Synergistic effect of three‐dimensional multi‐walled carbon nanotube–graphene nanofiller in enhancing the mechanical and thermal properties of high‐performance silicone rubber

The homogeneous dispersion of nanofillers and filler–matrix interfacial interactions are important factors in the development of high‐performance polymer materials for various applications. In the present work, a simple solution‐mixing method was used to prepare multi‐walled carbon nanotube (MWCNT)–graphene (G) (3:1, 1:1, 1:3) hybrids followed by their characterization through wide‐angle X‐ray diffraction, transmission electron microscopy and thermogravimetric analyses. Subsequently, MWCNT–G (1:1) hybrid was used as reinforcing filler in the formation of silicone rubber (VMQ) nanocomposites by solution intercalation, and their morphology and properties were investigated. Our findings showed that MWCNT–G (0.75 wt%)/VMQ composite exhibited significant improvements in tensile strength (110%) and Young's modulus (137%) compared to neat VMQ. The thermal stability of MWCNT–G (1 wt%)/VMQ was maximally improved by 154 °C compared to neat VMQ. Differential scanning calorimetry demonstrated the maximum improvement of glass transition temperature (4 °C), crystallization temperature (8 °C) and melting temperature (5 °C) for MWCNT–G (1 wt%)/VMQ nanocomposite with respect to neat VMQ. Swelling measurements confirmed that the crosslink density and solvent resistance were a maximum for hybrid nanocomposites. Such improvements in the properties of MWCNT–G/VMQ nanocomposites could be attributed to a synergistic effect of the hybrid filler. © 2013 Society of Chemical Industry     

On the structure and morphology of polyvinylidene fluoride-nanoclay nanocomposites

Polyvinylidene fluoride (PVDF)-nanoclay nanocomposites were prepared by both solution casting and co-precipitation methods with the nanoclay loading of 1-6 wt%. The structure and morphology of the nanocomposite were investigated by wide angle X-ray diffraction (WAXD), polarized light microscopy and transmission electron microscopy (TEM) techniques. PVDF phase transformation behavior was investigated using differential scanning calorimetry and in situ thermal WAXD. All the three typical nanoclay morphologies, namely, exfoliated, partially intercalated and phase separated morphologies, were observed in the PVDF-nanoclay nanocomposites prepared by different methods. In solution-cast samples, phase separation and intercalation occurred depending upon the organic modifiers while complete exfoliation of the nanoclays was observed in the co-precipitated nanocomposites. Furthermore, unique parallel orientation of the nanoclay layers and polymer film surface was achieved in solution-cast samples. β-form PVDF was observed in all the nanocomposites regardless of the nanoclay morphology and contents. Both crystallization and melting temperatures of PVDF were increased with the addition of nanoclay, possibly due to the formation of the β-form PVDF.     

Smart,lightweight, flexible NiO/poly(vinylidene flouride) nanocomposites film with significantly enhanced dielectric,piezoelectric and EMI shielding properties

We report a facile technique to fabricate flexible and self-standing NiO/PVDF nanocomposite films. Detail structural and thermal characterizations of nanocomposite films show the gradual increase of electroactive β-phase of PVDF with increasing NiO nanoparticles content. The enhancement of β phase in the NiO/PVDF nanocomposites has been explained from physicochemical point of view. Electrical properties of the nanocomposites indicate fair improvement in dielectric properties at low filler loading with less dielectric loss. The value of dielectric constant of 0.75 wt% NiO/PVDF films at 100 Hz is five times higher than that of neat PVDF. Series-parallel model was used to describe the filler concentration dependence of the dielectric constant of the nanocomposites. These nanocomposites also exhibit excellent ferroelectric properties. Nanocomposite films having thickness 300 μm were also successfully employed for microwave shielding application. This work suggests that these films would be very useful for thinner, lighter energy harvesting storage and EMI shielding applications.     

