高强度碳纳米管/聚合物复合材料的制备和应用

介绍了碳纳米管的结构和碳纳米管/聚合物复合材料的制备方法——溶液共混法、熔融法、原位聚合法和化学修饰法等。结合碳纳米管的特性,综述了碳纳米管/聚合物复合材料在力学性能的增强、电极材料、生物医学材料等方面的应用。     

多壁碳纳米管复合聚碳酸酯/苯乙烯系聚合物复合材料导电性能的研究

采用一步法将聚苯乙烯（PS）、苯乙烯-丙烯腈共聚物（SAN）和甲基丙烯酸甲酯-苯乙烯共聚物（MS）分别与聚碳酸酯（PC）、多壁碳纳米管（MWCNTs）熔融混合,得到PC/PS/MWCNTs、PC/SAN/MWCNTs和PC/MS/MWCNTs三种复合材料。透射电子显微镜和场发射扫描电子显微镜观察表明,MWCNTs选择性分散在PC相中,这与Sumita模型预测的结果完全吻合,且随着PS、SAN或MS含量的增加,体系的体积电阻率-苯乙烯系聚合物含量曲线能够很好地拟合到PC/MWCNTs体系的体积电阻率-MWCNTs有效体积浓度曲线上,体系的体积电阻率变化符合有效浓度的概念。     

改性碳纳米管对环氧树脂基复合材料热性能和力学性能的影响

通过对多壁碳纳米管(MWCNT)进行热处理和混酸处理,用超声分散和模具浇注成型法制备了MWCNT/环氧树脂复合材料。采用傅里叶红外光谱对MWCNT进行了表征,研究了不同MWCNT含量对环氧树脂热稳定性、导热性能和冲击性能的影响,并用扫描电镜观察了MWCNT在环氧基体中的分散情况。结果表明,经酸化的MWCNT在基体中分散性较好,复合材料的导热性能和力学性能都有明显提高,当酸处理的MWCNT填充量为1%时,复合材料的玻璃化转变温度(Tg)较纯环氧树脂升高了19.5℃。     

应力松弛对PET/炭黑/碳纤维复合材料影响规律分析

将聚对苯二甲酸乙二酯(PET)作为基体材料与炭黑和短切碳纤维熔融混合制备了PET/炭黑/碳纤维复合材料,研究了复合材料的导电性能、拉伸荷载下的应力–应变、应力松弛以及应力松弛对复合材料的应变–电阻响应规律。结果表明,PET/炭黑/碳纤维复合材料的电阻率为1.6Ω·cm,具有良好的导电性能;在拉伸应变3.5×10–3范围内,PET/炭黑/碳纤维复合材料的应力–应变呈线性,弹性模量为380.6 MPa;拉伸荷载为50 N时保持材料变形恒定,5 min后材料的应力松弛为11.2%;PET/炭黑/碳纤维复合材料在2.5×10–3拉伸应变作用下,拉应变与瞬时电阻具有较好的相关性,随着应变增加,电阻增加,且重复性较好;保持拉应变恒定,0.5 h后材料的电阻小于瞬时电阻,应力松弛使复合材料内部的导电颗粒重新分布,导致了材料整体电阻的变化。     

炭黑/碳纳米管并用比对天然橡胶复合材料物理性能和导热性能的影响

研究炭黑(CB)/碳纳米管(CNTs)并用比对天然橡胶(NR)复合材料物理性能和导热性能的影响,结果表明:与CB/NR复合材料相比,CB/CNTs/NR复合材料的性能提高;当CB/CNTs并用比为28/7时,复合材料的物理性能最佳、储能模量最大、损耗因子峰值最小、热导率最高。透射电子显微镜分析表明:当CB/CNTs并用比为28/7时,CB与CNTs分散均匀,CNTs无弯曲团聚,良好桥接CB,构成有效的填料网络;当CNTs用量继续增大,CNTs和CB出现团聚现象。NR复合材料的性能与填料网络协同作用密切相关。     

Ultrasonic-Assisted Method for the Preparation of Carbon Nanotube-Graphene/Polydimethylsiloxane Composites with Integrated Thermal Conductivity,Electromagnetic Interference Shielding,and Mechanical Performances

