Percolation model of reinforcement efficiency for carbon nanotubes dispersed in thermoplastics

Considerable experimental work on carbon nanotube-reinforced composites has shown that the reinforcement efficiency of carbon nanotubes (CNTs) becomes lower than the theoretical expectation when CNT content reaches a critical value. This critical volume fraction (percolation threshold) is considered related to the formation of percolating network. In this work, a percolation model is proposed to describe the observed sharp decrease in the reinforcement efficiency of multiwalled CNTs (MWCNTs) dispersed in thermoplastics when the CNT content exceeds the percolation threshold. The percolation threshold is estimated via a numerical simulation of randomly curved CNTs according to the statistics on geometrical features of real CNTs. The percolation model, integrated into the Halpin–Tsai equations, is verified using the experimental data of various thermoplastic composites reinforced with MWCNTs. The developed mechanical model achieves a good agreement with the measured moduli of nanocomposites, and demonstrates an excellent prediction capability over a wide range of CNT content.     

CNT-CF水泥基材料传感特性研究

将碳纳米管与碳纤维混杂掺入水泥基材料制备碳纳米管-碳纤维(CNT-CF)水泥基材料,并研究其温敏和压敏传感特性。结果表明,当碳纳米管掺量较低时(0.5%),碳纳米管能有效提高CNT-CF水泥基材料的温敏和压敏特性;CNT-CF水泥基材料的活化能、温敏系数以及压敏传感线性程度和重复度均随碳纳米管掺量增加而提高;随着碳纳米管掺量继续增加,CNT-CF水泥基材料各项传感性能均有所下降。碳纳米管掺量为0.5%的试样传感特性最优。利用CNT-CF水泥基材料开发水泥基温敏、压敏传感器有一定应用前景。     

Mechanical and electrical property improvement in CNT/Nylon composites through drawing and stretching

The excellent mechanical properties of carbon nanotubes (CNTs) make them the ideal reinforcements for high performance composites. The misalignment and waviness of CNTs within composites are two major issues that limit the reinforcing efficiency. We report an effective method to increase the strength and stiffness of high volume fraction, aligned CNT composites by reducing CNT waviness using a drawing and stretching approach. Stretching the composites after fabrication improved the ultimate strength by 50%, 150%, and 190% corresponding to stretch ratios of 2%, 4% and 7%, respectively. Improvement of the electrical conductivities exhibited a similar trend. These results demonstrate the importance of straightening and aligning CNTs in improving the composite strength and electrical conductivity.     

Combination effect of physical drying with chemical characteristic of carbon nanotubes on through-thickness properties of carbon fiber/epoxy composites

The present work studied the combination effect of physical drying with chemical modification of carbon nanotubes (CNTs) on some through-thickness properties of carbon fiber/epoxy composites. Different drying methods of heat drying and freeze drying were utilized to affect CNT organization form in carbon fiber/CNTs preforms and composites: The adoption of heat-drying method made CNTs more inclined to form aggregates accompanied with randomly scattered CNTs, while continuous CNT networks could always be assembled when freeze drying method was employed. The formation mechanism of such CNT networks was discussed, and could be described as “freeze drying within confined space.” Chemical characteristic of CNTs was controlled by choosing different solutions of non-functionalized CNTs (NOCNTs) or hydroxyl-modified CNTs (OHCNTs). As a consequence, CNT networks modified composites, especially that with OHCNTs formed networks, displayed significantly better electrical performance than composites with CNT aggregates and scattered CNTs; NOCNT networks and scattered OHCNTs made the corresponding composites possess higher interlaminar shear strength (ILSS) value, whereas OHCNT networks impaired ILSS while enhancing flexural strength and modulus of composites.     

Fabrication and effective thermal conductivity of multi-walled carbon nanotubes reinforced Cu matrix composites for heat sink applications

A novel particles-compositing method was used for the first time to disperse different contents of multi-walled carbon nanotubes (CNTs) in micron sized copper powders, which were subsequently consolidated into CNT/Cu composites by spark plasma sintering (SPS). Microstructural observations showed that the homogeneous distribution of CNTs and dense composites could be obtained for 0–10 vol.% CNT contents. The CNT clusters were appeared in the powder mixture with 15 vol.% CNTs, which resulted in an insufficient densification of the composites. The effective thermal conductivity of the composites was analyzed both theoretically and experimentally. The addition of CNTs showed no enhancement in overall thermal conductivity of the composites due to the interface thermal resistance associated with the low phase contrast of CNT to copper and the random tube orientation. Besides, the composite containing 15 vol.% CNTs led to a rather low thermal conductivity due possiblely to the combined effect of unfavorable factors induced by the presence of CNT clusters, i.e. large porosity, lower effective conductivity of CNT clusters themselves and reduction of SPS cleaning effect. The CNT/Cu composites may be a promising thermal management material for heat sink applications.     