Improving the dispersion of MWCNT and MMT in PVDF melts employing controlled extensional flows

Poly (vinylidene fluoride) (PVDF) has been widely explored to produce polymer nanocomposites possessing outstanding combinations of properties. In this work, the impact of extensional melt flows on the dispersion, relaxation and crystallinity of PVDF nanocomposites filled with multiwalled carbon nanotubes (MWCNT) and montmorillonites (MMT) was studied. Extrusion was employed to produce nanocomposites containing 3 wt% of fillers, named: (i) PVDF/3 wt% MWCNT, (ii) PVDF/3wt%MMT, and (iii) PVDF/1.5wt%MWCNT/1.5 wt% MMT. The results showed that applying a sequence of extensional flows through the melts improved the dispersion of both fillers in the PVDF matrix. Moreover, extensional flows significantly enhanced the viscosity and relaxation of MWCNT nanocomposite, but had marginal effects on MMT nanocomposite. On the other hand, MMT favored the crystallization of the β piezoelectric phase of PVDF over the α phase and the extensional flow enhanced its crystallinity content. Therefore, these new insights prospect a vast horizon toward the use of extensional flows for tailoring synergic combinations of properties in hybrid PVDF/MWCNT/MMT systems.     

Fabrication and characterization of functionally graded nanoclay/glass fiber/epoxy hybrid nanocomposite laminates

In this work, hardness, tensile, impact, bearing strength and water absorption tests were performed to study the mechanical properties of stepwise graded and non-graded hybrid nanocomposites. Three different stepwise graded nanocomposites and one non-graded (homogeneous) nanocomposite with the same geometry and total nanoclay content of 10 wt% were designed and prepared. Moreover, one neat glass fiber laminate was manufactured. The results of the tests indicated that addition of the graded and non-graded nanoclay improves hardness over neat glass fiber reinforcement. The maximum increase in hardness of about 53% over neat specimen is obtained for specimens that have the highest weight percentage (2 wt%) of the clay nanoparticles on its surface (S-specimen and the side of F-specimen that reinforced with 2 wt% nanoclay). The gradation process results in an increase in hardness of about 11% compared with non-graded (homogeneous) specimen. In addition, an improvement of 11.9% in strain-to-failure is achieved with specimen having greatest amount of nanoclay in the middle over neat glass fiber/epoxy composite. The other nanoclay-filled glass fiber composites have strain-to-failure close to neat glass fiber/epoxy. The addition of nanoclay reinforcement has insignificant effect on ultimate tensile strength, tensile modulus, water absorption, bearing strength and impact strength compared with neat glass fiber/epoxy.     

Dielectric properties of multiwalled carbon nanotube/clay/polyvinylidene fluoride nanocomposites: Effect of clay incorporation

This study investigates the effect of clay addition on the broadband dielectric properties of multi‐walled carbon nanotube/polyvinylidene fluoride (MWCNT/PVDF) composites, that is, frequency range of 10¹−10⁶ Hz. Different loadings of MWCNT and clay were used for the preparation of three‐phase (MWCNT/Clay/PVDF) nanocomposites via melt‐mixing method. The crystalline structure and morphology of nanocomposites were examined by employing characterization techniques such as X‐ray diffraction, transmission electron microscopy, and differential scanning calorimetry. The dielectric spectroscopy showed that introducing clay into the MWCNT/PVDF nanocomposites at a critical MWCNT concentration improved dielectric properties tremendously. It was interestingly observed that the incorporation of a specific amount of clay, that is, 1.0 wt%, into the (MWCNT/PVDF) nanocomposite at a critical MWCNT loading, that is, 0.5 wt% MWCNT, resulted in a huge increase in the dielectric permittivity (670% at 100 Hz) and a considerable reduction in the dissipation factor (68% at 100 Hz). POLYM. COMPOS., 161–167, 2016. © 2014 Society of Plastics Engineers     

The influence of MWCNT and hybrid (MWCNT/nanoclay) fillers on performance of EPDM-CIIR blends in nuclear applications: Mechanical,hydrocarbon transport,and gamma-radiation aging characteristics

