碳纳米管材料导热性能的实验研究

本文对碳纳米管与环氧树脂(Epoxy-EP)复合材料的导热性能进行了定量的研究,探索了CNTs/EP复合材料的制备方法,运用Hotdisk热常数分析仪研究了CNTs/EP复合材料的导热系数;利用CNTs/EP两相复合材料的导热理论模型得到了室温下单壁碳纳米管(Single-Wall Carbon Nanotubes-SWCNTs)的导热系数为3980 W/(m.K),双壁碳纳米管的导热系数(Double-Wall Carbon Nanotubes-DWCNTs)为3580 W/(m.K),以及多壁碳纳米管(Multi-Wall Carbon Nanotubes-MWCNTs)的导热系数为2860 W/(m.K)。     

Effect of SWCNT dispersion on epoxy nanocomposite properties

In nanocomposites containing single wall carbon nanotubes (SWCNTs), the final properties strongly depend on the dispersion quality of these fillers. Various methods have been used to improve the dispersion of nanofillers; however, one of the most effective ways is to functionalize carbon nanotubes (CNTs) with covalent and noncovalent functional groups. In this work, the dispersion of SWCNTs in an epoxy system was studied by using surfactants, acid (COOH), and ester groups (PGE)‐modified CNTs. Rheological and scanning electron microscopy analysis showed that functionalization of CNTs helped in improving the dispersion of fillers in the epoxy matrix. Systems with surfactant modified SWCNTs (1 wt%) exhibited the highest storage modulus at low frequencies after 5‐min sonication. This behavior is associated to a stronger network of fillers as a result of a good dispersion. However, longer sonication times lowered the storage modulus, corresponding to a degradation of the tubes. The effect of the dispersion quality on mechanical properties was also studied using a three‐point bending set‐up. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

High-crystallization polyoxymethylene modification on carbon nanotubes with assistance of supercritical carbon dioxide: Molecular interactions and their thermal stability

As a typical engineering plastic and high-crystallization polymer, polyoxymethylene (POM) has been successfully wrapped on single-walled carbon nanotubes (SWCNTs) using a simple supercritical carbon dioxide (SC CO₂) antisolvent-induced polymer epitaxy method. The characterization results of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveal that the SWCNTs are coated by laminar POM with the thicknesses of a few nanometers. The polymer adsorption on CNTs via multiple weak molecular interactions of CH groups with CNTs has been identified with FTIR and Raman spectroscopy. The experimental results indicate that the decorating degree of POM on the surface of CNTs increases significantly with the increase of SC CO₂ pressure, and accordingly the dispersion of SWCNT modified by POM at higher pressure are more excellent than that of obtained at lower pressure. Further the processing stability of POM/CNTs composites are investigated by differential scanning calorimetry and thermogravimetric analysis. The experimental results obtained show that their thermal stability behavior is closely related to surface properties of CNTs. Apparently, the composites with POM-decorating SWCNTs as the filler shows higher melting points compared to the POM composites with pristine SWCNTs as the filler. Therefore, we anticipate this work may lead to a controllable method making use of peculiar properties of SC CO₂ to help to fabricate the functional CNTs-based nanocomposites containing highly crystalline thermoplastic materials such as POM.     

The influence of single-walled carbon nanotube functionalization on the electronic properties of their polyaniline composites

The “in situ” preparation and characterization of composites of polyaniline (PANI) and single-walled carbon nanotubes (SWCNTs) are reported. To improve the dispersion and compatibility with the polymer matrix the raw SWCNTs were modified following different routes. SWCNTs oxidized by chemical or thermal treatments (nitric acid and air oxidation, respectively) were subjected to covalent functionalization with octadecylamine (ODA). SWCNT/PANI composites were prepared either from just oxidized SWCNTs, or from ODA functionalized SWCNTs. Temperature-programmed desorption, elemental analyses, ultraviolet-visible (UV-vis), UV-vis with near infrared and Raman spectroscopy, X-ray diffraction, scanning and transmission electron microscopy and conductivity measurements were used to characterize the functionalized SWCNT materials, dispersions and composites. The PANI composite prepared from air oxidized SWCNTs showed the best electrical conductivity indicating a better interaction with polyaniline than ODA functionalised SWCNTs. The improvement of conductivity is attributed to the doping effect or charge transfer of quinoide rings from PANI to SWCNTs.     

