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     

Electrical and mechanical behaviors of carbon nanotube‐filled polymer blends

Four carbon nanotube (CNT)‐filled polymer blends, i.e., CNT‐filled polyethylene terephthalate (PET)/polyvinylidene fluoride, PET/nylon 6,6, PET/polypropylene, and PET/high‐density polyethylene blends, have been injection‐molded and characterized in terms of their microstructures, electrical conductivities, and mechanical properties. The distribution of CNTs in the polymer blends has been examined based on their wetting coefficients and minimization of the interfacial energy. The electrical conductivity and mechanical properties have been related to the cocontinuous polymer blends, the conductive path formed by CNTs, the CNT distribution, and the intrinsic properties of the constituent polymers. It is found that to obtain a CNT‐filled polymer composite with both high electrical conductivity and good mechanical properties, it is preferred that most CNTs distribute in one polymer phase, while the other polymer phase(s) remain neat. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 477–488, 2006     

Micro‐injection molding of CNT nanocomposites obtained via compounding process

Many research efforts have gone in the production of carbon nanotubes (CNT) composites for functional and structural applications and many processing methodologies have been experimented. Twin‐screw extrusion appears to be the most suitable way from the perspective of production scale up and commercialization of these composites. At the same time, micro‐injection molding process is considered as the key manufacturing technology for the mass production of miniaturized components and devices. Despite the massive literature about nanocomposites and microinjection molding process, few articles focus on the interaction between the compounding process and the following micro‐injection molding transformation processes. This article aims at analyzing the influence of the screw configuration used in compounding process on the rheological and technological properties of the resulting nanocomposites. Two different combinations of screw elements have been tested to incorporate CNTs in two different resins: LCP (liquid crystal polymer) and POM (polyoxymethylene) typically used in micro‐injection molding. The effects of the process set up have been observed studying first the rheology and then the moldability of nano‐compounds microinjected ribs with high aspect ratio. The nanofiller dispersion has been evaluated via light and transmission electron microscopy. The results confirm that, the screws show different capacity at promoting the dispersion of the nanofiller, which affects the moldability of micro‐injected CNT nanocomposites. The viscosity of the polymer seems a critical factor as well, because it influences first the dispersion of CNT bundle during extrusion and then the injection moldability of the composites in the micro‐channels. POLYM. COMPOS., 38:349–362, 2017. © 2015 Society of Plastics Engineers     

Highly efficient electrically conductive networks in carbon‐black‐filled ternary blends through the formation of thermodynamically induced self‐assembled hierarchical structures

Highly efficient electrical conductive networks were constructed in carbon‐black (CB)‐filled polyoxymethylene (POM)–thermoplastic polyurethane (TPU)–polyamide 6 (PA6) ternary blends through the formation of a hierarchical structure composed of a minor PA6 phase as droplets inside one major phase (TPU) and CB particles localized at the TPU–PA6 interface by thermodynamically induced self‐assembly. The hierarchical structure was thermodynamically predicted on the basis of the minimization of total interfacial energies and confirmed by electron microscopy. The degrees of the TPU phase continuity before and after the addition of PA6 were determined by solvent‐extraction experiments. The percolation threshold of CB decreased by 50% compared to that in the POM–TPU binary blend because of the more efficient formation of a CB conductive network through CB‐covered PA6 domains inside the TPU phase. The hierarchical structure not only increased the electrical conductivity of the composites but also improved their thermal stability in comparison with the simple structure formed by the homogeneously dispersed CB particles in POM. The method reported in this article can offer possibilities for improving the comprehensive properties of the conductive composites and the widening of their applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45877.     

Impact of injection‐molding processing parameters on the electrical,mechanical, and thermal properties of thermoplastic/carbon nanotube nanocomposites

Thermoplastic nanocomposites, based on high‐density polyethylene, polyamide 6, polyamide 66, poly(butylene terephthalate), or polycarbonate and containing multiwalled carbon nanotubes (CNTs), were compounded with either neat CNTs or commercial CNT master batches and injection‐molded for the evaluation of their electrical, mechanical, and thermal properties. The nanocomposites reached a percolation threshold within CNT concentrations of 2–5 wt %; however, the mechanical properties of the host polymers were affected. For some nanocomposites, better properties were achieved with neat CNTs, whereas for others, master batches were better. Then, polycarbonate and poly(butylene terephthalate), both with a CNT concentration of 3 wt %, were injection‐molded with a screening design of experiments (DOE) to evaluate the effects of the processing parameters on the properties of the nanocomposites. Although only a 10‐run screening DOE was performed, such effects were clearly observed. The volume resistivity was significantly dependent on the working temperature and varied up to 4 orders of magnitude. Other properties were also dependent on the processing parameters, albeit in a less pronounced fashion. Transmission electron microscopy indicated that conductive samples formed a percolation network, whereas nonconductive samples did not. In conclusion, injection‐molding parameters have a significant impact on the properties of polymer/CNT nanocomposites, and these parameters should be optimized to yield the best results. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrical properties of FeII‐terpyridine‐Modified cellulose nanocrystals and polycaprolactone/FeII‐CTP nanocomposites