Blends of EPDM and chlorobutyl (CIIR) rubbers are used in nuclear plants where they have to withstand the combined effect of radiation and hydrocarbon aging. To improve their mechanical properties as well as hydrocarbon and gamma radiation resistance, the blends are reinforced with 0.5, 1, 1.5, and 2 phr of MWCNT. The increase in mechanical properties was highest for 1.5 phr MWCNT with 69% increase in tensile strength. The improvement in properties was correlated to MWCNT dispersion and filler–polymer interactions, which were confirmed by TEM and FTIR analysis. Hydrocarbon transport coefficients decreased on addition of MWCNT. The nanocomposites were exposed to 0.5, 1, and 2 MGy cumulative doses of gamma radiation. Depending on the radiation dose, crosslinking and/or chain scission occurred causes changes in physical properties. MWCNT reinforcement reduced the magnitude of changes in mechanical and transport properties after γ-irradiation. ESR and FTIR spectra provided qualitative information on free radical formation and chemical changes due to γ-rays exposure. To further enhance the properties, hybrid nanocomposites with 1.5 phr MWCNT and varying nanoclay contents (0.5, 1, 1.5, 2, and 5 phr) were prepared. Due to synergism between MWCNT and nanoclay, the hybrid composites had superior properties with hybrid containing 5 phr nanoclay giving 98% increase in tensile strength.     

Polyvinylidene fluoride nanofibers obtained by electrospinning and blowspinning: Electrospinning enhances the piezoelectric β-phase – myth or reality?

Considerable effort has been devoted to improving the properties of PVDF (polyvinylidene fluoride), arguably the most technologically important piezoelectric polymer. Electrospinning has been found to be a particularly effective method of producing PVDF nanofibers with superior piezoelectric properties due to the resulting exceptionally high fraction of the piezoelectrically active crystalline β-phase. It is typically assumed that the high external electric fields applied during electrospinning enhance the formation of this β-phase, with the confused literature offering various unsatisfactory mechanistic explanations. However, by comparing PVDF nanofibers produced by two different processes (electrospinning and blowspinning), we show that the electric field is entirely unnecessary; indeed, the crystallization dynamics are principally driven by the applied mechanical stress, as evidenced by structurally identical 200 nm diameter PVDF fibers produced with and without external electric fields.     

Preparation of PVDF/PVP core–shell nanofibers mats via homogeneous electrospinning

The polyvinylpyrrolidone (PVP)/poly(vinylidene fluoride) (PVDF) core–shell nanofiber mats with superhydrophobic surface have been prepared via electrospinning its homogeneous blending solutions, and the formation of the core–shell structure was achieved by the thermal induced phase separation assisted with the low surface tension of PVDF. The electrospinnability of the blending solutions was also investigated by varying the blending ratio of the PVP and PVDF, and it enhanced with the increase of PVP content. SEM and TEM results showed that the fibers size was varied in the range of 100 nm–600 nm with smooth surface and core–shell structure. The composition of the shell layer was determined by the XPS analysis, and further confirmed by water contact angle (WCA) testing. As the fraction of PVDF exceeding PVP in the electrospinning solutions, the nanofiber mats showed superhydrophobic property with the WCA above 120°. It indicated that the PVDF was concentrated in the shell layer of the fibers. X-Ray diffraction (XRD) and attenuated total reflection infrared spectroscopy (ATR-IR) analysis indicated that the PVDF was aggregated with the β-phase crystallite as dominant crystallite. The nanofiber mats with the gas breathability and watertightness ability due to the porous structure and superhydrophobic would be potential applied in wound healing.     

Solution blow spinning of piezoelectric nanofiber mat for detecting mechanical and acoustic signals

Solution blow spinning (SBS) technique can produce nanofibers (NFs) mat in large-scale production. In this work, the SBS was used to fabricate piezoelectric polyvinylidene fluoride (PVDF) NF membranes that can be utilized for energy harvesting applications. The effect of operating air pressure from (2–5 bar) on the surface morphology of the NFs has been studied. The structural analysis for crystalline polymorph β-phase for PVDF powder, casted film, electrospinning and SBS NFs has also been presented with the aid of Fourier-transform infrared spectroscopy and X-ray diffraction (XRD). Piezoelectric characteristics of PVDF NFs mats were tested by applying impact impulse with different weights from different heights between 1 and 10 cm. The sensitivity of the voltage response increased from 1.71 mV/g to 8.98 mV/g, respectively. Besides, the SBS generated PVDF mat is found to be sensitive to pressure forces in a range of few Newtons with the generated voltage according to detected sensitivity of 80 mV/N based on the analysis of the impact of a few Hertz mechanical vibrations. In addition, the produced SBS NFs were applied as an acoustic signal detector within different acoustic frequencies. The results suggest that the β-phase PVDF nanofibrous membrane produced via the SBS technique has a great potential to be used as a piezoelectric sensor.     