Preparation and properties of hierarchical composites based on carbon nanotubes‐coated glass babric preform

A strategy based on carbon nanotubes (CNTs)‐containing sizing dispersion has been implemented to fabricate nanocomposite preforms and their hybrid multiscale composites. The state of pristine CNTs and carboxylic acid functionalized CNTs (CNTs–COOH) in sizing dispersion was effectively monitored by on‐line measuring electrical conductivity. The effects of different CNTs coating applied onto glass fabric on wettability of nanocomposite fibrous reinforcement with epoxy matrix were evaluated using scanning electron microscopy and capillary experiment. A CNTs‐COOH loading of 0.5 wt% gave rise to 97% and 30°C increases in the storage modulus (G′) and glass transition temperature of the resulting hybrid composites, respectively. The enhanced thermomechanical properties of the CNTs hybrid composites are closely related to the stable CNTs sizing dispersion and uniform coating onto fiber reinforcement. The mechanism for reinforcing composites through toughening resin region with CNTs desorbing from primary fiber surface during impregnation has been identified. POLYM. COMPOS. 37:979–986, 2016. © 2014 Society of Plastics Engineers     

Facile way to disperse single‐walled carbon nanotubes using a noncovalent method and their reinforcing effect in poly(methyl methacrylate) composites

In this work, a noncovalent method was used to functionalize and thereby disperse single‐walled carbon nanotubes (SWCNTs) in dimethylformamide with poly[methyl methacrylate‐co‐(fluorescein O‐acrylate)] as a surfactant, and then the resultant poly(methyl methacrylate) (PMMA)‐based nanocomposites were fabricated via solution casting. The dispersion level of carbon nanotubes in the solvent was investigated by means of scanning electron microscopy and atomic force microscopy. The results showed that carbon nanotubes were well wrapped by the surfactant, and small carbon nanotube bundles several nanometers or less in diameter and several micrometers in length were obtained. Both scanning electron microscopy and transmission electron microscopy confirmed the uniform dispersion of SWCNTs in the PMMA matrix. The mechanical properties of the composites were determined with a universal tension tester. The PMMA composite containing 2 wt % SWCNTs showed improved tensile properties versus neat PMMA, showing 56 and 30% enhancements of the tensile modulus and tensile stress, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of dispersion states of carbon nanotubes on physical properties of epoxy nanocomposites

Effects of different dispersion states of carbon nanotubes (CNTs) on rheological, mechanical, electrical, and thermal properties of the epoxy nanocomposites were studied. The dispersion states were altered depending upon whether a solvent was employed or not. To characterize dispersion of the CNTs, field emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM) were used. It was found that the nanocomposites containing poorly dispersed CNTs exhibited higher storage modulus, loss modulus, and complex viscosity than ones with well dispersed CNTs. It means that the poorly dispersed CNTs/epoxy composites have, from a rheological point of view, a more solid-like behavior. Tensile strength and elongation at break of the nanocomposites with different dispersion of CNTs were measured. Both of the well and the poorly dispersed CNTs composites showed a percolation threshold of electrical conductivity at less than 0.5 wt.% CNTs loading and the former had higher electrical and thermal conductivities than the latter. Effects of the CNTs content on the physical properties were also examined experimentally. As loading of the CNTs increased, improved results were obtained. From the morphological observation by FESEM and TEM, it was found that when the solvent was not used in the CNTs dispersion process, aggregates of pristine CNTs remained in the nanocomposites.     

