Morphology and properties of electrically and rheologically percolated PLA/PCL/CNT nanocomposites

Poly(lactic acid)/poly(?‐caprolactone)/carbon nanotube (PLA/PCL/CNT) nanocomposites (NCs) were melt‐processed in a conventional industrial‐like twin‐screw extruder maintaining a constant PLA/PCL 80/20 wt. ratio. CNTs located in the thermodynamically favored PCL phase and, as a result, the “sea–island” morphology of the unfilled blend was replaced by a more continuous PCL dispersed phase in the ternary NCs. Rheological and electrical percolation took place at the same CNT contents (over 1.2 wt %) that TEM images suggest continuity of the PCL phase. The electrical and the low‐strain mechanical behaviors upon CNT addition were similar in the reference binary PLA/CNT and ternary PLA/PCL/CNT NCs. In the percolated NCs, the conductivity became 10⁶–10⁷ times higher than in the insulating compositions, while the Young modulus increased linearly upon the addition of CNT (12% increase at 4.9 wt % loading). Moreover, all the PLA/PCL/CNT NCs showed a ductile behavior (elongation at break >130%) similar to that of the unfilled PLA/PCL blend (140%), in contrast to the brittle behavior of binary PLA/CNT NCs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45265.     

麦羟硅钠石/聚合物纳米复合材料研究进展

麦羟硅钠石（magadiite）是一种新型的层状纳米硅酸盐材料,由于其具有制备工艺简单、比表面积大、阳离子交换性能高、吸附性能强、层间膨胀性能好等优点,成为纳米材料提升聚合物性能最具有发展潜力的材料之一。本文主要综述了麦羟硅钠石/聚合物纳米复合材料的常用制备方法及其优缺点,包括聚合物插层法、单体原位插层聚合法、锚固插层聚合法。浅谈了国内外利用3种方法制备的基于聚苯乙烯、聚丙烯、环氧树脂、尼龙6、聚己内酯和聚甲基丙烯酸甲酯等多种聚合物的麦羟硅钠石/聚合物纳米复合材料,对在纳米复合材料结构中出现界面不相容、麦羟硅钠石分布不均匀的问题提出了解决方法,并阐述了麦羟硅钠石对纳米复合材料结构和性能的影响,最后展望了麦羟硅钠石/聚合物纳米复合材料的发展前景。     

Preparation,structure and properties of thermoplastic olefin nanocomposites containing functionalized carbon nanotubes

The morphology and properties of multiwalled carbon nanotube modified polypropylene (PP)/ethylene–octene copolymer blends were studied. Polypropylene chains are covalently grafted onto the surface of carbon nanotubes (CNTs) in order to improve their interaction with the polymer matrix. It is observed that functionalization of CNTs improves their dispersion and increases the interfacial bonding between CNTs and polymer matrix. The functionalized CNTs are selectively distributed in the continuous polypropylene phase. The size of the dispersed elastomer phase decreases after the addition of CNTs. Functionalized CNTs act as a nucleating agent and increase the crystallinity of the polypropylene. More importantly, an important increase in impact strength, stiffness and toughness can be achieved through introducing functionalized CNTs. Copyright © 2011 Society of Chemical Industry     

聚合物/蒙脱土纳米复合材料的研究进展

聚合物/蒙脱土纳米复合材料是近十年来研究最为广泛的复合材料之一,优异的热力学性能,独特的气 液阻隔性及阻燃性赋予它广泛的工业应用前景。本文就该复合材料在蒙脱土的有机改性处理、制备、制备条件对性能的影响、表征方法及手段、材料性能特征及应用等方面作一些简单总结。     