Montmorillonite–multiwalled carbon nanotube nanoarchitecture reinforced thermoplastic polyurethane

Montmorillonite (MMT)–multiwalled carbon nanotube (MWCNT) hybrids were prepared in different weight ratios by simple dry grinding method and characterized. Subsequently, MMT–MWCNT (1:1) hybrid was used as reinforcing filler in developing thermoplastic polyurethane (TPU) nanocomposites by solution blending method. Thermogravimetric analysis showed that 0.25 wt% hybrid‐loaded TPU nanocomposite exhibited maximum enhancement of 31°C corresponding to 50 wt% loss in thermal stability when compared with neat TPU. Differential scanning calorimetry of this composite also indicated that its crystallization and melting temperatures are enhanced by 37 and 13°C, respectively. Mechanical data showed that tensile strength and Young's modulus of 0.50 wt% filled TPU were maximum improved by 57 and 87.5%, respectively. Dynamic mechanical analysis (DMA) measurements indicated 174% (50°C) improvement in storage modulus of 0.50 wt% hybrid‐loaded TPU. Such improvements in thermal and mechanical properties have been attributed to homogeneous dispersion, strong interfacial interaction, and synergistic effect. POLYM. COMPOS., 37:1775–1785, 2016. © 2014 Society of Plastics Engineers     

The effect of secondary nanofiller on mechanical properties and formulation optimization of HDPE/nanoclay/nanoCaCO3 hybrid nanocomposites using response surface methodology

Mechanical properties were evaluated in high-density polyethylene (HDPE) containing plate-like nanoclay (NC) and particulate nano calcium carbonate (nCaCO₃). A two-step melt mixing method was utilized to prepare nanocomposites withNC/nCaCO₃ hybrid content varying from 7 to 15 wt%. Optimization of the morphological, rheological and mechanical characteristics was carried out via Response Surface Methodology by considering nanofiller loadings and compatibilizer (PE-g-MA) content as independent variables. The findings revealed that a nanocomposite composed of 9 wt% PE-g-MA, 3.5 wt%NC, and 10 wt%nCaCO₃ was optimal. This composition exhibited 50% enhancement in Young's modulus and 8% improvement in yield strength over neat HDPE. Despite the reduced impact strength in all of the prepared nanocomposites, the incorporation ofnCaCO₃ prevented a sudden decrease in the toughness caused by the nanoclay. Further, the fracture behavior observed by scanning electron microscopy (SEM) images suggested that nCaCO₃ activated new toughening mechanisms.     

Influence of Copper Nanoparticles Concentration on the Properties of Poly(vinylidene fluoride)/Cu Nanoparticles Nanocomposite Films

In this study, the nanocomposite films of polyvinylidene fluoride/copper nanoparticles were prepared by mixing of copper nanoparticles in a solution of dimethylformamide and polyvinylidene fluoride. The prepared nanocomposites were investigated by fourier transform infrared spectroscopy and X-ray diffraction techniques, showed an obvious α- to β-phase transformation compared to pure PVDF. Scanning electron microscope micrographs showed spherulitic crystal structure of PVDF. The spherulitic morphology of the pure PVDF is maintained for the PVDF nanocomposites; the size of the spherulites decreased by increasing weight fraction of copper nanoparticles. The optical band gap values deduced from the UV–Visible absorption spectra were found to reduce from 4.77 eV in pure PVDF to 3.2 eV after embedding 1 wt% of copper nanoparticles. The surface resistivity values were decreased with increasing copper nanoparticles content. Thermal stability of the nanocomposites was studied by thermogravimetric analysis (TGA). TGA curves showed that nanocomposite films have higher resistance to thermal degradation compared to pure PVDF.     