Interface tailoring to enhance mechanical properties of carbon nanotube reinforced magnesium composites

This study highlights the use of a metallic coating of nanoscale thickness on carbon nanotube to enhance the interfacial characteristics in carbon nanotube reinforced magnesium (Mg) composites. Comparisons between two reinforcements were targeted: (a) pristine carbon nanotubes (CNTs) and (b) nickel-coated carbon nanotubes (Ni–CNTs). It is demonstrated that clustering adversely affects the bonding of pristine CNTs with Mg particles. However, the presence of nickel coating on the CNT results in the formation of Mg₂Ni intermetallics at the interface which improved the adhesion between Mg/Ni–CNT particulates. The presence of grain size refinement and improved dispersion of the Ni–CNT reinforcements in the Mg matrix were also observed. These result in simultaneous enhancements of the micro-hardness, ultimate tensile strength and 0.2% yield strength by 41%, 39% and 64% respectively for the Mg/Ni–CNT composites in comparison with that of the monolithic Mg.     

碳纳米管对激光选区熔化成形Al基复合材料的影响

基于激光选区熔化（SLM）方式,通过改变扫描速度,制备不同碳纳米管（CNTs,质量分数分别为0、0.5wt%、1.0wt%、1.5wt%、2.0wt%）含量的CNTs/Al复合材料试件,探究不同CNTs含量与激光扫描速度对试件性能的影响。结果表明,CNTs含量小于1.0wt%时,分散效果较好,大部分CNTs以单根状态黏附于Al粉表面;含量大于1.0wt%时,CNTs团聚尺寸增大、数量增多。相同SLM成形工艺下,低CNTs含量的CNTs/Al复合材料试件内部孔隙较少,致密度较高;高CNTs含量的CNTs/Al复合材料试件内部孔隙逐渐增多,致密度降低。激光扫描速度为1 300 mm/s工艺下,随着CNTs质量分数的增加,CNTs/Al复合材料试件硬度呈先上升后下降趋势,在CNTs含量为1.0wt%显微硬度达到最高。CNTs/Al复合材料试件平均晶粒尺寸相对于铝合金试件更加细化,在CNTs含量大于1.0wt%时,尽管晶粒依然细化,但试件致密度降低造成显微硬度下降明显。     

Dispersion assessment and studies on AC percolative conductivity in polymer-derived Si–C–N/CNT ceramic nanocomposites

Nanocomposites comprise polysilazane-derived SiCN ceramic charged with carbon nanotubes (CNTs) have been prepared by dispersion of multi-walled CNTs with a diameter of 80 nm in a cross-linked polysilazane (HTT 1800, Clariant) using a simple roll-mixer method. Subsequently, the composites were warm pressed and pyrolyzed in argon atmosphere. Scanning electron microscopy (SEM) and 3D Raman imaging techniques were used as major tools to assess the dispersion of CNTs throughout the ceramic matrix. Furthermore, studies on the effect of the volume fraction of CNTs in the nanocomposites on their electrical properties have been performed. The specific bulk conductivities of the materials were analyzed by AC impedance spectroscopy, revealing percolation thresholds (ρ_c) at CNT loadings lower than 1 vol%. Maximum conductivity amounted to 7.6 × 10⁻² S/cm was observed at 5 vol% CNT. The conductivity exponent in the SiCN/CNT composites was found equal to 1.71, indicating transport in three dimensions.     

Carbon fiber/epoxy composite property enhancement through incorporation of carbon nanotubes at the fiber–matrix interphase – Part I: The development of carbon nanotube coated carbon fibers and the evaluation of their adhesion

A new method to realize the uniform coating of carbon nanotubes (CNTs) to carbon fibers (CFs) has been developed, which enables the scalable fabrication of CNT containing CF/epoxy composites. In this method, CNTs are treated by cationic polymers, then, the CNTs are coated to CFs by immersion into a CNT/water suspension. Good dispersion is achieved by repulsive force between positively charged CNTs and uniform coating of the CNTs is achieved by attractive forces between positively charged CNTs and negatively charged CFs. It is found that the use of specific cationic polymers including polyethyleneimine (PEI) results in stable CNT/water suspensions, and uniform coating of the CNTs. Single fiber fragmentation tests of the CF/epoxy composites were conducted to evaluate the strength of interface and interphase under shear loading. The results show that the combination of epoxy resin sizing and PEI treated CNT coating to CFs results in high interfacial shear strength.     