Development and characterization of PEEK/carbon nanotube composites

New poly(ether ether ketone) (PEEK) based composites have been fabricated by the incorporation of single-walled carbon nanotubes (SWCNTs) using melt processing. Their structure, morphology, thermal and mechanical properties have been investigated. Scanning electron microscopy observations demonstrated a more uniform distribution of the CNTs for samples prepared following a processing route based on polymer ball milling and CNT dispersion in ethanol media. Thermogravimetric analysis indicated a remarkable improvement in the thermal stability of the matrix by the incorporation of SWCNTs. Differential scanning calorimetry showed a decrease in the crystallization temperature with increasing SWCNT content, whilst no significant changes were observed in the melting of the composites. The crystallite size determined by X-ray diffraction decreased at high SWCNT loading, which is attributed to the spatial limitations on crystal growth by confinement within the CNT network. Dynamic mechanical analysis revealed an increase in the storage moduli, hence in the rigidity of the systems, with increasing SWCNT content. Their addition shifts the glass transition peak to higher temperatures due to the restriction in chain mobility imposed by the CNTs. Higher thermal stability and mechanical strength were found for composites with improved dispersion of the SWCNTs.     

Effects of surface modification on rheological and mechanical properties of CNT/epoxy composites

Despite superior properties of carbon nanotubes (CNTs), physical properties of the CNT/epoxy composites are not improved significantly because interfacial bonding between the CNTs and the polymer matrix is weak. CNTs were treated by an acidic solution to remove impurities and modified subsequently by amine treatment or plasma oxidation to improve interfacial bonding and dispersion of nanotubes in the epoxy matrix. The functional groups on the surface of treated CNTs were investigated by X-ray photoelectron spectroscopy. The surface modified CNTs were embedded in the epoxy resin by ultra-sonication and the cured nanotube containing composites were characterized by field emission scanning electron microscopy. Rheological properties of nanotube containing epoxy resin and mechanical properties of the modified CNT/epoxy composites were improved because the modification of CNTs improved dispersion and interaction between the CNT and the epoxy resin.     

Influence of the Processing Route on the Carbon Nanotubes Dispersion and Creep Resistance of 3YTZP/SWCNTs Nanocomposites

3YTZP matrix composites containing 2.5 vol% of single‐walled carbon nanotubes (SWCNT) were fabricated by Spark Plasma Sintering (SPS) at 1250°C, following different processing routines with the aim of optimizing the SWCNTs dispersion throughout the ceramic matrix. Microstructural characterization of the as‐fabricated samples has been performed by means of scanning electron microscopy (SEM). The specimens have been crept at 1200°C to correlate creep resistance and SWCNTs distribution. There are no creep experimental results on these nanocomposites reported in literature. Mechanical results show that the incorporation of SWCNTs into a 3YTZP matrix produces an increase in the strain rate at high temperature with respect to monolithic zirconia. The creep resistance of these nanocomposites decreases with the improvement of the SWCNTs dispersion, where a smaller SWCNTs agglomerate size and consequently a higher concentration of carbon nanotubes surrounding the 3YTZP grain boundaries is found. This fact indicates that SWCNTs act as a lubricant making grain‐boundary sliding easier during deformation of these composites.     

Electrical conductivity and tensile properties of block‐copolymer‐wrapped single‐walled carbon nanotube/poly(methyl methacrylate) composites

Poly(methyl methacrylate) (PMMA) composites containing raw or purified single‐walled carbon nanotubes (SWCNTs) are prepared by in situ polymerization and solution processing. The SWCNTs are purified by centrifugation in a Pluronic surfactant, which consists of polyethyleneoxide and polypropyleneoxide blocks. Both the effects of SWCNT purity and non‐covalent functionalization with Pluronic are evaluated. Electrical conductivity of PMMA increases by 7 orders of magnitude upon the integration of raw or purified SWCNTs. The best electrical properties are measured for composites made of purified SWCNTs and prepared by in situ polymerization. Strains at fracture of the SWCNT/PMMA composites are nearly identical to those of the neat matrix. A certain decrease in the work to fracture is measured, particularly for composites containing purified SWCNTs (?31.6%). Fractography and Raman maps indicate that SWCNT dispersion in the PMMA matrix improves upon the direct addition of Pluronic, while dispersion becomes more difficult in the case of purified SWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41547.     