Morphology, structure and properties of conductive PS/CNT nanocomposite electrospun mat

The morphologies and properties of Polystyrene (PS)/Carbon Nanotube (CNT) conductive electrospun mat were studied in this paper. Nanocomposite fibers were obtained through electrospinning of PS/Di-Methyl Formamide (DMF) solution containing different concentrations and types of CNTs. The dispersion condition of CNTs was correlated to morphologies and properties of nanocomposite fibers. A copolymer as an interfacial agent (SBS, Styrene-butadiene-styrene type) was used to modify the dispersion of CNTs in PS solution before electrospinning. The results showed that the presence of the copolymer significantly enhances CNT dispersion. The fiber diameters varied between 200 nm and 800 nm depending on CNT type, polymer concentration and copolymer. The final morphological study of the fibers showed that CNT addition caused a decrease in beads formation along fiber axis before percolation threshold. However, addition of CNTs above percolation increased the beads formation, depending on the dispersion condition. The presence of SBS modified the dispersion, reduced the fiber diameter and the number of bead structures. Electrical conductivity measurements on nanocomposite mats of 15-300 μm in thickness showed an electrical percolation threshold around 4 wt% MWCNT; while the samples containing SBS showed higher values of conductivities below percolation compared to the samples with no compatibilizer. Enhancement in mechanical properties was observed by the addition of CNTs at concentrations below percolation.     

Synthesis of β-myrcene-based macroporous nanocomposite foams: Altering the morphological and mechanical properties by using organo-modified nanoclay

Organo-modified nanoclay incorporated high internal phase emulsions (HIPEs) were successfully used for the preparation of macroporous nanocomposite foams. Due to the aim of obtaining mechanically improved foams, HIPEs were prepared by using a monomer mixture composed of β-myrcene and ethylene glycol dimethacrylate. Accordingly, two groups of macroporous nanocomposite foams were synthesized depending on the nanoclay type. The morphological analysis demonstrated that the pore openness of the resulting nanocomposites were significantly improved due to the decrease in the average cavity size and increase in the interconnected pore size. In terms of mechanical properties, it was found that filling 1 wt% of nanoclay which is surface modified by hydrogenated tallow lead to a 33% of increment in the compression modulus, as compared to the neat foam. However, loading 5 wt% of nanoclay having octadecylamine and aminopropyltriethoxysilane surface groups caused only 11% of increment in the compression modulus, as compared to the neat foam.     

Suppression of AC conductivity by crystalline transformation in poly(vinylidene fluoride)/carbon nanofiber composites

Poly(vinylidene fluoride) (PVDF) is an important ferroelectric semi-crystalline polymer with multiple-phase behavior. In this study, remarkable effects of the various crystalline structures of PVDF nanocomposites on alternating current (AC) conductivity were discovered using carbon nanofibers (CNF). It was found that the transformation from α-phase to β-phase in PVDF, induced by the addition of CNFs, had a surprisingly suppressive effect on the AC conductivity of the nanocomposites. These unexpected results indicate that the decline in conductivity occurs after re-crystallization treatment (annealing) of the nanocomposites, and the reduction levels increase with increasing amounts of CNFs. Interestingly, the AC conductivity of annealed 5 wt% CNF/PVDF composites becomes even lower than that of re-crystallized nanocomposites with 3 wt% CNFs. These findings are believed to be very significant for fabrication and long-term service of PVDF composites in industry, which often involves exposure to repeated thermal cycling.     

Morphology, polymorphism behavior and molecular orientation of electrospun poly(vinylidene fluoride) fibers

The morphology, polymorphism behavior and molecular orientation of electrospun poly(vinylidene fluoride) (PVDF) fibers have been investigated. We found that electrospinning of PVDF from its N,N-dimethylformamide/acetone solutions led to the formation of β-phase. In contrast, only α- and γ-phase was detected in the spin-coated samples from the same solutions. In the aligned electrospun PVDF fibers obtained using a rotating disk collector, the β-phase crystallites had a preferred orientation along the fiber axis. The degree of orientation did not, however, vary significantly with the speed of the rotation disk collector, and the β-phase was also not significantly enhanced with the increase in the rotation speed or the decrease in the size of spinnerets. These facts indicated that the orientation was likely to be caused by Columbic force rather than the mechanical and shear forces exerted by the rotating disk collector and spinnerets. The Columbic force may induce local conformational change to straighter TTTT conformation, and hence promote the β-phase. The addition of 3 wt.% of tetrabutylammonium chloride (TBAC) into the polymer solutions effectively improved the morphology of the electrospun fibers, and led to almost pure β-phase in the fibers. With spin coating, PVDF-TBAC did not, however, show any strong β-phase diffraction peak. The synergistic β-enhancement effect of TBAC and electrospinning is possibly due to the fact that while TBAC could induce more trans conformers, electrospinning promotes parallel packing, and hence inter-chain registration.     