Due to the rapid development of the miniaturization and portability of electronic devices, the demand for polymer composites with high thermal conductivity and mechanical flexibility has significantly increased. A carbon nanotube (CNT)-graphene (Gr)/polydimethylsiloxane (PDMS) composite with excellent thermal conductivity and mechanical flexibility is prepared by ultrasonic-assisted forced infiltration (UAFI). When the mass ratio of CNT and Gr reaches 3:1, the thermal conductivity of the CNT-Gr(3:1)/PDMS composite is 4.641 W/(m·K), which is 1619% higher than that of a pure PDMS matrix. In addition, the CNT-Gr(3:1)/PDMS composite also has excellent mechanical properties. The tensile strength and elongation at break of CNT-Gr(3:1)/PDMS composites are 3.29 MPa and 29.40%, respectively. The CNT-Gr/PDMS composite also shows good performance in terms of electromagnetic shielding and thermal stability. The PDMS composites have great potential in the thermal management of electronic devices.     

Morphology,Thermal Stability,and Electrical Conductivity of Polymer Nanocomposites of Isotactic Polypropylene/Multi-Walled Carbon Nanotubes

Molecular weight of isotactic polypropylene (iPP) and concentration of multi-walled carbon nanotubes (MWCNT) effects on the morphology, thermal stability, and electrical conductivity for iPP/MWCNT nanocomposites were evaluated. Nanocomposites were prepared by solution mixing followed by non-isothermal crystallization from the melt. The samples were characterized by different physical-chemical techniques. Electrical conductivity was obtained from electrical resistance measured using a source meter. It was determined that the morphology of the nanocomposites shows a change from spherulitic to fibrillar to undefined depending on the molecular weight of iPP and concentration of MWCNT. Morphology was correlated with thermal stability and electrical conductivity.     

Formation of Liquid Crystalline Order and Its Effect on Thermal Conductivity of AlN/Liquid Crystalline Epoxy Composite

The liquid crystalline (LC) order was introduced on aluminum nitride particles by the surface effect to increase the thermal conductivities of aluminum nitride/LC epoxy composites. X-ray diffraction and grazing incidence small-angle X-ray scattering analyses revealed that the LC epoxy resin cured on the surface of an α-Al₂O₃ substrate formed homeotropically aligned smectic layers to increase the thermal conductivity. Therefore, thermally treated aluminum nitride particles, which formed α-Al₂O₃ layers on their surfaces, were applied to prepare the composites with high thermal conductivity. The thermal conductivities of the resulting composites were 11–36% higher than those with the composites prepared using untreated aluminum nitride particles.     

The Effect of Superimposed Dynamic and Static Stresses on the Stress Relaxation Rates of Model Epoxy Resins

Model epoxy resins with controlled crosslinking densities were prepared from a commercially available DGEBA (Epon Resin 825® from Shell Chemical) and α,ω-aliphatic diamines having different lengths of the aliphatic chain. The mixtures were always prepared in stoichiometric ratio. Dumbbell specimens, either with a cylindrical (with thin walls) or a rectangular cross section, have been subjected to combined static tensile strains (applied vertically) and dynamic torsional strains (applied horizontally). The experiments were performed at temperatures encompassing the glassy and the rubbery range of each investigated resin. The apparatus, by which the combined dynamic and static stresses were applied, was equipped with load cells for measurement of stresses developed in the specimens, both in tension and in shear. In this paper, results concerning the effect of the above combinations of stresses on stress relaxation rates in tension are shown. The main conclusion of this study is that combinations of dynamic and static stresses affect the network chain mobility, as it is expressed by the stress relaxation rate, in a way depending on temperature and frequency of torsional oscillations, as well as the crosslinking density of the polymer. For the most flexible epoxy resins investigated in this work, the superimposed stressing experiments led to a stiffening of the structure in the glassy state, while an opposite effect has been observed for the most rigid resins in similar conditions. It seems that the behavior of the investigated epoxy resins in complex fields of stresses is governed by a balance between two competitive processes: free volume increase (by a strain-induced dilatation mechanism), and physical aging and short range orientation.     