Supramolecular crosslinked Fe^II‐terpyridine cellulose nanocrystals (Fe‐CTP) were prepared by surface modification of cellulose nanocrystals with 4′‐chloro‐2,2′:6′,2″‐terpyridine and subsequent reaction with Fe(II)SO₄. The prepared complex was characterized using transmission electron microscopy (TEM), ultraviolet spectroscopy (UV), thermogravimetric analysis (TGA), and measuring its electrical properties at temperatures from 25 to 70°C. Use of Fe‐CTP at loadings from 1% to 10% (wt. ratio) in nanocomposites with polycaprolactone polymer was investigated; the nanocomposites were characterized regarding their electrical properties, which studied using broadband AC‐relaxation spectroscopy in the frequency range between 0.1 Hz and 1 MHz. The results were compared to that of PCL nanocomposites containing multiwalled carbon nanotubes (CNT). Variation in real and imaginary parts of permittivity has been explained on the basis of interfacial polarization of fillers in the polymer medium. The percolation limit of the conductive CNT and Fe‐CTP as studied by ac conductivity measurements has also been reported. Fe‐CTP showed conductivity values in the range of semiconductors. PCL/Fe‐CTP nanocomposites showed conductivity values from 1.98 × 10⁻¹¹ to 3.76 × 10⁻⁶ while PCL/CNT nanocomposites showed conductivity values from 1.4 × 10⁻¹⁰ to 3.67 × 10⁻⁴ S/m for 1–10 wt% CNT content. POLYM. COMPOS., 37:2734–2743, 2016. © 2015 Society of Plastics Engineers     

Thermal conductivity and stability of a three‐phase blend of carbon nanotubes,conductive polymer,and silver nanoparticles incorporated into polycarbonate nanocomposites

Metallic and non‐metallic nanofillers can be used together in the design of polycarbonate (PC) nanocomposites with improved electrical properties. Here, the preparation of three‐phase blend (carbon nanotubes (CNT), silver nanoparticles, and conductive polymer) in a two‐step process before incorporation in the PC is reported. First, ethylene diamine functionalized multiwall carbon nanotubes (MWCNT‐EDA) were decorated with Ag nanoparticles. Next, the Ag‐decorated CNTs were coated with poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT : PSS). Due to the high thermal conductivity instrinsic to both metallic and non‐metallic phases, it is expected that the thermal properties of the resulting nanocomposite would largely differ from those of pristine PC. We thus investigated in detail how this hybrid conductive blend affected properties such as the glass transition temperature, the thermal stability, and the thermal conductivity of the nanocomposite. It was found that this strategy results in improved thermal conductivity and thermal stability of the material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42281.     

Effect of annealing treatment on the structure and properties of polyurethane/multiwalled carbon nanotube nanocomposites

The thermoplastic polyurethane/multiwalled carbon nanotube (TPU/CNT) nanocomposites with high conductivity and low percolation threshold value were prepared by melting blending and annealing treatment. The effect of annealing process on the microphase structure and the properties of TPU/CNT nanocomposites was studied. It has been shown that CNT flocculation can occur in TPU/CNT nanocomposites during the annealing process. At a critical CNT content, which defined the percolation threshold, CNTs could form conductivity network. The conductive percolation threshold value of TPU/CNT nanocomposites was decreased from 10 to 4% after annealing process, and the conductivity of TPU/CNT nanocomposites with 10 vol % of CNT could reach 1.1 S/m after an annealing time of 1 h. The significant enhancement of electrical conductivity was influenced by the annealing time and the content of CNTs. The formation of CNT networks was also verified by dynamic viscoelastic characterization. The results of X‐ray diffraction and differential scanning calorimetry indicated that annealing process reinforced the microphase separation of the nanocomposites. Mechanical properties test showed that the annealing treatment was in favor of improving the mechanical properties; however, further increase in the annealing time has negative effect on the mechanical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Constructing the core–shell structured island domain in polymer blends to achieve high dielectric constant and low loss