From carbon nanotube coatings to high‐performance polymer nanocomposites

Since their discovery at the beginning of the 1990s, carbon nanotubes (CNTs) have been the focus of considerable research by both academia and industry due to their remarkable and unique electronic and mechanical properties. Among numerous potential applications of CNTs, their use as reinforcing materials for polymers has recently received considerable attention since their exceptional mechanical properties, combined with their low density, offer tremendous opportunities for the development of fundamentally new material systems. However, the key challenge remains to reach a high level of nanoparticle dissociation (i.e. to break down the cohesion of aggregated CNTs) as well as a fine dispersion upon melt blending within the selected matrices. Therefore, this contribution aims at reviewing the exceptional efficiency of CNT coating by a thin layer of polymer as obtained by an in situ polymerization process catalysed directly from the nanofiller surface, known as the ‘polymerization‐filling technique’. This process allows for complete destructuring of the native filler aggregates. Interestingly enough, such surface‐coated carbon nanotubes can be added as ‘masterbatch’ in commercial polymeric matrices leading to the production of polymer nanocomposites displaying much better thermomechanical, flame retardant and electrical conductive properties even at very low filler loading. Copyright © 2007 Society of Chemical Industry     

Electrical properties of polymer nanocomposites containing rod-like nanofillers

We present an in-depth critical review of major experimental, simulation, and theoretical work in the field of conducting polymer nanocomposites containing rod-like particles such as carbon nanotubes and metal nanowires. These are a versatile class of materials that are of interest for a wide range of applications. Commercialization of various classes of conducting polymer nanocomposites is growing, yet achieving their full technological potential will hinge on the ability to engineer composites with controllable and well-defined properties, as well as aggressive exploration of new application areas. Thus, the focus of this review is to clarify key structure–property relationships, and to discuss the major gaps and greatest opportunities in the field.     

Poly(trimethylene terephthalate‐block‐tetramethylene oxide) elastomer/single‐walled carbon nanotubes nanocomposites: Synthesis,structure, and properties

Nanocomposites based on poly(trimethylene terephthalate)‐block‐poly(tetramethylene oxide) (PTT‐PTMO)‐segmented copolymer and COOH‐functionalized single‐walled carbon nanotubes (SWCNTs) were prepared by in situ polymerization method. The obtained nanocomposites were characterized by thermogravimetric analysis, scanning electron microscopy, differential scanning calorimetry (DSC), DMTA, wide‐angle x‐ray scattering (WAXS), small‐angle X‐ray scattering, and tensile testing. The nanocomposites with low SWCNTs loading (<0.5 wt %) shows uniform dispersion of CNT in polymer matrix. As the SWCNTs loading in the nanocomposites increase, the significant improvement of thermo‐oxidative stability was observed. It was found that the nanocomposites have slightly higher degree of crystallinity (determined by DSC and WAXS) of poly(trimethylene terephthalate) (PTT) hard phase than neat PTT‐PTMO copolymer. The melting point of PTT hard phase and glass transition temperature of poly(tetramethylene oxide)‐rich phase were not affected by the presence of CNTs in polymer matrix. The SWCNTs played a role as nucleating agent in PTT‐PTMO matrix, which led to increase in the crystallization rate. Tensile tests showed that the tensile strength of the nanocomposites with 0.05–0.3 wt % loading of SWCNTs have improved tensile strength in comparison to the neat PTT‐PTMO copolymer without reduction elongation at break. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of poly(vinylidene fluoride) nanocomposites containing multiwalled carbon nanotubes

Poly(vinylidene fluoride) (PVDF) nanocomposites with different loadings of multiwalled carbon nanotubes (MWNT) were prepared by melt‐compounding technique. A homogeneous dispersion of MWNT throughout PVDF matrix was observed on the cryo‐fractured surfaces by scanning electron microscopy. Thermogravimetric analysis results indicated that the thermal stability of neat PVDF was improved with the incorporation of MWNT. Dynamic mechanical analysis showed a significant improvement in the storage modulus over a temperature range from ?125 to 75°C with the addition of MWNT. The melt‐rheological studies illustrated that incorporating MWNT into PVDF matrix resulted in higher complex viscosities (|η*|), storage modulus (G′), loss modulus (G″), and lower loss factor (tan δ) than those of neat PVDF. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of alkylated carbon nanotube/polyimide nanocomposites