Dual strengthening mechanisms induced by carbon nanotubes in roll bonded aluminum composites

The dual role of carbon nanotubes (CNTs) in strengthening roll bonded aluminum composites has been elucidated in this study. An increase in the elastic modulus by 59% has been observed at 2 vol.% CNT addition in aluminum, whereas tensile strength increases by 250% with 9.5 vol.% CNT addition. CNTs play a dual role in the strengthening mechanism in Al–CNT composite foil, which can be correlated to the degree of dispersion of CNTs in the matrix. Better CNT dispersion leads to improvement of elastic properties. In contrast, CNT clusters in the aluminum matrix impede dislocation motion, causing strain hardening and thus improvement in the tensile strength. Dislocation density of the composites has been computed as a function of CNT content to show the effect on strain hardening of the metal matrix–CNT composite.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

Hybrid network structure and thermal conductive properties in poly(vinylidene fluoride) composites based on carbon nanotubes and graphene nanoplatelets

A small quantity of carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs) were introduced into the poly(vinylidene fluoride) (PVDF)/GNP and PVDF/CNT composites, respectively, to prepare the corresponding ternary PVDF/CNT/GNP and PVDF/GNP/CNT composites. The results demonstrated that adding CNTs into the PVDF/GNP composites greatly promoted the formation of the hybrid network structure of fillers. This was much different from the scenario that adding GNPs into the PVDF/CNT composites. GNPs and CNTs exhibited excellent nucleation effects for the crystallization of PVDF matrix; however, the variation of the PVDF crystallinity was small. Adding CNTs into the PVDF/GNP composites greatly enhanced the electrical conductivity of the PVDF/CNT/GNP composites. This was also different from the scenario of the PVDF/GNP/CNT composites. Furthermore, the PVDF/CNT/GNP composites exhibit higher thermal conductivity and higher synergistic efficiency compared with the PVDF/GNP/CNT composites. The conductive mechanisms and the synergistic effects of the ternary composites were then analyzed.     

Mechanical,electrical and thermal properties of aligned carbon nanotube/polyimide composites

Carbon nanotubes (CNTs) have high strength and modulus, large aspect ratio, and good electrical and thermal conductivities, which make them attractive for fabricating composite. The poly(biphenyl dianhydride-p-phenylenediamine) (BPDA/PDA) polyimide has good mechanical and thermal performances and is herein used as matrix in unidirectional carbon nanotube composites for the first time. The strength and modulus of the composite increase by 2.73 and 12 times over pure BPDA–PDA polyimide, while its electrical conductivity reaches to 183 S/cm, which is 10¹⁸ times over pure polyimide. The composite has excellent high temperature resistance, and its thermal conductivity is beyond what has been achieved in previous studies. The improved properties of the composites are due to the long CNT length, high level of CNT alignment, high CNT volume fraction and good CNT dispersion in polyimide matrix. The composite is promising for applications that require high strength, lightweight, or high electrical and thermal conductivities.     

In situ polymerized nanocomposites: Polystyrene/CNT and Poly(methyl methacrylate)/CNT composites

Carbon nanotubes (CNTs) were incorporated into polystyrene (PS) and poly(methyl methacrylate) (PMMA) matrices via in situ emulsion and emulsion/suspension polymerization methods. The polymerizations were carried out using various initiators, surfactants, and carbon nanotubes to determine their influence on polymerization and on the properties of the composites. The loading of CNTs in the composites varied from 0 to 15 wt.%, depending on the CNTs used. Morphology and dispersion of the CNTs were analyzed by transmission and scanning electron microscopy techniques. The dispersion of multi-walled carbon nanotubes (MWCNT) in the composites was excellent, even at high CNT loading. The mechanical properties, and electrical and thermal conductivities, of the composites were also analyzed. Both electrical and thermal conductivities were improved.     