Carbon nanotubes (CNTs) and barium titanate (BaTiO₃) (BT) were simultaneously introduced into the immiscible blend poly(ethylene‐co‐vinyl acetate)/thermoplastic urethane (EVA/TPU), and the EVA/TPU/CNT/BT quaternary polymer composite blends with core–shell structured island TPU domain were successfully prepared, in which CNTs in the TPU domain act as the core and the BT spheres at the interface of the TPU and EVA act as the shell. A core–shell structured island can lead to the formation of micro‐capacitors and further accumulate electron storage owing to the incorporation of CNTs and BT; on the other hand, a BT shell can be assembled along the TPU spheres, reducing the possibility of formation of a conductive CNT network, resulting in suppressed dielectric loss. Therefore, CNTs and BT were tailor‐made into blend composites with a core–shell structured domain, which can achieve an increased dielectric constant by 176% and decreased low dielectric loss by 80% compared with the blend composites with only CNTs in the TPU domain. © 2019 Society of Chemical Industry     

Characterization and thermal degradation kinetics of poly(l‐lactide) nanocomposites with carbon nanotubes

The purpose of this research was to study the thermal degradation kinetics of nanocomposites of poly(l ‐lactide) (PLLA) with carbon nanotubes (CNT) in order to provide further insight into their thermal stability. Nanocomposites were prepared by solvent casting with 1, 3, and 5% by weight of pristine CNT (P‐CNT) or functionalized CNT (F‐CNT), and were characterized using infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic‐mechanical‐thermal analysis. The kinetic parameters of thermal decomposition were determined employing Coats‐Redfern method to calculate the reaction order and E₂ function model to calculate the activation energy (Ea). We found no major changes in PLLA glass transition temperatures due to CNT presence, but melt‐crystallization temperature increased slightly in some composites. In general, composites consisting of 3% or 5% of F‐CNT had superior thermal stability than did pure polymer or P‐CNT composites. This improved thermal stability was revealed by slightly higher degradation and onset temperatures, and Ea obtained from kinetic analysis. In addition, 3% or 5% of F‐CNT in PLLA composites slightly enhanced the storage modulus above the glass transition. Therefore, functionalization promoted, in some extent, better morphology and dispersion of CNT into the matrix, which was responsible for improved thermal stability and thermomechanical performance of composites at higher temperatures relative to pure polymer. POLYM. ENG. SCI., 55:710–718, 2015. © 2014 Society of Plastics Engineers     

Effect of flow induced alignment on the thermal conductivity of injection molded carbon nanotube‐filled polystyrene nanocomposites

Carbon nanotube (CNT) nanocomposites with a polystyrene thermoplastic matrix were injection molded and the high shear stress exerted during the injection process partially enabled the alignment of the CNTs in the flow direction. Nanocomposites with different CNT loadings and degrees of alignment were produced, and their thermal conductivities were measured based on ASTM D5470. The results were compared with compression molded samples featuring random alignments of CNTs. The results showed that the injection molded samples possessed anisotropic thermal conductivities, due to the partial alignment of the CNTs in the flow direction. The effective medium approach was used to analytically estimate the thermal conductivity of the molded samples. Good agreement was observed between the experimental and analytically simulated results in lower CNT concentrations (less than 5 wt% of CNT). Using transmission electron microscopy pictures taken of the nanocomposites, the alignment of CNTs in the thermoplastic matrix were modeled; and their thermal conductivities were simulated using the finite element method. Good agreement was observed between the experiments and simulated results. POLYM. ENG. SCI., 55:753–762, 2015. © 2014 Society of Plastics Engineers     

Selective Laser Sintering 3D Printing: A Way to Construct 3D Electrically Conductive Segregated Network in Polymer Matrix

Selective laser sintering (SLS), which can directly turn 3D models into real objects, is employed to prepare the flexible thermoplastic polyurethane (TPU) conductor using self‐made carbon nanotubes (CNTs) wrapped TPU powders. The SLS printing, as a shear‐free and free‐flowing processing without compacting, provides a unique approach to construct conductive segregated networks of CNTs in the polymer matrix. The electrical conductivity for the SLS processed TPU/CNTs composite has a lower percolation threshold of 0.2 wt% and reaches ≈10⁻¹ S m⁻¹ at 1 wt% CNTs content, which is seven orders of magnitude higher than that of conventional injection‐molded TPU/CNTs composites at the same CNTs content. The 3D printed TPU/CNTs specimen can maintain good flexibility and durability, even after repeated bending for 1000 cycles, the electrical resistance can keep at a nearly constant value. The flexible conductive TPU/CNTs composite with complicated structures and shapes like porous piezoresistors can be easily obtained by this approach.     

