Synthesis and properties of poly(methyl methacrylate)/carbon nanotube composites covalently integrated through in situ radical polymerization

Poly(methyl methacrylate) (PMMA)/single‐walled carbon nanotube (SWNT) composites were synthesized by the grafting of PMMA onto the sidewalls of SWNTs via in situ radical polymerization. The free‐radical initiators were covalently attached to the SWNTs by a well‐known esterification method and confirmed by means of thermogravimetric analysis and Fourier transform infrared spectroscopy. Scanning electron microscopy and transmission electron microscopy were used to image the PMMA–SWNT composites; these images showed the presence of polymer layers on the surfaces of debundled, individual nanotubes. The PMMA–SWNT composites exhibited better solubility in chloroform than the solution‐blended composite materials. On the other hand, compared to the neat PMMA, the PMMA–SWNT nanocomposites displayed a glass‐transition temperature up to 6.0°C higher and a maximum thermal decomposition temperature up to 56.6°C higher. The unique properties of the nanocomposites resulted from the strong interactions between the SWNTs and the PMMA chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tensile modulus modeling of carbon black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated graphite nanoplatelet/polycarbonate composites

Conductive fillers are often added to thermoplastic polymers to increase the resulting composite's electrical conductivity (EC) which would enable them to be used in electrostatic dissipative and semiconductive applications. The resulting composite also exhibits increased tensile modulus. The filler aspect ratio plays an important role in modeling composite EC, and tensile modulus. It is difficult to measure the filler aspect ratio after the manufacturing process (often extrusion followed by injection molding) in the composite, especially when nanomaterials are used. The EC percolation threshold is a function of the filler aspect ratio; hence, knowledge of this percolation threshold provides a means to extract the filler aspect ratio. In this study, the percolation threshold of the composite was determined from EC measurements and modeling, which in turn was used to determine the filler aspect ratio for tensile modulus modeling. Per the authors' knowledge, this approach has not been previously reported in the open literature. The fillers; carbon black (CB: 2–10 wt %), multiwalled carbon nanotubes (CNT: 0.5–8 wt %), or exfoliated graphite nanoplatelets (GNP: 2–12 wt %); were added to polycarbonate (PC) and the resulting composites were tested for EC and tensile modulus. With the filler aspect ratio determined from EC values for CNT/PC and GNP/PC composites, the three‐dimensional randomly oriented fiber Halpin‐Tsai model accurately estimates the tensile modulus for the CNT/PC composites and the Nielsen model predicts the tensile modulus well for the CB/PC and GNP/PC composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dynamic mechanical and morphological properties of polycarbonate/multi-walled carbon nanotube composites

Dynamic mechanical and morphological properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) composites were studied by dynamic mechanical thermal analysis (DMTA) and X-ray diffractometry, respectively. For the without annealed PC/MWNT composites containing the higher content of the MWNT (≥7.0 wt%), double tan δ peaks were observed, which could be explained by the phase separation morphology model. For the annealed PC/MWNT composites, a broad single tan δ peak was observed. From the X-ray diffraction of the annealed PC/MWNT composites, it was observed that more regular structure of the PC was obtained, which was consistent with the result of the thermal analysis of the annealed PC/MWNT composites. From the dynamic mechanical properties, thermal analysis, and X-ray diffraction of the annealed PC/MWNT composites, it is suggested that PC/MWNT composites show a broad single tan δ peak and partially crystalline structure of the PC in the PC/MWNT composites by annealing.     

离子液体中制备碳纳米管复合材料的研究

与传统的溶剂相比,离子液体作为一种新型的绿色环保溶剂及优良电解质,在碳纳米管复合材料制备中得到了广泛的应用.对近年来利用离子液体合成出的碳纳米管/金属复合材料、碳纳米管/纤维素复合材料、碳纳米管/聚合物复合材料,以及在高分子离子液体、离子液凝胶中制备的碳纳米管复合材料进行了综述,介绍它们的优势及特点.对今后离子液体在碳...     