基于空间限域强制组装法制备短切碳纤维-碳纳米管/聚二甲基硅氧烷导电复合材料性能

采用空间限域强制组装（SCFNA）法制备短切碳纤维-碳纳米管/聚二甲基硅氧烷（SCF-CNTs/PDMS）导电复合材料,研究SCFNA方法制备SCF-CNTs/PDMS复合材料对断面形态变化、导电性能和力学性能的影响。结果表明,通过SCFNA制备的SCF-CNTs/PDMS导电复合材料得到了密实有效的导电网络,由于缩短了导电填料之间的距离,实现了在低浓度填料下增大复合材料的导电性能和力学性能。在填料总量不变的前提下,SCF/PDMS复合材料中添加少量的CNTs,SCF与CNTs之间能形成较好的协同作用。并发现SCF质量分数为8wt%、CNTs质量分数为2wt%的SCF-CNTs/PDMS复合材料与SCF质量分数为10wt%的SCF/PDMS复合材料相比,其导电性能提高了33%,力学性能提高了144%;在SCF/PDMS复合材料中添加较多的CNTs,由于CNTs之间发生团聚现象,SCF-CNTs/PDMS复合材料的导电性能和力学性能均有所下降。SCF质量分数为5wt%、CNTs质量分数为5wt%的SCF-CNTs/PDMS复合材料随着密炼转速由40 r/min逐步增加到80 r/min,CNTs团聚现象有所改善,但是由于扭矩的增大,SCF受到的剪切作用力增大,SCF大部分被搅碎,在导电复合材料中,SCF起主要连接导电网络的作用。因此,SCF质量分数为5wt%、CNTs质量分数为5wt%的SCF-CNTs/PDMS复合材料导电性能反而随着密炼转速的提高而降低。      

纳米碳管与活性炭复合电极电吸附脱盐性能的研究

为考察纳米碳管（CNTs）、活性炭（AC）及其复合电极的电吸附脱盐性能，将其粉末压制成电极，组装成脱盐器，比较电极电吸附脱盐能力和脱盐能耗。结果表明，在活性炭电极中添加纳米碳管有效地降低了电极电阻和脱盐能耗，少量纳米碳管的添加能在一定程度上提高其电极比表面积、孔容以及在盐水中的比电容；当复合电极中纳米碳管的含量为10％时，其电极在盐水中的电吸附比电容达到113.5F/g，其电极脱盐效果最为显著，其脱盐耗能比活性炭电极降低约67％左右。     

Poly(vinyl alcohol) reinforced with large-diameter carbon nanotubes via spray winding

For practical application of carbon nanotube (CNT)/polymer composites, it is critical to produce the composites at high speed and large scale. In this study, multi-walled carbon nanotubes (MWNTs) with large diameter (∼45 nm) and polyvinyl alcohol (PVA) were used to increase the processing speed of a recently developed spraying winding technique. The effect of the different winding speed and sprayed solution concentration to the performance of the composite films were investigated. The CNT/PVA composites exhibit tensile strength of up to 1 GPa, and modulus of up to 70 GPa, with a CNT weight fraction of 53%. In addition, an electrical conductivity of 747 S/cm was obtained for the CNT/PVA composites. The good mechanical and electrical properties are attributed to the uniform CNTs and PVA matrix integration and the high degree of tube alignment.     

碳纳米管在超级电容器中的应用研究进展

超级电容器是近年来发展起来的一种新型储能装置。碳纳米管由于具有独特的中空结构，良好的导电性和高的比表面积，被认为是超级电容器理想的电极材料之一，引起了广泛的关注。通过介绍碳纳米管在超级电容器中的应用研究进展，评述了碳纳米管、活化碳纳米管、碳纳米管／金属氧化物复合物以及碳纳米管／导电聚合物复合物用做超级电容器电极材料的特点和性能。认为单纯的碳纳米管由于比表面积小，比容量偏低。化学活化可以显著提高碳纳米管的比表面积，增大其比电容。将碳纳米管与准电容材料金属氧化物或导电聚合物复合。可以发挥各自的优势，从而得到低成本、高性能的复合电极材料，将是今后发展的一个方向。     

Maximum nanotube volume fraction and its effect on overall elastic properties of nanotube-reinforced composites

The potential capability of improving overall elastic modulus of nanotube-reinforced composites is a fundamental concern in nanotechnology applications. Based on geometric analysis and micromechanics estimation, this study reports that the ratio of surface-to-surface distance of adjacent carbon nanotubes (CNTs) to the CNT diameter plays a key role in improving the overall elastic modulus of the CNT-reinforced composites when the tubes are perfectly aligned, completely separated from other tubes, and ideally bonded with the composite matrix. With the decrease of this ratio, that is, decrease of the surface-to-surface distance of adjacent CNTs and/or increase CNT diameter, the improvement capability increases. However, theoretical and experimental results show that an increase of the CNT diameters degrades the elastic moduli of CNTs. This paper discusses the criterion of choosing CNTs with larger diameter and addresses the factors influencing the surface-to-surface distance of adjacent CNTs.     

Effect of Carbon Black on the Strain Sensing Property of 3D Printed Conductive Polymer Composites

Applied Composite Materials - In this work, carbon nanotubes (CNTs) and carbon black (CB) filled thermoplastic polyurethane (TPU) composites (CNT/TPU and CB/CNT/TPU) were used to prepare the...