BACKGROUND: The development of carbon nanotube‐reinforced composites has been impeded by the difficult dispersion of the nanotubes in polymers and the weak interaction between the nanofiller and matrices. Efficient dispersion of carbon nanotubes is essential for the formation of a functional nanotube network in a composite matrix. RESULTS: Multiwalled carbon nanotubes (MWNTs) were incorporated into a polyimide matrix to produce MWNT/polyimide nanocomposites. To disperse well the MWNTs in the matrix and thus improve the interfacial adhesion between the nanotubes and the polymer, ‘branches’ were grafted onto the surface of the nanotubes by reacting octadecyl isocyanate with carboxylated MWNTs. The functionalized MWNTs were suspended in a precursor solution, and the dispersion was cast, followed by drying and imidization to obtain MWNT/polyimide nanocomposites. CONCLUSION: The functionalized MWNTs appear as a homogeneous dispersion in the polymer matrix. The thermal stability and the mechanical properties are greatly improved, which is attributed to the strong interactions between the functionalized MWNTs and the polyimide matrix. Copyright © 2009 Society of Chemical Industry     

Interphasial viscoelastic behavior of CNT reinforced nanocomposites studied by means of the concept of the hybrid viscoelastic interphase

In this study the effect of carbon nanotubes content as well as of the tensile stress level applied upon the linear viscoelastic creep response of carbon nanotube polymer nanocomposites was investigated. Experimental findings were modeled by means of the newly developed hybrid viscoelastic interphase model, which constitutes an extension of the previously developed hybrid interphase model. According to this model, the viscoelastic interphase thickness has not of constant value but is dependent upon the property considered at the time as well as on the creep time. In addition, the parameter of imperfect bonding is introduced through the degree of adhesion. Experimental findings combined with analytical results gave a better understanding of the viscoelastic response of epoxy resin carbon nanotubes nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Carboxylated multiwall carbon nanotube-reinforced thermotropic liquid crystalline polymer nanocomposites

Thermotropic liquid crystalline polymer (TLCP) nanocomposites reinforced with carboxylated multiwall carbon nanotube (c-MWCNT) were prepared through melt compounding in a twin screw extruder. The thermal stability of TLCP/c-MWCNT nanocomposites increased with even a small amount of c-MWCNT added. The rheological properties of the TLCP/c-MWCNT nanocomposites were depended on the c-MWCNT contents. The contents of c-MWCNT have a slight effect on the complex viscosity of TLCP/c-MWCNT nanocomposites due to the high-shear thinning of TLCP. The storage modulus of TLCP/c-MWCNT nanocomposites was increased with increasing c-MWCNT content. This result can be deduced that the nanotube–nanotube interactions were more dominant, and some interconnected or network-like structures were formed in the TLCP/c-MWCNT nanocomposites. Incorporation of very small amount of c-MWCNT improved the mechanical properties of TLCP/c-MWCNT nanocomposites, and this was attributed to the reinforcement effect of c-MWCNT with high aspect ratio and their uniform dispersion through acid treatment in the TLCP matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrical and mechanical properties of acrylonitrile‐butadiene‐styrene/multiwall carbon nanotube nanocomposites prepared by melt‐blending

