Improving dispersion of multiwalled carbon nanotubes in polyamide 6 composites through amino‐functionalization

The focus of this study is to investigate the state of dispersion of different treated multiwalled carbon nanotubes (MWNTs) in polyamide 6 (PA6). The MWNTs used in composites were grafted by 1,6‐hexamethylenediamine (HMD) via acid‐thionyl chloride to improve their compatibility with PA6 matrix. A microstructure transformation of MWNTs is found during the treatment process. Acidification makes the MWNTs compact and grafting HMD promotes the compact structure loose again. The MWNTs after different treatment were used to fabricate MWNTs/PA6 composites through melt blending. The dispersion of different MWNTs in PA6 was observed by a combination of scanning electron microscopy, optical microscopy, and transmission electron microscopy. The results show that the amino‐functionalized MWNTs are dispersed more homogeneously in PA6 than the purified MWNTs, and the poorest dispersion is achieved for acid treated MWNTs. It is indicated that the loose structure and functionalized surface of MWNTs benefit the dispersion of MWNTs in PA6. In addition, the amino‐functionalization of MWNTs improves the compatibility between the MWNTs and PA6, resulting in stronger interfacial adhesion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of carbon nanofiber functionalization on the in-plane mechanical properties of carbon/epoxy multiscale composites

In this work, vapor-grown carbon nanofibers (CNFs) were functionalized using an optimized route and dispersed in the matrix of carbon fabric-reinforced epoxy composites to develop multiscale carbon/epoxy composites. Functionalization was carried out through an oxidative treatment with a mixture of HNO₃/H₂SO₄ (1 : 3) using a combination of ultrasonication and magnetic stirring. Functionalized CNFs (F-CNFs) were characterized for their morphology, length, functional groups, and degradation due to oxidative treatment. The results showed that it was possible to efficiently functionalize CNFs without any degradation through proper selection of treatment duration. F-CNFs were dispersed homogeneously into the epoxy matrix using ultrasonication in combination with high-speed mechanical stirring. The incorporation of 0.1 wt % F-CNFs led to a 65% increase in Young's modulus and a 36% in tensile strength of neat carbon/epoxy composites. The fracture surfaces were studied using scanning electron microscopy to understand the property enhancement due to F-CNFs. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of phenol functionalization of carbon nanotubes on properties of natural rubber nanocomposites

This paper reports the results of studies on the effect of phenol functionalization of carbon nanotubes (CNTs) on the mechanical and dynamic mechanical properties of natural rubber (NR) composites. Fourier transform infrared spectrometry (FTIR) indicates characteristic peaks for ether and aromatic rings in the case of phenol functionalized CNT. Although differential scanning calorimetric (DSC) studies show no changes in the glass‐rubber transition temperature (T_g) of NR in the nanocomposites due to surface modification of CNT, dynamic mechanical studies show marginal shifting of T_g to higher temperature, the effect being pronounced in the case of functionalized CNT. Stress‐strain plots suggest an optimum loading of 5 phr CNT in NR formulations and the phenolic functionalization of CNT does not affect significantly the stress‐strain properties of the NR nanocomposites. The storage moduli register an increase in the presence of CNT and this increase is greater in the case of functionalized CNT. Loss tangent showed a decrease in the presence of CNT, and the effect is more pronounced in the case of phenol functionalized CNT. Transmission electron microscopy (TEM) reveals that phenol functionalization causes improvement in dispersion of CNT in NR matrix. This is corroborated by the increase in electrical resistivity in the case of phenol functionalized CNT/NR composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

碳纳米管填充聚合物基电磁屏蔽复合材料的研究进展

对碳纳米管填充聚合物基电磁屏蔽复合材料的研究进展进行了综述。在阐述研究电磁屏蔽材料必要性的基础上,介绍了复合材料的电磁屏蔽机理,重点论述了碳纳米管填充量、长径比及管径、屏蔽体的厚度、复合材料的加工方式等对复合材料电磁屏蔽性能的影响。最后对碳纳米管填充聚合物基复合电磁屏蔽材料的研究进行了展望,指出低成本填料与碳纳米管协同作用、可提高碳纳米管分散性的制备工艺的研究以及复合材料电磁屏蔽机理的研究等为未来的研究方向。     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Amino-functionalized carbon nanotubes for effectively improving the mechanical properties of pre-impregnated epoxy resin/carbon fiber