Thermosetting polyurethane multiwalled carbon nanotube composites

Thermosetting polyurethane (PU) multi‐walled carbon nanotube (MWCNT) nanocomposites at loadings up to 1 wt % were prepared via an addition polymerization reaction. The morphology of the nanocomposites and degree of dispersion of the MWCNTs was studied using a combination of scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and wide angle X‐ray diffraction (WAXD), and revealed the nanotubes to be highly dispersed in the PU matrix. Addition of just 0.1 wt % MWCNTs resulted in significant enhancements in stiffness, strength and toughness. Increases in Young's modulus, % elongation at break and ultimate tensile strength of 561, 302 and 397% were measured for the nanocomposites compared to the unfilled PU. The effect of the MWCNTs on the modulus of the PU was evaluated using the Rule of Mixtures, Krenchel and Halpin‐Tsai models. Only the Halpin‐Tsai model applied to high aspect ratio nanotubes was in good agreement with the modulus values determined experimentally. Strong interfacial shear stress was found between PU chains and nanotubes, up to 439 MPa, calculated using a modified Kelly‐Tyson model. Evidence for strong interfacial interactions was obtained from the Raman spectra of both the precursor materials and nanocomposites. When the MWCNTs were added to the isophorone diisocyanate an up‐shift of 14 cm^?1 and on average 40 cm^?1 was obtained for the position of the carbon‐hydrogen (C? H) out‐of plane bending (766 cm^?1) and isocyanate symmetric stretch (1420 cm^?1) modes respectively. Moreover, an up‐shift of 24 cm^?1 was recorded for the nanotube tangential mode (G‐band) for the 1.0 wt % nanocomposite because of the compressive forces of the PU matrix acting on the MWCNTs. The dynamic mechanical (DMA) properties of the PU thermoset and the nanocomposites were measured as a function of temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Impact damage sensing in glass fiber reinforced composites based on carbon nanotubes by electrical resistance measurements

In this article, we report an interesting employment of multi‐walled carbon nanotubes as a filler in the epoxy matrix of a glass fiber reinforced composite (FRP). The intrinsic electrical conductivity of carbon nanotubes made the development of a nanocomposite with enhanced electrical properties possible. The manufactured nanocomposite was subsequently employed in the production of a glass FRP. Due to the high aspect ratio of carbon nanotubes, very small amounts of these particles were sufficient to modify the electrical properties of the obtained glass fiber composites. Basically, a three‐phases material was developed, in which two phases were electrically insulating—epoxy matrix and glass fiber—and one phase highly conductive, the carbon nanotubes. The main goal of this study was to investigate the possibility of developing a glass fiber reinforced nanocomposite (GFRN), which is able to provide measurable electrical signals when subjected to a low‐velocity impact on its surface. Following this goal, the drop in the mechanical performance of the composite was evaluated before and after the impact. At the same time, the variation in its electrical resistance was measured. The results have shown that it is possible to associate the increase in electrical resistance of the composite with the formation of damages caused by impact. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal conductivity and dynamic mechanical property of glycidyl methacrylate‐grafted multiwalled carbon nanotube/epoxy composites

The well dispersed multiwalled carbon nanotube (MWCNT)/epoxy composites were prepared by functionalization of the MWCNT surfaces with glycidyl methacrylate (GMA). The morphology and thermal properties of the epoxy nanocomposites were investigated and compared with the surface characteristics of MWCNTs. GMA‐grafted MWCNTs improved the dispersion and interfacial adhesion in epoxy resin, and enhanced the network structure. The storage modulus of 3 phr GMA‐MWCNTs/epoxy composites at 50°C increased from 0.32 GPa to 2.87 GPa (enhanced by 799%) and the increased tanδ from 50.5°C to 61.7°C (increased by 11.2°C) comparing with neat epoxy resin, respectively. Furthermore, the thermal conductivity of 3 phr GMA‐MWCNTs/epoxy composite is increased by 183%, from 0.2042 W/mK (neat epoxy) to 0.5781 W/mK. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modeling and statistical understanding: The effect of carbon nanotube on mechanical properties of recycled polycaprolactone/epoxy composites