Dispersion,Mechanical and Thermal Properties of Epoxy Resin Composites Filled with the Nanometer Carbon Black

The nanometer carbon black (CB) was employed to prepare epoxy resin/carbon black (EP/CB) composites by blending-casting method. The different modified methods of silicone coupling agent were used to improve the dispersion of CB in epoxy resin. The mechanical and thermal properties of EP/CB composites were investigated. Experimental results showed that the mechanical properties increased at first, but decreased with excessive addition of CB. When the mass fraction of CB was 2%, the mechanical properties were maximum. The use of modified CB significantly enhanced the mechanical properties of the composites. For given CB loading, the CB modified by pretreatment method displayed better dispersion in the epoxy resin than that of the direct mixing method. SEM observation revealed that the tensile fracture surface of the composite filled with 2 wt% modified CB held more microcracks than that of 5 wt% modified CB, and the formed microcracks could consume more energy of rupture, finally to have better tensile strength. DSC analysis showed that the glass transition temperature (Tg) of the composites increased with the increasing mass fraction of CB.     

The Effect of Low Power Nitrogen Plasma Treatment of Carbon Fibres on the Interfacial Shear Strength of Carbon Fibre/Epoxy Composites

Type II (high strength) carbon fibres have been given a low power nitrogen plasma treatment. It is shown that this plasma treatment has no effect on the fibre diameter, no detrimental effect on fibre strength and can significantly improve fibre/resin adhesion. It is proposed that this improvement is due to chemical interaction via amine/epoxy bonding at the edge sites together with the interaction of the epoxy with activated basal planes present on the fibre surface. This improvement is only achieved if the fibres are immersed in resin before being exposed to air. Exposing the treated fibres to air drastically reduces fibre/adhesion due to the adsorption of moisture from the environment. Heating these latter fibres in a vacuum at 130°C for one hour allows some recovery of the interfacial strength. It is also demonstrated that the interfacial shear strength falls dramatically when the nitrogen-containing functional groups are completely removed from the fibre surface.     

The Effect of Low Power Nitrogen Plasma Treatment of Carbon Fibres on the Interfacial Shear Strength of Carbon Fibre/Epoxy Composites

Type II (high strength) carbon fibres have been given a low power nitrogen plasma treatment. It is shown that this plasma treatment has no effect on the fibre diameter, no detrimental effect on fibre strength and can significantly improve fibre/resin adhesion. It is proposed that this improvement is due to chemical interaction via amine/epoxy bonding at the edge sites together with the interaction of the epoxy with activated basal planes present on the fibre surface. This improvement is only achieved if the fibres are immersed in resin before being exposed to air. Exposing the treated fibres to air drastically reduces fibre/adhesion due to the adsorption of moisture from the environment. Heating these latter fibres in a vacuum at 130°C for one hour allows some recovery of the interfacial strength. It is also demonstrated that the interfacial shear strength falls dramatically when the nitrogen-containing functional groups are completely removed from the fibre surface.     

Effect of Different Chemical Modification Systems on Thermal and Electrical Conductivity of Functionalized Multiwall Carbon Nanotube/Epoxy Nanocomposites

The use of polymeric materials in some applications is inhibited due to their low thermal conductivity. In this study epoxy nanocomposites of three differently modified carbon nanotubes were prepared and their thermal, electrical and mechanical properties were investigated. Acidic oxidation, amine grafting and Friedel-Crafts reactions were employed to prepare modified carbon nanotubes. It was found that nanocomposites obtained by Friedel-Crafts acylation reaction have superior thermal and electrical conductivity. Therefore, the addition of a very low amount of benzene tricarboxylic acid (BTC) nanotubes can result in a considerable improvement in the thermal and electrical conductivity of the resulting nanocomposite.     

Investigation on the Mechanical and Thermal Properties of Intercalated Epoxy/Layered Silicate Nanocomposites

Epoxy resin/layered silicate nanocomposites with various clay contents were prepared. The structural studies showed the intercalation of epoxy polymer chains into the clay galleries. The adhesion analysis of nanocomposite coating films on metallic substrates showed the excellent adhesion of epoxy-based nanocomposite coatings on iron plates, especially in lower clay loadings. According to the hardness test results, the organoclay minerals caused the increasing of the hardness of epoxy nanocomposites. The thermal properties of nanocomposites were evaluated by means of DSC and TGA analysis. The tensile and compression strengths of cured epoxy/clay systems were also investigated.     

