neat epoxy matrix for the ECC and DGEBA composites, respectively. © 2019 Society of Chemical Industry     

Increasing the thermoelectric power generated by composite films using chemically functionalized single-walled carbon nanotubes

We prepared and characterized flexible thermoelectric (TE) materials based on thin films of single-walled carbon nanotube (SWCNT) composites with polyvinylalcohol. While pristine SWCNTs incorporated in a polymer matrix generated a p-type TE material, chemical functionalization of SWCNTs by using polyethyleneimine produced an n-type TE material. TE modules made of both p- and n-type composite were fabricated to demonstrate TE voltage and power generation. A single p–n junction made of two composite strips containing 20 wt.% of SWCNTs generated a high TE voltage of 92 μV per 1 K temperature gradient (ΔT). By combining five electrically connected p–n junctions an output voltage of 25 mV was obtained upon the applying ΔT = 50 K. Furthermore, this module generated a power of 4.5 nW when a load resistance matched the internal module resistance of 30 kΩ. These promising results show the potential of TE energy conversion provided by the SWCNT composite films connected in scalable modules for applications that require light weight and mechanical flexibility.