Electrical and piezoresistive properties of multi-walled carbon nanotube/polymer composite films aligned by an electric field

Aligned multi-walled carbon nanotube (MWCNT)/polymer composite films are prepared by solution casting in the presence of an alternating electric field. Application of 7 kV/m at a frequency of 60 Hz to the polymer composite melt induces MWCNT alignment in the direction of the applied field, which is maintained after polymer crystallization. The electrical conductivity and piezoresistive response of electric-field-aligned and randomly oriented 0.1–0.75 wt% MWCNT/polysulfone films are evaluated. Electrical conductivity is 3–5 orders of magnitude higher for composites with electric-field-aligned MWCNTs than for randomly oriented composites. MWCNT alignment inside the polymer matrix also increases the film piezoresistive sensitivity, enhancing the strain sensing capabilities of the composite film.     

Preparation and properties of multi-walled carbon nanotube/carbon/polystyrene composites

Multi-walled carbon nanotube (MWCNT)/C/polystyrene (PS) composite materials were prepared by in situ polymerization of monomer in preformed MWCNT/C foams. MWCNT/C foams were preformed using polyurethane foam as template. The preformed MWCNT/C foams had a more continuous conductive structure than the carbon nanotube networks formed by free assembly in composites. The structure of the MWCNT/C foam network was characterized with scanning electron microscopy. The MWCNT/C/PS composites have an electric conductivity higher than 0.01 S/cm for a filler loading of 1 wt.%. Enhancement of thermal conductivity and mechanical properties by the preformed MWCNT/C foam were also observed.     

Viscoelastic and photo-actuation studies of composites based on polystyrene-grafted carbon nanotubes and styrene-b-isoprene-b-styrene block copolymer

Photoactuating composites based on the linear triblock copolymer polystyrene-b-polyisoprene-b-polystyrene (SIS) were prepared by incorporation of polystyrene-modified multiwalled carbon nanotubes (MWCNT–PS). Modification of MWCNT was performed by surface-initiated atom transfer radical polymerization (SI ATRP) of styrene. The presence of the polystyrene chains on the MWCNT surface facilitated their dispersion in the SIS matrix. Improved interactions of the modified MWCNT–PS compared to neat MWCNT were confirmed by dynamic mechanical analysis. The activation energy of glass transition of the polystyrene phase in the MWCNT–PS/SIS composite increased significantly compared to the neat SIS matrix, while the incorporation of neat MWCNT to the SIS matrix disturbed the physical cross-linking of the SIS and degraded its elastic properties. The photo-actuation ability of the MWCNT–PS/SIS composite was proved using atomic force microscopy.     

Thermosetting polyurethane‐multiwalled carbon nanotube composites: Thermomechanical properties and nanoindentation

In this study, composites based on a thermoset polyurethane elastomer (PU) and multiwalled carbon nanotubes (MWCNT) in the case of a PU of high elastic modulus (>200 MPa) are analyzed for the first time. As‐grown and modified nanotubes with 4 wt % of oxygenated functions (MWCNT‐ox) were employed to compare their effect on composite properties and maxima mechanical properties (elastic modulus and tensile strength) were reached at 0.5 wt % of MWCNT‐ox. Furthermore, by examining the morphology using optical and electron microscopies better dispersion and interaction of the nanotube‐matrix was observed for this material. DMTA data supports the observation of an increase in the glass transition temperature of ～20°C in the nanocomposites compared with the thermoset PU, which is an important result because it shows extended reliability in extreme environments. Finally, nanoindentation tests allowed a comparison with the conventional mechanical tests by measuring the elastic modulus and hardness at the subsurface of PU and the nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41207.     

Polystyrene composites containing crosslinked polystyrene‐multiwalled carbon nanotube balls

Crosslinked polystyrene‐multiwalled carbon nanotube (PS‐MWCNT) balls, which act as conductive microfillers, were prepared by the in situ suspension polymerization of styrene with MWCNTs and divinyl benzene (DVB) as a crosslinking agent. The diameters of the synthesized crosslinked PS‐MWCNT balls ranged from 10 to 100 μm and their electrical conductivity was about 7.7 × 10^?3 S/cm. The morphology of the crosslinked PS‐MWCNT balls was observed by scanning electron microscopy and transmission electron microscopy. The change in the chemical structure of the MWCNTs was confirmed by Raman spectroscopy and Fourier transform infrared spectroscopy. The mechanical and electrical properties of the PS/crosslinked PS‐MWCNT ball composites were investigated. It was found that the tensile strength, ultimate strain, Young's modulus, and impact strength of the PS matrix were enhanced by the incorporation of the crosslinked PS‐MWCNT balls. In addition, the mechanical properties of the PS/crosslinked PS‐MWCNT ball composites were better than those of the PS/pristine MWCNT composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influences of hybrid carbon nanofillers on structures and electrical properties of sulfonated poly(1,3,4‐oxadiazole)‐based composite films