Shape Memory and Physical Properties of Composites of Polyethylene Oxide/Poly(Propylene Glycol)-Block-Poly(Ethylene Glycol)-Block-Poly(Propylene Glycol)/2,4-Toluene Diisocyanate,Polypyrrole, and Modified MWCNT

Structural variation and its influence on morphology, mechanical, thermal, and electrical conductivity properties of polyethylene oxide/poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol)/2,4-toluene diisocyanate/polypyrrole (PEO/P(P-E-P)G/TDI/PPy) blends and nanocomposites with varying PPy content were reported. The chemical and fundamental linkages were confirmed by FTIR. SEM micrographs demonstrated homogeneous PEO/P(P-E-P)G/TDI/PPy blend formation and globular morphology for nanocomposites. The mechanical and DSC parameters were found to increase systematically with increasing PPy content in blend films. While for nanocomposites, better results were observed for 0.1% PPy content. Maximum electrical conductivity and good shape recovery of 94% was obtained for the nanocomposite with 1% PPy content.     

Compressive Fiber Fragmentation in Carbon/Polypropylene Composites: Effects of Residual Thermal Stresses and Transcrystallinity

The effects of fiber volume fraction and transcrystallinity in single fiber composites, on the phenomenon of compressive fiber fragmentation due to residual thermal stresses, are studied. A concentric cylinder model is used, jointly with experimental data, to predict the Weibull shape parameter of the compressive strength distribution of pitch-based high and medium modulus (HM and MM) carbon fibers, with isotactic polypropylene as the semi-crystalline embedding matrix. A severe effect of the fiber content on the thermal residual stress in the fiber and, thus, on the fiber break density, is predicted and experimentally confirmed. The effect of the presence of isothermally grown polypropylene transcrystalline interlayers (using pitch-based HM carbon fibers as a substrate) on the compressive stresses induced upon subsequent quenching is investigated, both experimentally and theoretically. Cooling rate results are also presented. The thermoelastic constants of the interlayer are predicted to have a severe effect on the residual stresses generated in the fiber, the interphase, and the matrix. There is therefore, a definite need for direct experimental measurements of these constants.     

碳纳米管/水泥基复合材料导电性与力敏特性研究

为改善水泥基复合材料的导电性,通过添加一定掺量的碳纳米管,制备了碳纳米管/水泥基复合材料。采用四电极伏安法和扫描电子显微镜的测试方法研究了碳纳米管的掺量对碳纳米管/水泥基复合材料的导电性和力敏特性的影响。试验结果表明,0.05%~0.5%的碳纳米管掺量处于渗流区内,此时试件的电阻率随碳纳米管掺量的增加而降低;在循环轴压应力作用下,试件的电阻率随应力的增大而减小,随应力的减小而增大,且变化曲线呈可回复近似单调的变化规律,同时试件的电阻相对变化率以及力敏灵敏度随碳纳米管掺量的增加而增大,显示出良好的力敏特性。这表明碳纳米管/水泥基复合材料的导电性与其受载过程有着密切的关联性,从而有望用于混凝土内部应力及损伤的监测。     

聚丙烯/膨胀石墨/碳纳米管复合材料电性能、微观结构及其流变学研究

研究了以膨胀石墨(EG)和多壁碳纳米管(MWNT)共同填充聚丙烯(PP)体系的电性能、微观结构及其流变行为。结果表明,EG和MWNT的协同导电作用显著降低了复合材料的体积电阻率和逾渗阀值,当MWNT用量为5 phr、EG为10 phr时,与PP/EG(15 phr)材料相比,复合材料的体积电阻率降低了1 600倍,通过其低频区流变行为的研究,表明EG同MWNT协同形成了更完善的三维网络结构,扫描电镜(SEM)分析表明,MWNT在复合体系中起到桥连作用,连接基体与EG,以及EG片层与片层,因此获得了更好的导电特性。     

Improvement of Hardness and Wear Resistance of Glass Fiber-Reinforced Epoxy Composites by the Incorporation of Silica/Carbon Hybrid Nanofillers

The tribological performance of hybrid composite (epoxy reinforced with woven, nonwoven tissue glass fibers, silica and carbon black nanoparticles) was investigated. Two methods were used to ensure good dispersion of nanoparticles in epoxy resin which were ultrasonic processor and magnetic stirrer. The effect of silica and/or carbon black nanoparticle content on microindentation hardness and wear properties of the neat glass fiber-reinforced epoxy composites was investigated. The results from the wear test indicated that, under all applied loads, incorporation of silica and carbon black nanoparticles either single or combined significantly improved the wear resistance of neat glass fiber reinforced epoxy. A significant increase in hardness of the hybrid nanocomposite laminates was achieved. Analysis of variance was developed to study the optimal wear testing parameters on composite samples. The most significant parameter is the time, followed by nanoparticle (silica and carbon black) content.