Improvement of dispersion of carbon nanotubes in epoxy resin through pyrogallol functionalization

Multiwalled carbon nanotubes (MWNTs) were functionalized with pyrogallol. The functionalized MWNTs were well‐dispersed in the epoxy/curing agent/ethanol solution, as demonstrated by UV‐vis spectra and optical micrographs. Epoxy resin/MWNTs composites were prepared via solution mixing method. The cure behavior was characterized using differential scanning calorimetry. Pyrogallol‐functionalized carbon nanotubes (CNTs) reacted with the epoxy through the mediation reaction of pyrogallol with the curing agent, leading to the interfacial bonding between the functionalized carbon nanotubes (CNTs) and the resin matrix. Due to the excellent dispersion and interfacial bonding, the mechanical strength and electrical conductivity of the epoxy resin/CNTs composites have been improved. POLYM. ENG. SCI. 56:1079–1085, 2016. © 2016 Society of Plastics Engineers     

Effect of carbon nanotube addition on morphology of SHS synthesized materials

During the past few years, a considerable amount of research has been focused on the addition of carbon nanotubes (CNTs) to various matrix materials including polymers, ceramics, metals, and intermetallics. However, the processing methodologies for ceramics, metals, and intermetallics have been primarily those used in traditional power technology. In this paper combustion synthesis (CS), also known as self-propagating high temperature synthesis (SHS) or volume combustion synthesis (VCS) was explored as a route for the formation of carbon nanotube reinforced composites. The effect of single-walled carbon nanotube (SWCNT) addition on the product morphology is presented for the following reactive systems: (i) Ni-Al and (ii) 3Ti-B₄C. It was determined that the SWCNTs survive a short exposure to the high temperatures associated with the combustion synthesis of NiAl (1911 K) and TiB₂-TiC (3200 K) and effectively act as a diluent which results in grain refinement of the resulting product. The results also show that effective dispersion of the SWCNTs is achieved; however, the SWCNTs are not well embedded in the matrix. Based on the survival of the SWCNTs in the above reactive systems it was shown that metal coated nanotubes may be a very promising reinforcement material for combustion synthesized materials and could effectively solve the issue of CNT to matrix adhesion.      

A comparison of the effects of multi-wall and single-wall carbon nanotube additions on the properties of zirconia toughened alumina composites

The use of multi-wall carbon nanotubes (MWCNTs) or single-wall carbon nanotubes (SWCNTs) as filler in ceramic matrices could create composites with exceptional mechanical properties. We have prepared dense monolithic alumina (Al₂O₃) and zirconia-toughened alumina (ZTA) composites with additions of 0.01 wt% of MWCNTs or 0.01 wt% of SWCNTs by conventional sintering and have demonstrated that the mechanical properties depend on (a) the distribution of CNTs in the matrix and (b) the interaction between the ceramic phases and CNTs. The fracture toughness of Al₂O₃ ceramics reinforced with SWCNTs was significantly better than those reinforced with MWCNTs. However, fracture toughness in MWCNT-reinforced ZTA increased 41% over ZTA free of the toughening agent and 44% over ZTA reinforced with SWCNTs. A well dispersed and small amount of MWCNTs was enough to produce an increase of fracture toughness in ZTA composites.     

Preparation and mechanical properties of waterborne polyurethane/carbon nanotube composites

Waterborne polyurethane (WBPU) and multiwalled carbon nanotubes (CNTs) composite films with 0–4.0 wt% CNTs were prepared by ultrasonic dispersion of carboxylic acid‐functionalized CNTs in WBPU followed by emulsion casting process. The elongations at break of the WBPU/CNTs composites increase with the incorporation of CNTs. The tensile strength and crystallinity of the nanocomposite films with lower CNTs contents (<2 wt%) increase obviously; while the tensile strengths of the composites with more CNTs (≥2 wt%) decrease, in contrast to the pure PU film. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicated that the CNTs are uniformly dispersed in the composites incorporated with lower CNTs contents (≤1.5 wt%). However, aggregation of CNTs increased with increasing CNTs content in the WBPU/CNTs composites, causing the macrophase separation. The dispersion state of the CNTs affects the crystallinity of the PU matrix and the phase separation of the composites, which are two key factors to influence the mechanical properties of the WBPU/CNTs composites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Effect of filler dispersion on the electrical conductivity and mechanical properties of carbon/polypropylene composites

