碳纳米管改性环氧树脂的导热和阻燃性能

以双酚A二缩水甘油醚(DGEBA)环氧树脂(Epoxy Resin,EP)为基体、甲基六氢苯酐(MHHPA)为固化剂、以多壁碳纳米管(MWCNTs)为添加剂制备了环氧树脂/碳纳米管纳米复合材料。通过对微观结构、玻璃化转变温度(Tg)、热失重、热导率和锥形量热测试结果分析,研究了质量分数少于1.5%的MWCNTs对环氧树脂的导热和阻燃性能影响,结果表明,MWCNTs质量分数为1.5%时,复合材料发生团聚;纳米复合材料随着MWCNTs质量分数的增加Tg值先增加后降低;失重5%时,对应的温度先增加后降低,残炭量增加;样品的热导率呈现先升高后降低的趋势,当MWCNTs质量分数为1%时,复合材料的热导率最大;MWCNTs加入后环氧树脂的总释热量减少,释烟量增加,阻燃性得到一定程度的提高。     

Improved flame retardant properties of epoxy resin by fluorinated MMT/MWCNT additives

Flame retardant additives of montmorillonite (MMT) and multi-walled carbon nanotube (MWCNT) were embedded in epoxy resin to improve the resin's flame retardant properties. MMT was fluorinated to exfoliate its layers and enhance its dispersion into the epoxy resin. The MWCNT was also fluorinated to create hydrophobic functional groups for improved dispersion into the epoxy resin. The MWCNT reduced the degradation rate of the epoxy resin and increased the char yield. Limiting oxygen index also increased showing first order against char yield. The exfoliated MMT acted as an energy storage medium to hinder thermal transfer within the epoxy resin. The activation energy increased almost two times by fluorinated MMT/MWCNT additives. The fluorination of the additives, MMT and MWCNT significantly improved the flame retardant properties of the epoxy resin.     

Preparation and Properties of Pyrene-Modified Multi- Walled Carbon Nanotube/Epoxy Resin Nanocomposites

Nanocomposites of multi-walled carbon nanotube (MWCNT)/bis-phenol A type epoxy resin were prepared and physical properties of the nanocomposites were investigated. For the fine dispersion of MWCNT in the epoxy resin, MWCNT was modified with pyrene butyric acid (PBA) in the supercritical carbon dioxide (CO₂). The physical adsorption of PBA on the surface of MWCNTs was studied with a thermogravimetric analyzer and a transmission electron microscopy. The electrical surface resistivities of the nanocomposites showed threshold decreases due to percolations above the critical concentration of the MWCNT. The resistivities showed maximum depending on the concentration and the modification of the surface of the MWCNT with PBA. It is postulated that the dispersion of the MWCNT in epoxy resins resulted in dispersion systems which exhibit rheological properties similar to lyotropic liquid crystalline polymers. The surface resistivities of the MWCNT/epoxy systems reflected the morphological characteristics of the systems which also determined rheological properties of the systems.     

Complementary effects of multiwalled carbon nanotubes and conductive carbon black on polyamide 6

This article introduces a newly innovative idea for preparation of superconductive ternary polymeric composites of polyamide 6 (PA6), conductive carbon black (CCB), and multiwalled carbon nanotubes (MWCNTs) with different weight ratios by a melt‐mixing technique. The complementary effects of CCB and MWCNTs at different compositions on rheological, physical, morphological, thermal, and dynamic mechanical and electrical properties of the ternary composites have been examined systematically. We have used a novel formulation to produce high‐weight fraction ternary polymer composites that show extremely higher conductivity when compared with their corresponding binary polymer composites at the same carbon loading. For example, with an addition of 10 wt % MWCNTs into the CCB/PA6 composite preloaded with 10 wt % CCB, the electrical conductivity of these ternary composites was about 5 S/m, which was 10 times that of the CCB/PA6 binary composite (0.5 S/m) and 125 times that of the MWCNT/PA6 binary composite (0.04 S/m) at 20 wt % carbon loading. The incorporation of the MWCNTs effectively enhanced the thermal stability and crystallization of the PA6 matrix in the CCB/PA6 composites through heterogeneous nucleation. The MWCNTs appeared to significantly affect the mechanical and rheological properties of the PA6 in the CCB/PA6 composites, a way notably dependent on the MWCNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1203–1212, 2010     

Strengthening of liquid crystalline polymer by functionalized carbon nanotubes through interfacial interaction and homogeneous dispersion