Sulfonated poly(1,3,4‐oxadiazole) (sPOD)‐based composite films, including 10 wt % hybrid carbon nanofillers composed of different weight ratios of multiwalled carbon nanotube (MWCNT) and graphene sheets, were manufactured via an efficient ultrasonication‐assisted solution mixing and casting. Fourier transform infrared (FTIR) spectra of the composite films confirmed the existence of specific interactions between sPOD backbone and MWCNT or graphene sheet. Transmission electron microscopic (TEM) images of cross sections of the composite films showed that 2‐dimensional (2D) graphene sheets formed an anisotropically oriented structure in the sPOD matrix film, but they are randomly dispersed owing to the introduction of 1‐dimensional (1D) MWCNT. Accordingly, the electrical resistivity of the composite films decreased largely from ～10³ Ω cm to ～10¹ Ω cm with the increment of the relative MWCNT content in hybrid carbon nanofillers due to the synergistic bridging effect. Thus, sPOD‐based composite films with 10 wt % hybrid carbon nanofillers exhibited high performance in electric heating by attaining rapid temperature responsiveness, high electric power efficiency, and stable maximum temperatures under given applied voltages. It was also revealed that the hybrid composite films were operationally stable over a long‐term stepwise electric heating experiment. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44499.     

Electrical conductivity and mechanical performance of multiwalled CNT‐filled polyvinyl chloride composites subjected to tensile load

This article reports a study on the strain‐sensitive conductivity (tensoresistivity) and mechanical properties of polyvinyl chloride/multiwalled carbon nanotube (PVC/MWCNT) composites subjected to tensile loading at different strain rates for potential use in sensor‐enabled geosynthetics and other applications involving electrically conductive polymer composites. Results indicate that adding 0.5 wt % MWCNT to the composite results in 57% reduction in its ultimate (failure) strain and a fivefold increase in its tensile modulus while leaving its ultimate strength almost unchanged. Laser scanning confocal microscopy is used to investigate the microscopic failure mechanism of the composite and how it contributes to the strain‐sensitive conductivity of the composites. It is observed that tensile fractures are initiated from inside the largest bundles between 18% and 36% strain and continue through further fractal‐like fracturing in smaller bundles. Gauge factors (e.g., 3.17) comparable to or exceeding those of typical strain gauges are obtained for the composite, indicating its strong potential for structural performance monitoring and damage detection applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43665.     

Improving the electrical conductivity of a carbon nanotube/polypropylene composite by vibration during injection-moulding

An isotactic polypropylene/multi-wall carbon nanotube (iPP/MWCNT) composite was prepared by a vibration injection moulding technique. The effect of the vibration field on the electrical conductivity property of samples was investigated. The results show that the electrical conductivities of the samples prepared by vibration injection moulding was far higher than those of samples prepared by conventional injection moulding when the CNT concentration are above 2 wt.% and below 6 wt.%. Besides the electrical conductivity of vibration injection moulded samples are a little higher than those of the compression moulded samples. The higher conductivity was resulted from the MWCNT movement induced by the periodical shear during vibration injection moulding. The agglomerates or individual MWCNT were disentangled, stretched and oriented along the flow direction, resulting in better conducting paths thus greatly increased the electrical conductivity. The electrical conductivity increased with increasing vibration frequency. The difference in the voltage–current relationships among the samples prepared at different vibration frequencies suggests that the mechanism of electrical conductivity of iPP/MWCNT composite changed from a tunnel to an ohmic effect. Compared with conventional injection moulded samples, there was no loss of mechanical properties.     