Conducting carbon/polypropylene composites containing a mixed filler of crystalline natural graphite powder, carbon black, and multiwalled carbon nanotubes have been prepared. The effect of the filler dispersion on the electrical conductivity and mechanical properties has been studied. Keeping the graphite content constant and increasing the ratio of carbon black to nanotubes, the conductivity and the flexural modulus increased linearly at different graphite contents. Graphite aggregates on the cross sections were analyzed by optical microscopy to characterize the dispersion of graphite. The results of the optical microscopy studies showed that the dispersion of graphite is affected by the composition and amount of the nanofiller system. Based on the observations simplified morphological models were set up, that allowed to explain the change in the electrical and mechanical properties of the composites of different compositions. POLYM. COMPOS., 34:1195–1203, 2013. © 2013 Society of Plastics Engineers     

碳纳米管填充复合材料体系的导热模型研究进展

综述了以聚合物为基体的碳纳米管填充复合材料导热模型，分析了复合材料热传导体系中碳纳米管(CNTs)填料的作用机制，归纳了均质模型、非均质模型和随机分散模型等，总结了导热模型常用的数值计算方法。这些模型丰富了导热理论，可以对复合材料导热系数进行初步预测，但在数值上都存在近似或者简化处理，对碳纳米管复合材料预测广谱性较差，若要提高预测准确性，需要更深入探究分子界面处的热阻。     

Carbon nanotube/polymer nanocomposites: A study on mechanical integrity through nanoindentation

Carbon nanotubes (CNTs) are under intense investigation in materials science owing to their potential for modifying the mechanical proprieties of their composites. In this work, nanomechanical and nanotribological properties of polymer composites, reinforced with multiwall carbon nanotubes (MWCNTs) and single wall carbon nanotubes (SWCNTs), have been studied using the nanoindentation and nanoscratch technique. In particular, three different epoxy resins reinforced using several percentage of two different types of MWCNTs have been studied (range 0–7 wt%). Another resin was reinforced using MWCNTs (range 0–2.5 wt%) and SWCNTs (range 0–5 wt%) as fillers. Hardness and elastic modulus using nanoindenter instrument have been evaluated, while the coefficient of friction of the nanocomposites is obtained using nanoscratch. The results show an evident dependence with the percentage of CNTs. For all types of resins, an optimum in nanomechanical properties is found at intermediate levels of CNTs filling. POLYM. COMPOS., 36:1432–1446, 2015. © 2014 Society of Plastics Engineers     

Tailored dielectric and mechanical properties of noncovalently functionalized carbon nanotube/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) nanocomposites

The preparation of high‐dielectric poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) composites containing functionalized single‐walled carbon nanotubes (f‐SWCNTs) noncovalently appended with dibutyltindilaurate are reported herein. Transmission electron microscopy and X‐ray photoelectron and Raman spectroscopy confirmed the noncovalent functionalization of the SWCNTs. The SEBS‐f‐SWCNT composites exhibited enhanced mechanical properties as well as a stable and high dielectric constant of approximately 1000 at 1 Hz with rather low dielectric loss at 2 wt% filler content. The significantly enhanced dielectric property originates from the noncovalent functionalization of the SWCNTs that ensures good dispersion of the f‐SWCNTs in the polymer matrix. The f‐SWCNTs also acted as a reinforcing filler, thereby enhancing the mechanical properties of the composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

碳纳米管纳米复合材料的研究现状及问题

文章介绍了碳纳米管的结构和性能,综述了碳纳米管聚合物复合材料的制备方法及其聚合物结构复合材料和聚合物功能复合材料中的应用研究情况,在此基础上,分析了碳纳米管在复合材料制备过程中的纯化、分散、损伤和界面等问题,并展望了今后碳纳米管/聚合物复合材辩的发展趋势.