Multiwalled carbon nanotubes (MWCNTs) were functionalized with two types of chemical moieties (i.e. carboxylic, ? COOH and hydroxyl benzoic acid groups, ‐HBA) on their sidewalls in order to improve their interaction with a liquid crystalline polymer (LCP) and dispersion in LCP. We have investigated the rheological, mechanical, dynamic mechanical, and thermal properties in detail with variation of HBA‐functionalized MWCNTs in the LCP matrix. Effect of the dispersion state of the functionalized MWCNTs in the LCP matrix on the rheological behavior was also studied. The composites containing HBA‐functionalized MWCNTs showed higher complex viscosity, storage, and loss modulus than the composites with the same loading of raw MWCNTs and MWCNT‐COOH. It was suggested that the HBA‐functionalized MWCNTs exhibited a better dispersion in the polymer matrix and formed stronger CNT‐polymer interaction in the composites than the raw MWCNTs and MWCNT‐COOH, which was also confirmed by FESEM and FTIR studies. As a result, the overall mechanical performance of the HBA‐MWCNT‐LCP composites could be improved significantly. For example, the addition of 4 wt% HBA‐MWCNT to LCP resulted in the considerable improvements in the tensile strength and modulus of LCP (by 66 and 90%, respectively). Copyright © 2010 John Wiley & Sons, Ltd.     

多壁碳纳米管对聚甲醛性能的影响

将多壁碳纳米管(MWCNTs)和聚甲醛(POM)在转矩流变仪中熔融混合得到POM/MWCNT复合材料.研究了复合材料的形态,导热性能,导电性能,流变性能和结晶性能.结果表明,MWCNTs在没有经过处理的情况下能够均匀地分散在POM基体中;当向POM中添加1.0 wt%含量MWCNTs时,复合材料的导热系数上升到0.5289 W/(K m),比纯POM的导热系数0.198 W/(K m)提高1.5倍,通过有效介质方法(EMA)验证了体系导热系数提高幅度不大的原因是MWCNTs与POM之间形成了很高的界面热阻;当MWCNTs的含量为1.0 wt%时,体系产生了导电逾渗效应,逾渗值在0.5 wt%~1.0 wt%之间;MWCNTs对POM有显著的成核作用,当向POM中添加0.5 wt%含量的MWCNTs时,POM的结晶温度提高6℃左右,但当MWCNTs的添加量进一步增加时,结晶温度几乎不再变化,成核效果呈现"饱和"状态.另外,材料的复数黏度,储能模量和损耗模量随MWCNTs含量的增加而增加.     

Influence of organo-clay on electrical and mechanical properties of PP/MWCNT/OC nanocomposites

The electrical, thermal and mechanical properties of nanocomposites, based on polypropylene (PP) filled by multi-walled carbon nanotubes (MWCNTs) and organo-clay (OC), were studied with the purpose of finding out the effect of OC on the microstructure of MWCNTs dispersion and PP/MWCNT/OC composites. It was found that addition of organo-clay nanoparticles improved nanotube dispersion and enhanced electrical properties of PP/MWCNT nanocomposites. Addition of organo-clay (MWCNT/OC ratio was 1/1) reduced the percolation threshold of PP/MWCNT nanocomposites from ?_c = 0.95 vol.% to ?_c = 0.68 vol.% of carbon nanotubes, while the level of conductivity became 2–4 orders of magnitude higher. The DSC and DMA analyses have shown that the influence of organo-clay on the thermal and mechanical properties of material was not significant in composites with both fillers as compared to PP/OC. Such an effect can be caused by stronger interaction of OC with carbon nanotubes than with polymer matrix.     

Combined effect of graphene oxide and MWCNTs on microwave absorbing performance of epoxy composites

Currently, carbon nanotube (CNT) ‐based composites have been considered as microwave absorbers because of the fascinating properties of CNTs. In this work, multi‐walled CNTs (MWCNTs) and graphene oxide (GO) ‐based epoxy composites (i.e. MWCNT/EPr and GO‐MWCNT/EPr), with sample thickness of 2 mm, were prepared to study microwave absorbing properties in the frequency band of 8–18 GHz. Uniform dispersion of MWCNTs in the organic solvent and polymer matrix was achieved by preparation of GO. The test for electromagnetic parameters, i.e. complex permittivity and the permeability of the samples, was carried out with vector network analyzer (VNA) using reflection‐transmission waveguides. Results showed that GO‐MWCNT/EPr composites have better absorption capability than MWCNT/EPr composites. The improved reflection loss for the composites with 0.4 wt% and 0.6 wt% of GO (out of total filler loading 6 wt%) were ?14.32 dB and ?14.29 dB, respectively. The improvement in reflection loss and absorption bandwidth for GO‐MWCNTs composites suggested that MA features are synergistically effected by GO and MWCNTs. Further skin depth and shielding effectiveness terms are studied to observe overall mechanism of electromagnetic (EM) shielding which showed that multiple reflections also play a role in EM shielding. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of MWCNT morphology on dispersion and thermal properties of polyethylene nanocomposites