The effect of temperature on fatigue strength of poly(ether-imide)/multiwalled carbon nanotube/carbon fibers composites for aeronautical application

This work concerns the fatigue behavior at three different temperature conditions (−40, 20, and 80°C) and the addition of multiwalled carbon nanotube (MWCNT) into a carbon-fiber reinforced poly(ether-imide) composite. The incorporation of MWCNT into the composite increased the tensile strength and Young's modulus by up 5 and 2%, respectively. At low temperature, the incorporation of the nanoparticles improved the fatigue strength of the laminates by 15%. The shear strength results obtained by interlaminar shear strength and compression shear test tests have shown an increase of about 16 and 58%, respectively, by the introduction of nanotubes into the laminates. Fractographic observations revealed that the surface of carbon nanotube laminate (PEI/MWCNT/CF) presented a ductile behavior, and differences in the fracture aspects of the material compared to the traditional PEI/CF laminate have been observed.     

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     

Dynamic mechanical characterization of PC/MWCNT composites under variable temperature conditions

A dynamic mechanical analysis has been performed on composite materials of polycarbonates (PC) and multi-walled carbon nanotubes (MWCNT) for evaluation of their mechanical hardness and storage modulus under the combined effects of variable loading frequencies and temperature conditions. The PC-based engineering machine components that are subjected to variable external loads and temperature conditions are not durable owing to the viscoelastic properties of PC. Composites of PC with MWCNT (2, 5 and 10 wt%) were fabricated and their mechanical characterization tests revealed that with increase in MWCNT composition both storage modulus and hardness enhanced significantly in comparison to pure PC. For 10 wt% PC/MWCNT composite, the average storage modulus increased in the range of 40–92%, while the average hardness was enhanced in a range of 88–121% for the combined effect of temperature range of 30–90 °C and loading frequency range of 30–230 Hz. With increase in temperature, the maxima of storage moduli and hardness for these composites shifted toward higher loading frequencies, indicating that these composites can be used for wider loading frequency range. Therefore, the experimental results of this paper have shown that the mechanical properties of PC-based composite materials with minor MWCNT compositions are enhanced significantly and hence can be used for automotive and aerospace engine parts where loading frequencies are high and temperature conditions are variable.     

Synthesize procedures,mechanical and electrical properties of poly(vinylidene fluoride) nanocomposite thin films containing multiwalled carbon nanotubes

A procedure is proposed to prepare poly(vinylidene fluoride) (PVDF) multiwalled carbon nanotubes (MWCNTs) nanocomposite thin films with improved mechanical and dielectric properties compared to the pure PVDF films. The PVDF/MWCNT mixture with a composition range from 0.0 to 5.0% MWCNTs by weight was formed using solution blending and the ultrasonic dispersion method and then spin coated on a rotating glass substrate to produce films nearly 20 μ thick. Results indicate that the appropriate addition of MWCNTs (up to 3.0 wt%) to PVDF can significantly increase its elastic modulus while decrease its fracture toughness. The elastic modulus shows softening at a 5.0 wt% MWCNT loading. The DC and AC conductivity of the composite films were also examined with various MWCNTs concentrations. The dielectric constants were found more than doubled for 0.5 wt% MWCNTs composite compared to the values for the pure PVDF. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Prediction of the mechanical characteristics of multi-walled carbon nanotube/epoxy composites using a new form of the rule of mixtures

Multi-walled carbon nanotubes (MWCNTs) were used in the low-viscosity, thermosetting polyester epoxy/amine resin LY-5052 with high temperature resistance to fabricate MWCNT/epoxy composites. Tensile tests of the specimens were carried out to obtain mechanical properties of MWCNT/epoxy composites for various weight-percents (wt.%) of MWCNTs. Experimental results show that the Young’s modulus and the tensile strength of the composites can be significantly improved by adding a small percentage of MWCNT. A new form of the rule of mixtures, including an exponential shape function, length efficiency parameter, orientation efficiency factor and a waviness parameter, is proposed for a more accurate prediction of the mechanical properties of MWCNT-reinforced epoxy composites, for both low and high wt.% ranges. In order to verify the suitability of the model, the ensuing predictions are compared to the available experimental data in the literature. Results demonstrate a good predictability of the modified form over a wide range of tests.     