Recycling of polymer composites has been explored in an attempt to reutilize materials. Several efforts have opted to address this subject from many perspectives including mechanical, chemical, and thermal recycling. Others have also delved into the self-healing materials to remedy this dilemma. However, few studies have delved into understanding the role of carbon nanotube (CNT) in self-healing based recycled polymer composites. Therefore, in this study, experimental and simulation tools were utilized to understand the recycling process when CNTs were incorporated within recycled polycaprolactone/epoxy composites. A polynomial regression model, as a facile approach, was established to simulate the process-property relationship, which is essential for the successful implementation of the future of manufacturing. It found that, by adding CNTs, a reduction in the determined degree of crystallization was induced which correlated with the obtained reduction in the modulus and toughness. Strategies for enhancing mechanical properties have been pointed out for future endeavors.     

碳纳米管/聚合物纳米复合纤维静电纺丝研究进展

简述了静电纺丝装置的发展及其基本原理;介绍了静电纺丝制备碳纳米管/聚合物纳米复合纤维的技术进展,主要技术是碳纳米管在聚合基体中的分散性以及二者之间的界面结合力;详述了碳纳米管/聚丙烯腈纳米复合纤维和碳纳米管/聚氧乙烯(PEO)纳米复合纤维的制备及技术进展。指出今后应进一步发挥碳纳米管的性能,改进静电纺丝装置。     

碳纳米管预处理方法对天然橡胶/纯化碳纳米管复合材料力学性能的影响

纯化后的碳纳米管(CNT)分别经过球磨、表面活性剂十二烷基苯磺酸钠或分散-黏合体系预处理,再与100份(质量)天然橡胶(NR)混炼,可制备NR/纯化CNT复合材料。结果表明,纯化CNT直接与NR混炼,前者在NR中的分散效果不好,二者的界面结合欠佳。纯化CNT经球磨后,团聚程度增加,对复合材料力学性能影响不大。经表面活性剂十二烷基苯磺酸钠处理后的纯化CNT,内聚能下降,用差示扫描量热法(DSC)测定复合材料的DSC曲线表明,复合材料的结晶熔融峰面积增大,力学性能降低。用分散-黏合体系处理纯化CNT,可同时提高纯化CNT在橡胶中的分散效果及界面黏合性,试样结晶熔融峰变得不明显,因此该复合材料的邵尔A型硬度提高,拉伸强度、300％定伸应力和撕裂强度等优于其他试样。     

Morphology,thermal stability,and dynamic mechanical properties of atactic polypropylene/carbon nanotube composites

Nanocomposites based on atactic polypropylene (aPP) and multiwall carbon nanotubes were prepared by melt blending at 80°C with a Barabender mixer. The morphology, thermal stability, and dynamic mechanical properties of the obtained composites were studied subsequently. SEM observations indicate that the nanotubes are well dispersed in the aPP matrix. Each nanotube is covered by a layer of aPP molecules. Thermal stability of the aPP in nitrogen is found to be enhanced significantly by the addition of nanotubes. Peak temperature of the DTG curve for the nanocomposite with 5 wt % nanotube loading shows about 70°C higher than that of pure aPP. Dynamic mechanical properties of aPP are also influenced by nanotubes, as shown by the increase in the storage modulus as well as significantly broadened loss tanδ peak. These effects of nanotubes on the thermal stability and mechanical properties of aPP are explained by the adsorption effect of the aPP molecules on the nanotube surfaces in this study. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1087–1091, 2005     

Rheological and dielectrical characterization of melt mixed polycarbonate-multiwalled carbon nanotube composites

A series of composites of polycarbonate (PC) with 23 different contents of multiwalled carbon nanotubes (MWNT) was produced by melt mixing using the masterbatch dilution method. In dielectric measurements, AC conductivity and complex permittivity data obtained in the frequency range between 10⁻³ and 10⁷ Hz at room temperature indicated the electrical percolation threshold at about 1.0 wt%.