In this study a series of multi-walled carbon nanotube (MWCNT)/Polyethylene (PE) composites with different kinds and several concentrations of carbon nanotubes (CNTs) were investigated. The morphology and degree of dispersion of the fillers in the polymer matrix at different length scales was investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Both individual and agglomerated MWCNTs were evident but a good dispersion was observed for some of them. TGA measurements were performed on nanocomposites in order to understand if CNTs affect the stabilization mechanism during thermal and oxidative degradation. The analysis demonstrates that MWCNTs presence slightly delays thermal volatilisation (15-20 °C) without modification of thermal degradation mechanism. In contrast, thermal oxidative degradation in air is delayed up to about 100 °C dependently from MWCNTs concentration, in the range used here (0.1-2.0 wt%), and degree of dispersion. The stabilization is due to the formation of a thin protective layer of entangled MWCNTs kept together by carbon char generated on the surface of the nanocomposites as shown by SEM images taken on degradation residues.     

Rheological and electrical properties of polypropylene/MWCNT composites prepared with MWCNT masterbatch chips

Melt compounded PP/MWCNT (polypropylene/multi-walled carbon nanotube) composites were prepared by diluting highly concentrated masterbatch chips. Maleic anhydride grafted polypropylene (PP-g-MAH) was used as a compatibilizer to promote dispersion and interaction of MWCNTs. Rheological properties were investigated with respect to the MWCNT and compatibilizer loadings, and related to morphological and electrical properties. As the MWCNT loading was increased, shear viscosity and yield stress were increased at low shear rate region because of increased interaction between MWCNT particles. When the MWCNT loading was low, MWCNT dispersion was improved by the PP-g-MAH compatibilizer because MWCNTs were wetted sufficiently due to the presence of the compatibilizer. However, rheological and electrical properties of highly concentrated MWCNT composites with the compatibilizer were not improved compared with PP/MWCNT composites without the compatibilizer because the compatibilizer did not provide sufficient wrapping of MWCNT particles. Electrical and morphological properties of PP/MWCNT composites were correlated with the rheological properties in steady and dynamic oscillatory shear flows.     

Properties of matrix-grafted multi-walled carbon nanotube/poly(methyl methacrylate) nanocomposites synthesized by in situ reversible addition-fragmentation chain transfer polymerization

Multi-walled carbon nanotubes (MWCNT)/poly(methyl methacrylate) (PMMA) nanocomposites were synthesized by the in situ reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) in the presence of MWCNTs, at which the bulk polymer was grafted onto the surface of nanotubes through the ??grafting through?? strategy. For this purpose, MWCNTs were formerly functionalized with polymerizable MMA groups. MMA and PMMA-grafted MWCNTs were characterized by Fourier-transform infrared spectroscopy, Raman, X-ray photoelectron spectroscopy, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Dissolution of nanotubes was examined in chloroform solvent and studied by UV?Cvis spectroscopy. Thermogravimetric and degradation behavior of prepared nanocomposites was investigated by TGA. MWCNTs had a noticeable boosting effect on the thermal stability of nanocomposites. TGA thermograms showed a two-step weight loss pattern for the degradation of MWCNT-PMMA/PMMA nanocomposites which is contrast with neat PMMA. Introduction of MWCNTs also improved the dynamic mechanical behavior and electrical conductivity of nanocomposites. TEM micrograph of nanocomposite revealed that the applied methods for functionalization of nanotubes and in situ synthesis of nanocomposites were comparatively successful in dispersing the MWCNTs in PMMA matrix.     

A facile rheological approach for the evaluation of “super toughness point” of compatibilized HDPE / MWCNT nanocomposites

Fast and efficient determination of the optimal mechanical property of a polymer/CNT nanocomposite is crucial to develop polymer conductive nanocomposites. This work establishes a rheological approach to evaluate the super-toughness point of compatibilized high density polyethylene (HDPE)/multi-walled carbon nanotube (MWCNT) nanocomposites. Results illustrate that three types of HDPE/MWCNT nanocomposites exhibit obvious gel plateaus in the dynamic rheological curves and the gel points of nanocomposites with compatibilizer shift to the low MWCNTs loading. The super-toughness points of HDPE/MWCNT nanocomposites with compatibilizers show the correspondence with the gel points acquired from the rheological data, indicating that dynamic rheology is an effective way to determine the super-toughness points of HDPE/MWCNT nanocomposites with compatibilizers. Furthermore, unique network structure at the gel points is directly observed and the new mechanism of toughness is proposed. This study provides new insights for effective control of the structures and properties of polymer/CNT nanocomposites.     