Thermal conductivity of carbon nanotubes and their polymer nanocomposites: A review

Thermally conductive polymer composites offer new possibilities for replacing metal parts in several applications, including power electronics, electric motors and generators, heat exchangers, etc., thanks to the polymer advantages such as light weight, corrosion resistance and ease of processing. Current interest to improve the thermal conductivity of polymers is focused on the selective addition of nanofillers with high thermal conductivity. Unusually high thermal conductivity makes carbon nanotube (CNT) the best promising candidate material for thermally conductive composites. However, the thermal conductivities of polymer/CNT nanocomposites are relatively low compared with expectations from the intrinsic thermal conductivity of CNTs. The challenge primarily comes from the large interfacial thermal resistance between the CNT and the surrounding polymer matrix, which hinders the transfer of phonon dominating heat conduction in polymer and CNT.This article reviews the status of worldwide research in the thermal conductivity of CNTs and their polymer nanocomposites. The dependence of thermal conductivity of nanotubes on the atomic structure, the tube size, the morphology, the defect and the purification is reviewed. The roles of particle/polymer and particle/particle interfaces on the thermal conductivity of polymer/CNT nanocomposites are discussed in detail, as well as the relationship between the thermal conductivity and the micro- and nano-structure of the composites.     

Effect of solid state grinding on properties of PP/PET blends and their composites with carbon nanotubes

In this study, it was aimed to improve electrical conductivity and mechanical properties of conductive polymer composites, composed of polypropylene (PP), poly(ethylene terephthalate) (PET), and carbon nanotubes (CNT). Grinding, a type of solid state processing technique, was applied to PP/PET and PP/PET/CNT systems to reduce average domain size of blend phases and to improve interfacial adhesion between these phases. Surface energy measurements showed that carbon nanotubes might be selectively localized at PET phase of immiscible blend systems. Grinding technique exhibited improvement in electrical conductivity and mechanical properties of PP/PET/CNT systems at low PET compositions. Ground composites molded below the melting temperature of PET exhibited higher tensile strength and modulus values than those prepared above the melting temperature of PET. According to SEM micrographs, micron‐sized domain structures were obtained with ground composite systems in which PET was the minor phase. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of carbon nanotube/binary‐polymer composites with a double‐segregated structure

A carbon nanotube (CNT)/poly(methyl methacrylate) (PMMA)/ultrahigh molecular weight polyethylene (UHMWPE) composite containing a double‐segregated structure was formalized by means of a facile mechanical mixing technology. In the composite, the CNTs were decorated on the surfaces of PMMA granules, and the CNTs decorated granules formed the continuous segregated conducting layers at the interfaces between UHMWPE particles. Morphology observations confirmed the formation of a specific double‐segregated CNT conductive network, resulting in an ultralow percolation threshold of ～0.2 wt %. The double‐segregated composite containing only 0.8 wt % CNT loading exhibited a high electrical conductivity of ～0.2 S m^?1 and efficient electromagnetic shielding effectiveness of ～19.6 dB, respectively. The thermal conductivity, temperature‐resistivity behaviors, and mechanical properties of the double‐segregated composites were also studied. This work provided a novel conductive network structure to attain a high‐performance conducting polymer composite at low filler loadings. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39789.     

Improved dispersion of carbon nanotubes in poly(vinylidene fluoride) composites by hybrids with core–shell structure

Core–shell structure hybrids of carbon nanotubes (CNTs)/BaTiO₃ (H‐CNT‐BT) and commercial multi‐wall CNTs are respectively incorporated into poly(vinylidene fluoride) (PVDF) for preparing the composites near the percolation thresholds. A comprehensive investigation for CNT's dispersion and composite's conductivity is conducted between H‐CNT‐BT/PVDF and CNT/PVDF at different depths vertical to the injection's direction. Gradual increases of the conductivity in two composites are observed from the out‐layer to the core part which infers an inhomogeneous CNT's dispersion in the interior of composites due to their migration under flow during the injection. However, the use of H‐CNT‐BT fillers with core–shell structure enables to reduce this inhomogeneous dispersion in the composite. Furthermore, the conductive network of CNTs in H‐CNT‐BT/PVDF is less sensitive to the thermal treatment than the one in CNT/PVDF composite, which infers the core–shell structure of hybrids can ameliorate the sensitivity of the conductive network. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45693.     