The dynamic mode melt rheological measurements for the same samples at eight temperatures between 170 and 280 °C showed a visible change in the frequency dependence of dynamic moduli and the absolute value of the complex viscosity |η*| particularly at low frequencies. In literature these changes are sometimes related to so called ‘percolation threshold concentration’. Applying this picture to our experimental data we have to assume that the percolation threshold is strongly dependent on the measurement temperature. It changes from about 5 to 0.5 wt% MWNT by increasing the measurement temperature from 170 to 280 °C, respectively. This temperature dependence cannot be explained by a classical liquid-solid transition but may be related to the existence of a combined nanotube-polymer network.     

Nanotube surface functionalization effects in blended multiwalled carbon nanotube/PVDF composites

A mixed fill system of multiwalled carbon nanotubes (MWCNT) and hydroxylated MWCNT (HO‐MWCNT) in a poly(vinylidene fluoride) (PVDF) matrix was investigated to improve nanotube dispersion and enhance electrical percolation for the bulk nanocomposites. Nonfunctionalized MWCNT were blended at various concentrations into dimethylformamide solutions containing PVDF with 0, 5, or 10 wt % HO‐MWCNT. Composite samples prepared from these solutions were examined by four‐point probe resistivity measurements. The percolation threshold decreased from 0.49 wt % MWCNT in binary MWCNT/PVDF composites to 0.25 wt % for ternary composites containing MWCNT/HO‐MWCNT/PVDF, with either 5 or 10 wt % HO‐MWCNT. In the case of the ternary composite with 10 wt % HO‐MWCNT, the lowest fill percent of MWCNT (0.25 wt %) measured a conductivity that was three orders of magnitude higher than the binary MWCNT/PVDF composite containing twice the concentration of MWCNT (0.5 wt %). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization behavior of polyamide 11/multiwalled carbon nanotube composites

Differential scanning calorimetry (DSC) was used to investigate the isothermal and nonisothermal crystallization kinetics of polyamide11 (PA11)/multiwalled carbon nanotube (MWNTs) composites. The Avrami equation was used for describing the isothermal crystallization behavior of neat PA11 and its nanocomposites. For nonisothermal studies, the Avrami model, the Ozawa model, and the method combining the Avrami and Ozawa theories were employed. It was found that the Avrami exponent n decreased with the addition of MWNTs during the isothermal crystallization, indicating that the MWNTs accelerated the crystallization process as nucleating agent. The kinetic analysis of nonisothermal crystallization process showed that the presence of carbon nanotubes hindered the mobility of polymer chain segments and dominated the nonisothermal crystallization process. The MWNTs played two competing roles on the crystallization of PA11 nanocomposites: on the one hand, the MWNTs serve as heterogeneous nucleating agent promoting the crystallization process of PA11; on the other hand, the MWNTs hinder the mobility of the polymer chains thus retarding the crystal growth process of PA11. The activation energies of PA11/MWNTs composites for the isothermal and nonisothermal crystallization are lower than neat PA11. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Microwave absorbing properties of a radar absorbing structure composed of carbon nanotube papers/glass fabric composites

In this study, carbon nanotube papers were employed in fabricating thin and broadband radar absorbing structures (RAS). Different concentrations of the CNT papers have been made by using a vacuum filtration method, with 20 × 20 cm in size and 21-27 μm in thickness. An epoxy resin was added into the CNT paper and then cured to become a composite with 1-5 wt.% of CNTs and 83-309 μm in thickness. The complex permittivity and permeability (ε′, ε″, μ′, μ″) of the CNT paper composites were measured using the transmission/reflection method in the frequency range of 2-18 GHz. The results reveal that the real (ε′) and imaginary (ε″) parts of the complex permittivity are increased with the CNT concentration. The ε′ of 5 wt.% CNT sample reaches 323 at 2 GHz and then decreases to 49.0 at 18 GHz. The ε″ reaches 321 at 2 GHz and decreases to 26.0 at 18 GHz. The CNT paper composite combined with a glass fabric composite used for a dielectric spacer is fabricated for an innovative RAS and the reflection loss is measured using the arch method in a microwave anechoic chamber. The results show that the 5 wt.% CNT paper composite/glass fabric composite absorbers attain maximum reflection loss of −13.3 dB at 12.0 GHz, −13.8 dB  at 10.0 GHz, and −16.0 dB at 7.5 GHz for spacer thickness of 1.5, 2.0, and 3.0 mm, respectively.     