High dielectric constant epoxy nanocomposites containing ZnO quantum dots decorated carbon nanotube

Zinc oxide (ZnO) quantum dot (QD) decorated multi-walled carbon nanotube (MWCNT) hybrid was utilized in the fabrication of high dielectric constant epoxy nanocomposites. Because of the shielding effect of ZnO QD, the well-dispersed epoxy hybrid nanocomposites exhibit frequency insensitive high dielectric constant as well as greatly reduced dielectric loss. With only 1.5 wt% of MWCNT addition, the epoxy/MWCNT-ZnO nanocomposite possesses dielectric constant as high as 31 and dielectric loss as low as 0.01 at 1 kHz. In addition, the epoxy nanocomposite exhibits greatly enhanced tensile properties. The role of ZnO QD decorated MWCNT in the preparation and property improvement of multi-functional polymer nanocomposites is discussed.     

PVDF/BaTiO3/carbon nanotubes ternary nanocomposites prepared by ball milling: Piezo and dielectric responses

Nanocomposites based on poly(vinylidene fluoride) (PVDF) filled with barium titanate, BaTiO₃, (BT) particles, and multiwalled carbon nanotubes (MWCNTs) were prepared by high-energy ball milling (HEBM) and subsequent hot pressing. This method of materials preparation allowed obtaining uniform dispersions of the nanofillers. The influence of the particles on the polymer structure and morphology was studied. To understand the origin of changes in the PVDF properties, thermal and electrical behaviors of the PVDF/BT/MWCNT nanocomposites were studied as a function of composition. The addition of BT, MWCNT, or its mixture had not any influence on the PVDF polymorphism. However, calorimetric results pointed out that the presence of the nanofillers exerted nucleation mainly ascribed to the surface to volume ratio of the nanoparticles. The capacitance of the composites increased as the nanofiller content increased, being the effect mainly dependent on the surface to volume ratio of the nanoparticles. The dielectric behavior of the materials as a function of frequency was modeled by a Debye equivalent circuit only below the percolation threshold respect to the amount of MWCNT. The piezoelectric behavior of the ternary nanocomposites was highly affected by the incorporation of the nanofillers only when high dielectric losses occurred above the percolation threshold. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47788.     

Remarkable change in the broadband electrical behavior of poly(vinylidene fluoride)–multiwalled carbon nanotube nanocomposites with the use of different processing routes

Poly(vinylidene fluoride) (PVDF) nanocomposites have plenty of applications in the electronic realm. In this study, we produced nanocomposites based on PVDF and multiwalled carbon nanotubes (MWCNTs), with various MWCNT loadings, using three different processing routes: solution mixing, melt mixing, and electrospinning. The broadband electrical behavior of these nanocomposites was studied and compared via impedance spectroscopy. The morphologies of the nanocomposites were characterized by transmission electron microscopy and scanning electron microscopy. The results reveal that the electrical behaviors of the samples were completely different according to the processing route used. Solution mixing was the most suitable method for producing nanocomposites with the highest conductivities, at low MWCNT loadings, whereas electrospinning was the most suitable method for producing nanocomposites with the lowest dielectric permittivity. These differences were attributed to the different arrangements of the MWCNTs caused by the different processes. Although the solution-mixed samples exhibited long and twisted MWCNTs, the melt-mixed samples had shorter MWCNTs, and the electrospun samples had MWCNTs embedded and aligned inside the insulating polymer nanofibers. Thus, these results project a vast horizon for tailoring the structure and thereby the broadband electrical behavior of PVDF–MWCNT nanocomposites for different types of applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47409.