Preparation and properties of plasticized starch/multiwalled carbon nanotubes composites

In this work we have studied the utilization of multiwalled carbon nanotubes (MWCNTs) as filler‐reinforcement to improve the performance of plasticized starch (PS). The PS/MWCNTs nanocomposites were successfully prepared by a simple method of solution casting and evaporation. The morphology, thermal behavior, and mechanical properties of the films were investigated by means of scanning electron microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, and tensile testing. The results indicated that the MWCNTs dispersed homogeneously in the PS matrix and formed strong hydrogen bonding with PS molecules. Compared with the pure PS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 2.85 to 4.73 MPa and from 20.74 to 39.18 MPa with an increase in MWCNTs content from 0 to 3.0 wt %, respectively. The value of elongation at break of the nanocomposites was higher than that of PS and reached a maximum value as the MWCNTs content was at 1.0 wt %. Besides the improvement of mechanical properties, the incorporation of MWCNTs into the PS matrix also led to a decrease of water sensitivity of the PS‐based materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

The preparation of cation-functionalized multi-wall carbon nanotube/sulfonated polyurethane composites

Covalent functionalization of multi-wall carbon nanotubes (MWCNTs) with minimal alteration to the MWCNT surface is important to achieve homogenously dispersed carbon nanotubes while maintaining their unique mechanical and electrical properties. Carboxylic acid derivatized MWCNTs (MWCNT-COOH) were covalently functionalized with 3,3′-iminobis(N,N-dimethylpropylamine) (DMPA). Upon subsequent quaternization of DMPA, dendritic ammonium cation-functionalized MWCNTs (MWCNT-DMPA⁺) were formed, where two ammonium cations were incorporated per amide site. Thermogravimetric analysis and X-ray photoelectron spectroscopy demonstrated successful covalent functionalization and formation of the surface-bound ammonium salt. Raman spectroscopy and atomic force microscopy indicated the absence of an appreciable decrease in the MWCNT aspect ratio. Compared with pristine MWCNTs and MWCNT-COOH, MWCNT-DMPA⁺ exhibited enhanced dispersibility in N,N-dimethylformamide (DMF) as observed with UV–Visible spectroscopy and transmission electron microscopy (TEM). In addition, blending the cation-bound MWCNT-DMPA⁺ with anion-bound sulfonated polyurethane in DMF generated novel composites with a nanotube content ranging from 0.5 to 5 wt.%. Characterization of the composite films using both field emission scanning electron microscopy and TEM revealed that MWCNT-DMPA⁺ exhibited uniform dispersion in sulfonated polyurethane matrices even at 5 wt.%. Tensile analysis showed that the modulus of the sulfonated polyurethane matrix linearly increased with MWCNT-DMPA⁺ content.     

Mechanical properties and thermal stability of porous polyimide/hollow mesoporous silica nanoparticles composite films prepared by using polystyrene microspheres as the pore-forming template

The porous polyimide/hollow mesoporous silica nanoparticles (PI/HMSNs) composite films were fabricated via blending polymerization by using polystyrene (PS) microspheres as the pore-forming template. The morphologies, microstructures, thermal stability, thermal expansion coefficient (TEC), and mechanical performances of the porous PI/HMSNs films were characterized in detail. Results showed that the uniform dispersion of HMSNs benefits from the strong hydrogen-bonding interaction between the hydroxyl groups of HMSNs and poly(amic acid) chains. Both weight loss and TEC of the porous PI/HMSNs films are lower than those of the pure porous PI film. When 0.8 wt % HMSNs and 7.0 wt % PS were added into the PI matrix, the Young's modulus and tensile strength of composite film increased by about 32.4% and 68.1% compared with those of the pure porous PI film. Conclusively, the introduction of HMSNs in the porous PI matrix is an important strategy to enrich the diversity of porous structure, improve the thermal and mechanical properties of the porous PI material simultaneously. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48792.     

Mechanical and water binding properties of carboxymethyl cellulose/multiwalled carbon nanotube nanocomposites