Effects of organo-montmorillonite dispersion on thermal stability of epoxy resin nanocomposites

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo-montmorillonite (O-MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The dispersion state of the MMT in the matrix was investigated by X-ray diffraction and scanning electronic microscopy. The thermal stability of the epoxy nanocomposites was examined by TGA. Thermal stability of the epoxy nanocomposite is dependent upon the dispersion state of the OMMT in the epoxy matrix although all the epoxy nanocomposites had enhanced thermal stability compared with the neat epoxy resin. The thermal stability of the epoxy resin nanocomposites was correlated with the dispersion state of the MMT in the epoxy resin matrix.     

Thermal Degradation Behavior and Kinetic Analysis of Ultra High Molecular Weight Polyethylene Based Multi-Walled Carbon Nanotube Nanocomposites Prepared Via in-situ Polymerization

Thermal degradation behavior of multi-wall carbon nanotubes (MWCNTs)/ultra high molecular weight polyethylene (UHMWPE) nanocomposites, with different nanotubes contents (0.5, 1.5 and 3.5 wt%) prepared via in-situ polymerization technique have been investigated using thermal gravimetric analysis (TGA). TGA spectra revealed that these nanocomposites had enhanced thermal stability and no significant mass loss (<0.4 wt%) occurred up to 350°C. Thermal degradation of these UHMWPE/MWCNT nanocomposites was investigated in terms of parameters such as the onset temperature of degradation (T₁₀), the decomposition temperature at 50% wt loss (T₅₀), the degradation temperature of maximum rate of the weight loss (T_m), and the residual yields (W_R) from TGA. The degradation activation energies (E) of virgin UHMWPE and its nanocomposites were estimated using the Friedman, the Ozawa, Flynn, and Wall (OFW), and the Kissinger's methods. Results indicated that the degradation activation energy for the virgin UHMWPE was 281.3 kJ/mol. The activation energy increased with increasing nanotube loading up to 1.5 wt% indicating that MWCNTs had a stabilizing effect on the degradation of the matrix. However, loadings of 3.5 wt% of nanotube or more could slightly decrease the activation energy. The decrease in the activation energy for degradation of nanocomposites with higher MWCNT concentrations might be attributed to the catalytic effects of nanotubes and polymerization catalyst residues. The “model fitting” method indicated a mechanism of n ^th-order auto-catalysis from the form of the conversion curves for UHMWPE/MWCNTs nanocomposites prepared via in-situ polymerization.     

The effect of mixing methods on the dispersion of carbon nanotubes during the solvent-free processing of multiwalled carbon nanotube/epoxy composites

Several solvent-free processing methods to disperse multiwalled carbon nanotubes (MWCNTs) in bisphenol F-based epoxy resin were investigated, including the use of a microfluidizer (MF), planetary shear mixer (PSM), ultrasonication (US) and combinations. The processed mixture was cured with diethyl toluene diamine. Three complimentary techniques were used to characterize the dispersion of the MWCNTs in cured composite samples: optical microscopy, micro Raman spectroscopy, and scanning electron microscopy (SEM). For sample MF + PSM, optical micrographs and Raman images showed reduced agglomeration and a homogeneous distribution of MWCNTs in the epoxy matrix. SEM analysis of fractured specimen after tensile testing revealed breakage of nanotubes along the fracture surface of the composite. A comparison of the MWCNT dispersion in the epoxy samples processed using different methods showed that a combination of MF and PSM processing yields a more homogeneous sample than the PSM or US + PSM processed samples. Mechanical testing of the composites showed about 15% improvement in the tensile strength of samples processed by the MF + PSM method over other methods. Thermogravimetric analysis (TGA) results showed a small decrease in the onset degradation temperature for poorly dispersed samples produced by PSM compared with the well-mixed samples (MF + PSM). These results strongly suggest that the MF + PSM processing method yield better-dispersed and stronger MWCNT/epoxy composites. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Influence of Mixing Conditions on Morphologies and Properties of MMT/Epoxy Resin Composite Materials

Montmorillonite(MMT) was directly modified with hexadecyl trimethyl ammonium bromide. The interlayer spacing of the organophilic montmorillonite(organo-MMT) corresponding to the d(001) plane peak was 2.21 nm. The influences of the content of organo-MMT and mixing conditions including mixing temperature and mixing time on the intercalation and exfoliation structures of MMT/epoxy resin composites were investigated by wide X-ray diffraction(WXRD). The X-ray patterns reveal that organo-MMT was intercalated by the epoxy resin during mixing process. Only under certain mixing conditions, could the exfoliation nanocomposites be formed. The mechanical and thermal properties of the composites were measured. The results indicate that the composites have better mechanical properties and higher Tg than those of the pristine epoxy resin.     