Pre-impregnated carbon fiber/epoxy resin (CF/epoxy prepreg) gained its popularity for significant stress applications, especially in the aerospace industry, owing to its excellent resistance and low specific mass. However, these CF/epoxy prepregs have a tendency to crack propagation. A solution for the prepregs fragility is the addition of carbon nanotubes (CNTs), especially those functionalized with amino groups, reinforcing the material due to its exceptional mechanical properties. In this work, the influence of the carbon chain length of two different amino-functionalized CNTs from diverse backgrounds (commercial and laboratory growth CNTs) is studied. The nanofillers were added in CF/epoxy prepregs by dry spraying without solvent aid. CNTs' samples were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, transmission electron microscopy, and thermogravimetric analysis (TGA), while the composites were analyzed by TGA, dynamic-mechanical analysis, and field emission scanning electron microscopy. The various surface treatment occurred at different levels according to the CNTs background, and all samples exhibited a distinct behavior. These differences were also observed in the composites' thermomechanical performance: CNTs functionalized with larger carbon chain amine presented the best results, with an increase of almost 100% in the storage moduli (E'), confirming the efficiency of amino-functionalized CNTs in the reinforcement of CF/epoxy prepregs.     

Thermal conductivity and electromagnetic shielding effectiveness of composites based on Ag‐plating carbon fiber and epoxy

Thermally conductive and electromagnetic interference shielding composites comprising low content of Ag‐plating carbon fiber (APCF) were fabricated as electronic packing materials. APCF as conductive filler consisting of carbon fiber (CF) employed as the structural component to reinforce the mechanical strength, and Ag enhancing electrical conductivity, was prepared by advanced electroless Ag‐plating processing on CF surfaces. Ag coating had a thickness of 450 nm without oxide phase detected. The incorporation of 4.5 wt % APCF into epoxy (EP) substrate yielded thermal conductivity of 2.33 W/m·K, which is approximately 2.6 times higher than CF–EP composite at the same loading. The APCF–EP composite performed electromagnetic shielding effectiveness of 38–35 dB at frequency ranging from 8.2 to 12.4 GHz in the X band, and electromagnetic reflection was the dominant shielding mechanism. At loading content of APCF up to 7 wt %, thermal conductivity of APCF–EP composites increased to 2.49 W/m·K. Volume resistivity and surface resistivity decreased to 9.5 × 10³ Ω·cm and 6.2 × 10² Ω, respectively, which approached a metal. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42306.     

High thermal conductive m‐xylylenediamine functionalized multiwall carbon nanotubes/epoxy resin composites

In this study, multiwall carbon nanotubes (MWNTs) functionalized by m‐xylylenediamine is used as thermal conductive fillers to improve their dispersibility in epoxy resin and the thermal conductivity of the MWNTs/bisphenol‐A glycidol ether epoxy resin composites. Functionalization with amine groups of MWNTs is achieved after such steps as carboxylation, acylation and amidation. The thermal conductivity, impact strength, flexural strength, and fracture surfaces of MWNTs/epoxy composites are investigated with different MWNTs. The results show that m‐xylylenediamine is successfully grafted onto the surface of the MWNTs and the mass fraction of the organic molecules grafted onto MWNTs is about 20 wt %. The thermal conductivity of MWNTs/epoxy composites is further enhanced to 1.236 W/mK with 2 wt % m‐MWNTs. When the content of m‐MWNTs is 1.5 wt %, the impact strength and flexural strength of the composites are 25.85 KJ/m², 128.1 MPa, respectively. Scanning electron microscope (SEM) results show that the fracture pattern of composites is changed from brittle fracture to ductile fracture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41255.     