Carboxymethyl cellulose (CMC) composite films were prepared from CMC solutions (2% w/v) containing multiwalled carbon nanotubes (MWCNT) as nanofiller and glycerol (25% w/w CMC) as plasticizer. Tensile strength, elongation at break (EAB), young's modulus, water solubility, water swelling, water uptake, and water vapor permeability (WVP) for CMC films were 27.5 ± 2.5 MPa, 11.2 ± 0.8%, 198 ± 18 MPa, 57 ± 1.5%, 738 ± 25%, 124 ± 4%, and 0.55 ± 0.036 g.mm/m².kPa.h, respectively. By increasing the relative humidity from 11.4 to 85.5%, the moisture absorption (MA) of CMC films was increased from 4 to 38%. Incorporation of MWCNT into the matrix caused a significant increase in the tensile strength, decrease in EAB, increase in young's modulus, decrease in water solubility, decrease in water swelling, decrease in water uptake, and decrease in MA. CMC/MWCNT films containing 1% MWCNT showed the lowest WVP. Scanning electron microscopy showed a good dispersion of MWCNT in the CMC matrix. CMC/MWCNT films containing >1% MWCNT showed significant antibacterial activities against both Gram‐positive and Gram‐negative bacteria in a dose‐dependent manner. Thus, good mechanical properties and water resistance along with strong antibacterial activities make CMC films grafted with MWCNT as a suitable packaging material. POLYM. COMPOS., 36:145–152, 2015. © 2014 Society of Plastics Engineers     

Thermal properties and transition studies of multi-wall carbon nanotube/nylon-6 composites

Transition behavior and thermal properties of a multi-wall carbon nanotube (MWCNT)/nylon-6 composite (P-composite) made by in situ polymerization and subsequently structurally modified by high-pressure–high-temperature treatment have been established. The thermal conductivity (κ) of nylon-6 improved ∼27% by the addition of 2.1 wt.% MWCNT filler simultaneously as the heat capacity per unit volume decreased ∼22% compared with that of nylon-6 at 1 atm and 298 K. Moreover, the MWCNT filler raises the glass transition temperature (T_g) of nylon-6, but the pressure dependence of T_g remains unchanged. A model for κ indicates that the interfacial thermal resistance between the MWCNT filler and the nylon-6 matrix decreases 20% up to 1 GPa and most significantly above 0.8 GPa. P-composite was structurally modified by a sluggish cold-crystallization transition at 1.0 GPa, 530 K, which further increased κ by as much as ∼37% as the crystallinity of nylon-6 improved from 31% to 58% with a preferred crystal orientation and increased crystal size.     

Preparation and characterization of extruded nanocomposite based on polycarbonate/butadiene‐acrylonitrile‐styrene blend filled with multiwalled carbon nanotubes

Nanocomposites of polycarbonate/acrylonitrile‐butadiene‐styrene (PC/ABS) with multiwall carbon nanotubes (MWCNT) prepared by masterbatch dilution are investigated in this work. Melt compounding with twin screw extruder is followed by complete characterization of morphology, rheological‐, mechanical‐, and thermal‐properties of the nanocomposites. Light‐transmission‐ and scanning electron microscopy shows the preferential location of MWCNT in the PC. Nevertheless, relatively good dispersion in the whole matrix is achieved, what is corroborated with the specific mechanical energy. The study of viscoelastic properties of PC/ABS‐MWCNT shows the fluid–solid transition below 0.5 wt % MWCNT. Beyond this point the continuous nanofiller network is formed in the matrix promoting the reinforcement. Addition of 0.5 wt % MWCNT reduces ductility of PC/ABS and enhances Young's modulus by about 30% and yield stress by about 20%. Moreover, theoretical values of stiffness calculated within this work agree with the experimental data. Electrical conductivity, showing percolation at 2.0 wt % MWCNT, are influenced by processing temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40271.     

Positive temperature coefficient to resistively characteristics of polystyrene/nickel powder/multiwall carbon nanotubes composites

Positive temperature coefficient to resistivity (PTCR) characteristics of polystyrene (PS)/Ni‐powder (40 wt%) composites in the presence of multiwall carbon nanotubes (MWCNTs) has been investigated with reference to PS/carbon black (CB) composites. The PS/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈110°C, above the glass transition temperature (T_g) of PS (T_g ≈95°C). Interestingly, the PTC trip temperature of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites appeared at ≈90°C (below T_g of PS), indicating better dimensional stability of the composites at PTC trip temperature. The PTC trip temperature of the composites below the T_g of matrix polymer (PS) has been explained in terms of higher coefficient of thermal expansion (CTE) value of PS than Ni that led to a disruption in continuous network structure of Ni even below the T_g of PS. The dielectric study of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites indicated possible use of the PTC composites as dielectric material. Dynamic mechanical analysis (DMA) and thermogravimetric analysis studies revealed higher storage modulus and improved thermal stability of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites than the PS/CB (10 wt%) composites. POLYM. COMPOS., 33:1977–1986, 2012. © 2012 Society of Plastics Engineers