Exploitation of introducing of catalytic centers into layer galleries of layered silicates and related epoxy nanocomposites. I. Epoxy nanocomposites derived from montmorillonite modified with catalytic surfactant‐bearing carboxyl groups

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (T_g's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher T_g's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004     

Core–shell functionalized MWCNT/poly(m‐aminophenol) nanocomposite with large dielectric permittivity and low dielectric loss

Core–shell carboxyl‐functionalized multiwall carbon nanotube (c‐MWCNT)/poly(m‐aminophenol) (PmAP) nanocomposite were prepared through in‐situ polymerization of m‐aminophenol (m‐AP) in the presence of MWCNTs, and explicated as a dielectric material for electronic applications. The formation of thin PmAP layer on individual c‐MWCNT with excellent molecular level interactions at interfaces was confirmed by morphological and spectroscopic analyses. Here we conducted a comparative study of the dielectric performances of PmAP based nanocomposite films with pristine MWCNTs and c‐MWCNTs as fillers. Compared to PmAP/MWCNT nanocomposites, the PmAP/c‐MWCNT nanocomposites exhibited higher dielectric permittivity and lower dielectric loss. The well dispersed c‐MWCNTs in PmAP/c‐MWCNT nanocomposite produce huge interfacial area together with numerous active polarized centers (crystallographic defects), which in turn intensified the Maxwell‐Wagner‐Sillars (MWS) effect based on excellent molecular level interactions and thus, produce large dielectric permittivity (8810 at 1 kHz). The percolation threshold of PmAP/c‐MWCNT nanocomposites is found lower than that of the PmAP/MWCNT nanocomposites, which could be attributed to homogeneous distribution of c‐MWCNTs and strong c‐MWCNT//PmAP interfacial interactions in the nanocomposites. Copyright © 2016 John Wiley & Sons, Ltd.     

The improvement in interfacial shear strength of wood fiber/epoxy composite by sizing with epoxy sizing agent containing MWCNTs

This paper discloses a feasible and high efficient strategy for wood fiber treatment to introducing multi‐wall carbon nanotubes (MWCNTs) to the surface of wood fibers for the aim of improving the interfacial shear strength of wood fiber/epoxy composite. Briefly, a layer of MWCNT was deposited on wood fibers through sizing wood fibers with epoxy sizing agent containing amine‐treated MWCNTs (MWCNT‐PEI). The surface functional groups, morphology, wettability, and interphase properties of MWCNTs on the surface of wood fiber were studied. The remarkable enhancements were achieved in interfacial shear strength of reinforced composites by dipping wood fiber in MWCNTCOOH suspension and wood fiber sizing containing MWCNT‐PEI.     

Melt‐crystallization mechanism of poly(ethylene terephthalate)/multi‐walled carbon nanotubes prepared by in situ polymerization

A series of poly(ethylene terephthalate)/multi‐walled carbon nanotubes (PET/MWCNTs) nanocomposites were prepared by in situ polymerization using different amounts of multi‐walled carbon nanotubes (MWCNTs). The polymerization of poly(ethylene terephthalate) (PET) was carried out by the two‐stage melt polycondensation method. The intrinsic viscosity (IV) of the composites is ranged between 0.31 and 0.63 dL/g depending on the concentration of the MWCNTs. A decrease of IV was found by increasing MWCNTs content. This is due to the reactions taking place between the two components leading to branched and crosslinked macromolecules. These reactions are, mainly, responsible for thermal behavior of nanocomposites. The melting point of the nanocomposites was shifted to slightly higher temperatures by the addition till 0.55 wt % of MWCNTs while for higher concentration was reduced. The degree of crystallinity in all nanocomposites was, also, reduced by increasing MWCNTs amount. However, from crystallization temperature, it was found that MWCNTs till 1 wt % can enhance the crystallization rate of PET, whereas at higher content (2 wt %), the trend is the opposite due to the formation of crosslinked macromolecules. From the extended crystallization analysis, it was proved that MWCNTs act as nucleating agents for PET crystallization. Additionally, the crystallization mechanism due to the existence of MWCNT becomes more complicated because two mechanisms with different activation energies are taking place in the different degrees of crystallization, depending on the percentage of MWCNT. The effect of molecular weight also plays an important role. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1452–1466, 2009