The electrical properties in polymer/carbon nanotube (CNT) nanocomposites are governed not only by the degree of dispersion but also to a greater extent on the aspect ratio of the CNTs in the final composites. Melt‐mixing of polymer and CNTs at high shear rate usually breaks the CNTS that lowers the aspect ratio of the nanotubes. Thus, homogeneous dispersion of CNTs while retaining the aspect ratio is a major challenge in melt‐mixing. Here, we demonstrate a novel method that involves melt‐blending of acrylonitrile‐butadiene‐styrene (ABS) and in situ polymerized polystyrene (PS)/multiwalled CNT (MWCNT) nanocomposites, to prepare electrically conducting ABS/MWCNT nanocomposites with very low CNT loading than reported. The rationale behind choosing PS/MWCNT as blending component was that ABS is reported to form miscible blend with the PS. Thus, (80/20 w/w) ABS/(PS/MWCNT) nanocomposites obtained by melt‐blending showed electrical conductivity value ≈1.27 × 10^?6 S cm^?1 at MWCNT loading close to 0.64 wt %, which is quite lower than previously reported value for ABS/MWCNT system prepared via solution blending. Scanning electron microscopy and differential scanning calorimetry analysis indicated the formation of homogenous and miscible blend of ABS and PS. The high temperature (100°C) storage modulus of ABS (1298 MPa) in the nanocomposites was increased to 1696 MPa in presence of 0.64 wt % of the MWCNT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of the dispersion state and aspect ratio of carbon nanotubes on their electrical percolation threshold in a polymer

The electrical percolation threshold of carbon nanotubes (CNTs) is correlated with their dispersion state and aspect ratio through modeling. An analytical percolation model based on excluded volume theory and developed for systems containing two types of fillers is used. CNTs are modeled as two types of fillers: single CNT and m‐CNT bundle, and a variable P representing the dispersion state of CNTs is introduced. An equation showing the effects of the dispersion state and aspect ratio on the electrical percolation threshold of CNTs is established and verified with some of the published experimental data. It is useful for predicting the conductive behavior of polymer/CNT composites and for the design of their processing conditions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure,properties, and applications of polyacrylonitrile/carbon nanotube (CNT) fibers at low CNT loading

Bi-component, polyacrylonitrile (PAN)/carbon nanotube (CNT) fibers were processed, at different core-sheath area ratios, by gel spinning. A percolated CNT network at 10 wt% CNT in the sheath enhanced electrical conductivity as compared to the neat PAN fiber, while PAN polymer in the core contributed to the good mechanical properties. Fibers with relatively thin sheath allowed overall CNT loading as low as 3.7 wt% to be made with good electrical conductivity, and PAN stabilization by Joule heating was demonstrated. Such fibers with combined good mechanical properties and electrical conductivity can also potentially be used for electrical heating of fabrics, for making smart textiles, and for electromagnetic interference shielding.     

Synthesis and properties of homogeneously dispersed polyamide 6/MWNTs nanocomposites via simultaneous in situ anionic ring‐opening polymerization and compatibilization

Toluene 2, 4‐diisocyanate (TDI) functionalized multiwalled carbon nanotubes (MWNTs‐NCO) were used to prepare monomer casting polyamide 6 (MCPA6)/MWNTs nanocomposites via in situ anionic ring‐opening polymerization (AROP). Isocyanate groups of MWNTs‐NCO could serve as AROP activators of ?‐caprolactam (CL) in the in situ polymerization. Fourier transform infrared (FTIR) showed that a graft copolymer of PA6 and MWNTs was formed in the in situ polymerization. MWNTs‐PA6 covalent bonds of the graft copolymer constituted a strong type of interfacial interaction in the nanocomposites and increased the compatibility of MWNTs and MCPA6 matrix. The nanocomposites were characterized for the morphology, mechanical, crystallization, and thermal properties through field emission transmission electron microscopy (FETEM), tensile testing, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). FETEM analysis showed that MWNTs were homogeneously dispersed in MCPA6 matrix. The initial tensile strengths and tensile modulus of the nanocomposite with 1.5 wt % loading of MWNTs were enhanced by about 16 and 13%, respectively, compared with the corresponding values for neat MCPA6. DSC analysis indicated that the crystallization temperature of the nanocomposites was increased by 8°C by adding 1.5 wt % MWNTs compared with pure MCPA6. Besides, it was found that the thermal stability of MCPA6 was improved by the addition of the MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and thermal properties of multiwalled carbon nanotube/polybenzoxazine nanocomposites