Facile covalent surface functionalization of multiwalled carbon nanotubes with poly(2‐hydroxyethyl methacrylate) and interface related studies when incorporated into epoxy composites

Carbon nanotubes (CNTs) have seen increased interest from manufacturers as a nanofiber filler for the enhancement of various physical and mechanical properties. A major drawback for widespread commercial use has been the cost associated with growing, functionalizing, and incorporating CNTs into commercially available polymeric matrices. Accordingly, the main objective of this study was to investigate the effects of adding commercially viable functionalized multiwalled carbon nanotubes (MWCNT) to a commercially available epoxy matrix. The mechanical behavior of the nanocomposites was investigated by mechanical testing in tensile mode and fractures were examined by scanning electron microscopy. The thermal behavior was investigated by differential scanning calorimetry and thermogravimetric analysis. Molecular composition was analyzed by attenuated total reflectance Fourier transform infrared spectroscopy. Mechanical testing of the epoxy/functionalized‐MWCNT indicated that the 0.15 wt % functionalized MWCNT composite possessed the highest engineering stress and toughness out of the systems evaluated without affecting the Young's modulus of the material. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of amino‐functionalization of multi‐walled carbon nanotubes on the dispersion with epoxy resin matrix

Amino‐functionalization of multiwalled carbon nanotubes (MWCNTs) was carried out by grafting triethylenetetramine (TETA) on the surfaces of MWCNTs through the acid–thionyl chloride way. The amino‐functionalized MWCNTs show improved compatibility with epoxy resin and, as a result, more homogenous dispersion in the matrix. The mechanical, optical, and thermal properties of the amino‐functionalized MWCNT/epoxy composites were also investigated. It was found that introducing the amino‐functionalized MWCNTs into epoxy resin greatly increased the charpy impact strength, glass transition temperature, and initial decomposing temperature of cured epoxy resin. In addition, introducing unfunctionalized MWCNTs into epoxy resin was found greatly depressing the light transmission properties, which would affirmatively confine the application of the MWCNTs/epoxy composites in the future, while much higher light transmittance than that of unfunctionalized MWCNTs/epoxy composites was found for amino‐functionalized MWCNTs/epoxy composites. SEM of the impact cross section and TEM of ultrathin film of the amino‐functionalized MWCNTs/epoxy composites showed that the amino‐functionalized MWCNTs were wetted well by epoxy matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 97–104, 2006     

Enhanced impact resistance and electromagnetic interference shielding of carbon nanotubes films composites

High reliability and high-performance electromagnetic interference (EMI) shielding polymeric composite was fabricated by introducing carbon nanotube films (CNT_f) into an epoxy (EP) matrix as mechanical and EMI shielding reinforcement simultaneously. According to the computed tomography (CT) detection recorded by a high-speed camera, CNT_f exhibited excellent mechanical behavior and good energy absorption. While being introduced into laminated EP composite, the CNT_f enhanced both the mechanical performance and EMI shielding performance. The damage mechanism of CNT_f/EP was studied by CT detection of the impact process, indicating that the CNT_f absorbed the impact energy by improving the delamination resistance. Additionally, the multilayered CNT_f can trap and attenuate the entered electromagnetic microwaves by repeated adsorption, reflection, and scattering in the composite, resulting in excellent EMI shielding performance. Consequently, the energy absorption and the total shielding effectiveness of the CNT_f/EP reached to 4.58 × 10⁻³ J and 52.31 dB, respectively. Therefore, we demonstrated that the CNT_f was an ideal functional reinforcement for mechanically strong and high-performance EMI shielding polymeric composites and the CNT_f reinforced EP composite is promising in practical EMI-shielding applications.     

Isothermal crystallization kinetics and melting behavior of multiwalled carbon nanotubes/polyamide‐6 composites

Pristine and functionalized multiwalled carbon nanotubes (MWNTs) were used to fabricate polyamide 6 (PA6) composites through melt blending. The functionalized MWNTs were obtained by grafting 1,6‐hexamethylenediamine (HMD) onto the pristine MWNTs to improve their compatibility with PA6 matrix. The effect of MWNTs on the isothermal crystallization and melting behavior of PA6 was investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). The Avrami and Lauritzen–Hoffmann equations are used to describe the isothermal crystallization kinetics. The values of the Avrami exponent found for neat PA6, the pristine MWNTs/PA6 and functionalized MWNTs/PA6 composite samples are about 4.0, 1.7, and 2.3, respectively. The activation energies are determined by the Arrhenius method, which is lower for the composites, ?320.52 KJ/mol for pristine MWNTs/PA6 and ?293.83 KJ/mol for functionalized MWNTs/PA6, than that for the neat PA6 (?284.71 KJ/mol). The following melting behavior reveals that all the isothermally crystallized samples exhibit triple melting endotherms at lower crystallization temperature and double melting endotherms at higher crystallization temperature. The multiple melting endotherms are mainly caused by the recrystallization of PA6 during heating. The resulting equilibrium melting temperature is lower for the composites than for neat PA6. In addition, polarizing microscopy (PLM) and small angle light scanning (SALS) were used to study the spherulite morphology. The results show that the MWNTs reduce the spherulite radius of PA6. This reduction is more significant for pristine MWNTs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Noncovalent functionalization of carbon nanotubes using branched random copolymer for improvement of thermal conductivity and mechanical properties of epoxy thermosets