Enhanced thermal conductivity of PLA‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid

Enhancing thermal conductivity of polymeric nanocomposites remains a great challenge because of the poor compatibility between nanofillers and the polymeric matrix and the aggregation effect of nanofillers. We report the enhanced thermal conductivity of poly(lactic acid) (PLA)‐based nanocomposites by incorporation of graphite nanoplatelets functionalized by tannic acid. Graphite nanoplatelets (GNPs) were noncovalently functionalized with tannic acid (TA) by van der Waals forces and π–π interaction without perturbing the conjugated sp² network, thus preserving the high thermal conductivity of GNPs. PLA‐based nanocomposites with different contents of TA‐functionalized GNPs (TA‐GNPs) were prepared and characterized, and the influences of TA‐GNPs content on the morphologies, mechanical properties, and thermal properties of the composites were investigated in detail. TA‐GNPs remarkably improved the thermal conductivity of PLA up to 0.77 W/(m K), showing its high potential as a thermally conductive filler for polymer‐based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46397.     

Electrical ac and dc behavior of epoxy nanocomposites containing graphene oxide

This article deals with the investigation of electrical properties of epoxy‐based nanocomposites containing graphene oxide nanofillers dispersed in the polymer matrix through two‐phase extraction. Broadband dielectric spectroscopy and dc electrical conductivity as a function of electric field have been evaluated in specimens containing up to 0.5 wt % of nanofiller. Nanocomposites containing pristine graphene oxide do not show significant changes of electrical properties. On the contrary, the same materials after a proper thermal treatment at 135°C, able to provoke the in situ reduction of graphene oxide, exhibit higher permittivity and electrical conductivity, without showing large decrease of breakdown voltage. Moreover, a nonlinear behavior of the electrical conductivity is observed in the range of electric fields investigated, i.e. 2–30 kV mm^?1. A new relaxation phenomenon with a very low temperature dependence is also evidenced at high frequency in reduced graphene oxide composites, likely associated to induced polarization of electrically conductive nanoparticles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41923.     

Thermal and mechanical properties of homogeneous ternary nanocomposites of regioregular poly(3‐hexylthiophene)‐wrapped multiwalled carbon nanotube dispersed in thermoplastic polyurethane: Dynamic‐ and thermomechanical analysis

An interesting correlation between initial loading and nature of wrapping of regioregular poly(3‐hexylthiophene) (rrP3HT) on multiwalled carbon nanotube and their combined effect on dynamic‐ and thermomechanical properties in ternary system (thermoplastic polyurethane as matrix) is highlighted. Wrapping of rrP3HT on carbon nanotube (CNT) makes the hexyl side chains thermally nonequivalent and composites more stable. Dynamic‐ and thermomechanical analysis ascertained the miscibility (single T_g = ?40°C), large mechanical reinforcement, and improved storage modulus of nanocomposites in the presence of CNT compared to its blends. Two breaks at ～ ?100 and ～ ?40°C for TPU‐P3HT composites (PHs) and TPU‐P3HT‐MWCNT composites (PHCs) in the loss modulus vs. temperature plot indicates two different types of transitions in P3HT chains. Dimensional stability by expansion probe technique measures low coefficient of thermal expansion of PHCs compared to its blends. Softening property by penetration probe technique suggests that 2.5 wt % loading of P3HT exhibits lowest degree of penetration compared to other nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Multiple percolation in a carbon‐filled polymer composites via foaming

This article describes an investigation into the effects of foaming on the electrical conductivity for a carbon‐filled cyclic olefin copolymer (COC) composite incorporating both chopped carbon fibers (cCF) and carbon black (CB). Foamed and solid samples were injection molded and then analyzed for cell size, fiber length, fiber orientation, and electrical conductivity. Foamed samples exhibited higher electrical conductivity in the through‐plane direction for materials containing only CB or composites containing both filler types, and reduced electrical conductivity in the cCF‐filled composites. The increased electrical property gained by foaming was attributed to multiple percolation with CB aggregates forming more effective conductive clusters and networks in the continuous polymer phase during growth of the gas domains. A mechanism for the phenomenon was proposed based on these experimental observations. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010