In this study, we prepared nanocomposites comprising multiwalled carbon nanotubes (MWCNTs) and polybenzoxazine (PBZ). The MWCNTs were purified through microwave digestion to remove most of the amorphous carbon and metal impurities. After purification, MWCNTs were treated with H₂SO₄/HNO₃ (3 : 1) to introduce hydroxyl and carboxyl groups onto their surfaces. Raman spectroscopy revealed the percentage of nanotube content improved after prolonged microwave treatment, as evidenced by the decrease in the ratio of the D (1328 cm^?1) and G (1583 cm^?1) bands. For the untreated MWCNTs, the I_D/I_G ratio was 0.56. After microwave treatment for 40 min, the value decreased to 0.29, indicating that the percentage of nanotube content improved. Dynamic mechanical analyses (DMAs) revealed that the storage moduli and the T_gs of the MWCNTs/PBZ nanocomposites were higher than that of the pristine PBZ. This is due to the nanometer‐scale MWCNTs restricting the motion of the macromolecular chains in the nanocomposites. Transmission electron microscopy (TEM) image revealed that the MWCNTs were well dispersed within the PBZ matrix on the nanoscale when the MWCNT content was less than 2.0 phr. The coefficient of thermal expansion (CTE) of the nanocomposites decreased on increasing the MWCNTs content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

The physical properties of carbon nanoparticles dispersed into NBR/LLDPE nanocomposites for corrosion protection applications

In this study, novel acrylonitrile butadiene rubber (NBR) nanocomposites with improved electrical conductivity and mechanical properties were synthesized. Carbon nanoparticles (CNP)/NBR composites and CNP‐polyethylene/NBR nanocomposites were prepared by mixing via two‐roll mill. The first type of the nanocomposite was produced to determine the percolation threshold concentration (V_c). The second type with constant CNP concentration, slightly over V_c (0.2 vol %), was synthesized to investigate the influence of polyethylene content on the mechanical, electrical and swelling behavior of nanocomposites. Only the nanocomposites with 3 vol % polyethylene loading showed electrical conductivity. However, the composites with higher polyethylene loadings showed insulating behavior due to hindrance of CNP network by polyethylene layers. Swelling measurements revealed that the change in entropy of the swelling increased with the increase in disorder level but decreased with the increase in intercalation level of CNP in the disordered intercalated nanocomposite. The increase in solvent uptake was comparable with the free volume in NBR matrix upon inclusion of nanoparticles, whereas the inhibition in solvent uptake for higher polyethylene loading was described by bridging flocculation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation by melt mixing and characterization of isotactic polypropylene/SiO2 nanocomposites containing untreated and surface‐treated nanoparticles

In the present study two series of isotactic polypropylene (iPP)/SiO₂ nanocomposites containing 1, 2.5, 5, 7.5, and 10 wt % SiO₂ nanoparticles were prepared by melt‐mixing on a twin‐screw corotating extruder. In the first series untreated fumed silica nanoparticles were used, whereas in the second nanoparticles were surface‐treated with dimethyldichlorosilane. In both cases, the average size of the primary nanoparticles was 12 nm. Tensile and impact strength were found to increase and to be affected mainly by the type and content of silica nanoparticles. A maximum was observed, corresponding to samples containing 2.5 wt % SiO₂. These findings are discussed in light of the SEM and TEM observations. By increasing the amount of nanoparticles, large aggregates of fumed silica could be formed, which may explain the reduction of mechanical properties with higher concentrations of SiO₂. However, it was found that surface‐treated nanoparticles produced larger aggregates than did those derived from untreated nanoparticles, despite the increased adhesion of the iPP matrix, as was postulated from yield strength. This behavior negatively affected mechanical properties. In addition, an effort was made to determine if toughening theories, mainly the critical interparticle distance for rubber toughening or composites, also might be applicable in nanocomposites. From DSC measurements it was demonstrated that silica nanoparticles acted as effective nucleating agents, increasing the crystallization rate and the degree of crystallinity of iPP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2684–2696, 2006     

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