A branched random copolymer, poly[(hydroxyethyl acrylate)‐r‐(N‐vinylcarbazole)] (BPHNV), was synthesized through a facile one‐pot free radical polymerization with hydroxyethyl acrylate and N‐vinylcarbazole monomers, using 4‐vinylmethylmercaptan as the chain transfer agent. BPHNV was employed to noncovalently modify multiwall carbon nanotubes (MWCNTs) by π–π interaction. The as‐modified MWCNTs were then incorporated into epoxy resin to improve the thermal conductivity and mechanical properties of epoxy thermosets. The results suggest that, due to both the conjugation structure and the epoxy‐philic component, BPHNV could form a polymer layer on the wall of MWCNTs and inhibit entanglement, helping the uniform dispersion of MWCNTs in epoxy matrix. Owing to the unprecedented thermal conductivity of MWCNTs and the enhancement in the interfacial interaction between fillers and matrix, the thermal conductivity of epoxy/MWCNTs/BPHNV composites increases by 78% at extremely low filler loadings, while the electrical resistivity is still maintained on account of the insulating polymer layer. Meanwhile, the mechanical properties and glass transition temperature (T_g) of the thermosets are elevated effectively, with no significant decrease occurring to the modulus. The addition of as little as 0.1 wt% of MWCNTs decorated with 1.0 wt% of BPHNV to an epoxy matrix affords a great increase of 130% in impact strength for the epoxy thermosets, as well as an increase of over 13 °C in T_g. © 2018 Society of Chemical Industry     

Morphological,mechanical, and electromagnetic interference shielding effectiveness characteristics of glass fiber/epoxy resin/MWCNT buckypaper composites

Glass fiber/epoxy resin composites (GF/EP) using one and three multi-walled carbon nanotube buckypapers (BP) were obtained and their complex parameters, reflectivity, and electromagnetic interference (EMI) shielding effectiveness (SE) at X-band (8.2–12.4 GHz) and Ku-band (12.4–18 GHz) were evaluated. The preparation of BP used polyacrylonitrile (PAN) nanofibers (PF These composites show both large storage and energy loss capacity in both bands revealing promising results related to EMI SE applications. Besides, a high attenuation of around 67% and 72% were achieved for BP based composites. The cross-section view of the buckypaper and the laminates was analyzed by scanning electron microscopy (SEM). The incorporation of the CNT film into the laminates showed no improvements in the elastic properties through dynamic mechanical analyses (DMA). Nevertheless, a decrease in the shear properties by the compression shear test (CST) and interlaminar shear strength (ILSS) has been observed. GF/EP/BP/PF composite presented a reduction of 29 and 39% in its ILSS properties compared to the base laminate (GF/EP). Also, the decrease was even more significant, revealing a steep reduction in its CST properties. On the other hand, the removal of the pan nanofiber (PF) led to better mechanical properties for GF/EP/BP/RPF composites. Results have shown ILSS values of 47.4 ± 2.2 MPa which are close to the base laminate (52.4 ± 3.1 MPa). The removal of the PF provided larger porous in the CNT network, making the impregnation by epoxy easier in the BP/RPF which resulted in improved shear properties compared to GF/EP/BP/PF samples.     