Electrochemical capacitance of well-coated single-walled carbon nanotube with polyaniline composites

Well-coated single-walled carbon nanotube (SWNT) with polyaniline (PANI) composite electrodes with good uniformity for electrochemical capacitors are prepared by the polymerization of aniline containing well-dissolved SWNTs. The capacitance properties are investigated with cyclic voltammetry, charge-discharge tests and ac impedance spectroscopy. The composite electrode shows much higher specific capacitance, better power characteristics and is more promising for application in capacitor than pure PANI electrode. The effect and role of SWNT in the composite electrode are also discussed in detail.     

Influence of nanoclays on electrical and morphological properties of thermoplastic polyurethane/multiwalled carbon nanotube/clay nanocomposites

Nanocomposites of thermoplastic polyurethanes (TPUs), multiwalled carbon nanotubes (MWCNTs) and clays were prepared via melt processing using polyether‐ and polyester‐based TPUs, MWCNTs, and organically modified nanoclays (Cloisite C30B and C25A). Coaddition of clays and MWCNTs to TPU nanocomposites increased their electrical conductivities above those without any clay. Nanoclay alone is shown to produce no effect on electrical conductivity. TEM results show that the coaddition of nanoclay affects the nanocomposite morphology by changing the MWCNT distribution. Clay C25A and MWCNTs were observed to form network structures in the nanocomposites, resulting in improved electrical conduction. Interaction between MWCNTs and clays as well as an increase in nanocomposite viscosity caused by the coaddition of clays may influence the morphology change. Most of the nanocomposites containing both MWCNTs and clay exhibited higher dielectric constants, indicating higher electrical conductivities. Tensile properties investigations confirmed the reinforcing effects of the MWCNTs and clays. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Cellulose acetate/multiwalled carbon nanotube nanocomposites with improved mechanical,thermal, and electrical properties

Cellulose acetate (CA)‐based nanocomposites with various contents of neat multiwalled carbon nanotube (MWCNT) or acid‐treated one (MWCNT‐COOH) are prepared via melt‐compounding method and investigated their morphology, thermal stability, mechanical, and electrical properties. SEM microphotographs reveal that MWCNT‐COOHs are dispersed uniformly in the CA matrix, compared with neat MWCNTs. FTIR spectra support that there exists a specific interaction between carboxyl groups of MWCNT‐COOHs and ester groups of CA, indicating good interfacial adhesion between MWCNT‐COOHs and CA matrix. Accordingly, thermal stability and dynamic mechanical properties of CA/MWCNT‐COOH nanocomposites were higher than those of CA/MWCNT composites. On the contrary, electrical volume resistivities of CA/MWCNT‐COOH nanocomposites are found to be somewhat higher than those of CA/MWCNT composites, which is because of the deterioration of graphene structures for MWCNT‐COOHs and the good dispersion of MWCNT‐COOHs in the CA matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dielectric spectroscopy on melt processed polycarbonate—multiwalled carbon nanotube composites

Complex permittivity and related AC conductivity measurements in the frequency range between 10⁻⁴ and 10⁷ Hz are presented for composites of polycarbonate (PC) filled with different amounts of multiwalled carbon nanotubes (MWNT) varying in the range between 0.5 and 5 wt%. The composites were obtained by diluting a PC based masterbatch containing 15 wt% MWNT by melt mixing using a Micro Compounder. From DC conductivity measurements it was found that for samples processed at a mixing screw speed of 150 rpm for 5 min, the percolation occurs at a threshold concentration (p_c) between 1.0 and 1.5 wt% MWNT. For concentrations of MWNT near the percolation threshold, the processing conditions (screw speed and mixing time) were varied. The differences in the dispersion of the MWNT in the PC matrix could be detected in the complex permittivity and AC conductivity spectra, and have been explained by changes in p_c. The AC conductivity and permittivity spectra are discussed in terms of charge carrier diffusion on percolation clusters and resistor-capacitor composites.