碳纳米管/聚氨酯复合材料的粘接性能

利用超声分散、酸处理以及表面活性剂分散的方法将碳纳米管分散到蓖麻油中,制备了蓖麻油型聚氨酯/碳纳米管(PUR/CNTs)复合材料,观察了该复合材料的微观结构,探讨了CNTs用量、酸处理时间以及表面活性剂的用量对复合材料粘接性能的影响。结果表明,随着蓖麻油中CNTs用量的增加,该复合材料的粘接强度不断提高,当增加到2%时,粘接强度提高84.4%;硝酸处理3 h的聚氨酯/碳纳米管复合材料的粘接强度最大,比未酸处理的复合材料增加15%;表面活性剂分散的聚氨酯/碳纳米管复合材料的粘接强度能得到进一步的提高。     

Dielectric and microwave properties of carbon nanotubes/carbon black filled natural rubber composites

Abstract

Natural rubber (NR) based nanocomposites containing a constant amount (50 phr) of standard furnace carbon black and carbon nanotube (CNT) at a concentration from 1 to 5 phr have been prepared. Their dielectric (dielectric permittivity and dielectric loss) and microwave properties (coefficients of absorption and reflection of the electromagnetic waves and electromagnetic interference shielding effectiveness) have been investigated in the 1–12 GHz frequency range. The results achieved allow recommending CNTs as second filler for NR based composites to afford specific absorbing properties.     

聚丙烯/碳纳米管复合材料的研究进展

聚丙烯（PP）作为通用型热塑性塑料,具有物理性能优异、成型加工简单、密度小以及原料来源丰富等优点,广泛应用于电器、汽车和包装等行业。但是PP具有韧性差、低温脆性突出、抗冲击性能不佳、介电常数低、制品尺寸稳定性差等诸多缺点。碳纳米管（CNT）不仅具有独特的管状结构,还具有优异的力学、导电、导热以及耐磨等性能。将CNT和PP进行复合并制备出具有导电、导热、耐磨等高性能复合材料具有广阔的应用前景。因此,本文重点综述PP和CNT复合材料的新进展,主要包括结晶行为、力学性能、电学性能、摩擦性能、导热性能以及其他性能。针对现阶段PP/CNT复合材料研究和开发过程中存在的问题提出意见和建议,并对PP/CNT复合材料的未来发展做出展望。     

Thermoplastic polyvinyl alcohol/multiwalled carbon nanotube composites: Preparation,mechanical properties,thermal properties,and electromagnetic shielding effectiveness

This study uses the solution mixing method to combine plasticized polyvinyl alcohol (PVA) as a matrix, and multiwalled carbon nanotubes (MWCNTs) as reinforcement to form PVA/MWCNTs films. The films are then laminated and hot pressed to create PVA/MWCNTs composites. The control group of PVA/MWCNTs composites is made by incorporating the melt compounding method. Diverse properties of PVA/MWCNTs composites are then evaluated. For the experimental group, the incorporation of MWCNTs improves the glass transition temperature (T_g), crystallization temperature, T_c), and thermal stability of the composites. In addition, the test results indicate that composites containing 1.5 wt % of MWCNTs have the maximum tensile strength of 51.1 MPa, whereas composites containing 2 wt % MWCNTs have the optimal electrical conductivity of 2.4 S/cm, and electromagnetic shielding effectiveness (EMI SE) of ?31.41 dB. This study proves that the solution mixing method outperforms the melt compounding method in terms of mechanical properties, dispersion, melting and crystallization behaviors, thermal stability, and EMI SE. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43474.     

Electrical conductivity and electromagnetic interference shielding effectiveness of carbon black/sisal fiber/polyamide/polypropylene composites

The effects of hybrid fillers on the electrical conductivity and electromagnetic interference (EMI) shielding effectiveness (SE) of polyamide 6 (PA6)/polypropylene (PP) immiscible polymer blends were investigated. Carbon black (CB) and steam exploded sisal fiber (SF) were used as fillers. CB was coated on the surface of SF, and this was exploded by water steam to form carbon black modified sisal fiber (CBMSF). CB/SF/PA6/PP composites were prepared by melt compounding, and its electromagnetic SE was tested in low‐frequency and high‐frequency ranges. We observed that SF greatly contributed to the effective decrease in the percolation threshold of CB in the PA6/PP matrix and adsorbed carbon particles to form a conductive network. Furthermore, an appropriate CB/SF ratio was important for achieving the best shielding performance. The results indicate that CBMSF was suitable for use as electronic conductive fillers and the CB/SF/PA6/PP composites could be used for the purpose of EMI shielding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42801.