COOH?MWCNTs‐induced BiFeO3‐poly(vinylidene fluoride) (PVDF) composites with enhanced dielectric and ferroelectric properties

In this work, flexible three phase composite films were prepared with surface functionalized multi‐walled carbon nanotubes (f‐MWCNTs) and bismuth ferrite (BiFeO₃;BFO) particles embedded into the poly(vinylidene fluoride) (PVDF) matrix via solution casting technique. The properties and the microstructure of prepared composites were investigated using an impedance analyzer and field emission scanning electron microscope. The micro‐structural study showed that the f‐MWCNTs and BFO particles were dispersed homogeneously within the PVDF matrix, nicely seated on the floor of the f‐MWCNTs separately. The dielectric measurement result shows that the resultant composites with excellent dielectric constant (≈96) and relatively lower dielectric loss (<0.23 at 100 Hz). Furthermore, the percolation theory is explored to explain the dielectric properties of the resultant composites. It says that the percolation threshold of f_MWCNTs = 0.9 wt % and the enhancement of the dielectric constant of the composite was also discussed. In addition, the remnant polarization of the un‐poled PVDF‐BFO‐f‐MWCNTs composites (2P_r ～1.34 µC/cm² for 1.1 wt % of f‐MWCNTs) is also improved. These three phase composites provide a new insight to fabricate flexible and enhanced dielectric properties as a promising application in modern electrical and electronic devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46002.     

Enhanced dielectric properties of poly(vinylidene fluoride)–surface functionalized BiFeO3 composites using sodium dodecyl sulfate as a modulating agent for device applications

In this work, we prepared a series of poly(vinylidene fluoride) (PVDF)–surface functionalized BiFeO₃ (h‐BFO)–Sodium dodecyl sulfate (SDS) composite films by solvent casting method to investigate the effect of SDS in the composites. The X‐ray diffraction confirmed that the structure of h‐BFO significantly changed in the PVDF‐(h‐BFO)‐SDS composite in comparison with the rhombohedral structure of pure BiFeO₃. The microscopic study illustrated that the composite with a higher percentage of SDS content facilitated the dispersion as well as proper distribution of ceramic particles in the polymer matrix. The presence of different functionalities of respective polymer and the modified fillers was confirmed by FTIR Spectrophotometer. The dielectric and electrical study done by Impedance Analyzer revealed that the SDS treated surface functionalized composites showed relatively higher dielectric properties than that of two phase composites and pure polymer. Finally, the ferroelectric properties of the composite films done by P‐E loop tracer revealed that the SDS‐treated composites showed an enhanced remanent polarization. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45040.     

New piezoelectric damping composites of poly(vinylidene fluoride) blended with clay and multi‐walled carbon nanotubes

Damping materials are used to control mechanical vibrations, and piezoelectric damping composite is a very promising material due to its unique mechanism. In this study, a potential piezoelectric damping composite was developed by simply melt mixing poly(vinylidene fluoride) (PVDF) with small amounts of organic modified montmorillonite (OMMT) and multi‐walled carbon nanotubes (MWCNTs). The piezoelectric, mechanical and electrical properties were investigated using a dynamic mechanical analyser, direct current electrical resistivity measurements, X‐ray diffraction, Fourier transform infrared spectroscopy and the direct quasi‐static d₃₃ piezoelectric coefficient method. It was found that the damping property of PVDF can be greatly improved by adding both MWCNTs and OMMT, and the composite containing 1.9 wt% of MWCNTs and 3 wt% of OMMT showed the best damping property. A model and an approximate calculation were applied to explain the improved damping property. Moreover, similar mechanical properties of PVDF composites were observed in the tensile testing and dynamic mechanical analyser measurements. Copyright © 2012 Society of Chemical Industry     

Facile preparation and properties of polyvinylidene fluoride dielectric nanocomposites via phase morphology control and incorporation of multiwalled carbon nanotubes conductive fillers

A novel PVDF dielectric nanocomposite was achieved by controlling phase morphology and incorporating conductive fillers simultaneously, and the mechanical, thermal, dielectric properties of the resultant dielectric nanocomposites were investigated. Mechanical analysis showed that incorporation of modified MWCNTs (MWCNTs-COOH) in the PVDF nanocomposites resulted in significant improvements on the tensile strength (T_s) and elasticity modulus (E_m). When the filler content was 12 wt%, the T_s of MWCNTs-COOH/PVDF could reach 64.6 MPa. XRD test showed that the addition of MWCNTs-COOH and MWCNTs promoted the formation of β-phase of PVDF. DMA analysis showed that the glass-transition temperature of the PVDF nanocomposites slightly increases on loading of original MWCNTs and this effect was more pronounced on loading MWCNTs-COOH. The dielectric property analysis showed that the original MWCNTs were more likely to form local conductive networks in the PVDF matrix, promoting the electron displacement polarization, and improving the dielectric constant. When the contents of MWCNTs was 12 wt%, the percolation threshold was obtained and the dielectric constant (ε′) reached 286, which was 36 times of pure PVDF. Our work provides a simple way to fabricate polymer blends with excellent dielectric performances, good mechanical properties as well as good processing capability but low cost. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48463.     

Properties and degradation behavior of surface functionalized MWCNT/poly(L‐lactide‐co‐ε‐caprolactone) biodegradable nanocomposites

In this research, poly(L ‐lactide‐co‐ε‐caprolactone) (PLACL) reinforced with well‐dispersed multiwalled carbon nanotubes (MWCNTs) nanocomposites were prepared by oxidization and functionalization of the MWCNT surfaces using oligomeric L ‐lactide (LA) and ε‐caprolactone (CL). It is found that the surface functionalization can effectively improve the dispersion and adhesion of MWCNTs in PLACL. The surface functionalization will have a significant effect on the physical, thermomechanical, and degradation properties of MWCNT/PLACL composites. The tensile modulus, yield stress, tensile strength, and elongation at break of composite increased 49%, 60%, 70%, and 94%, respectively, when the concentration of functionalized MWCNTs in composite is 2 wt %. The in vitro degradation rate of nanocomposites in phosphate buffer solution increased about 100%. The glass transition temperature (T_g) of composites was decreased when the concentration of functionalized MWCNTs is 0.5 wt %. With further increasing the concentration of functionalized MWCNTs, the T_g was increased. The degradation kinetics of nanocomposites can be engineered and functionalized by varying the contents of pristine or functionalized MWCNTs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrical properties of multi walled carbon nanotubes/ poly(vinylidene fluoride/trifluoroethylene) nanocomposites

Poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by the method of solution mixing/casting. The dispersity of the MWCNTs in the PVDF-TrFE matrix was investigated using transmission electron microscopy (TEM), revealing that MWCNT are well distributed in the PVDF matrix. Both individual and agglomerations of MWCNT’s were evident. The electrical properties were characterized by ac conductivity measurements. The conductivity was found to obey a percolation-like power law with a percolation threshold below 0.30 wt. %. The electrical conductivity of the neat PVDF-TrFE could be enhanced by seven orders of magnitude, with the addition of only 0.3 wt. % MWCNTs, suggesting the formation of a well-conducting network by the MWCNT’s throughout the insulating polymer matrix. The intercluster polarization and anomalous diffusion models were used to explain the dielectric behaviors of the composites near the percolation threshold, and the analyses of ac conductivity and dielectric constant imply that the intercluster polarization is more applicable to our systems.     

Integration of PDA Chemistry and Surface‐Initiated ATRP to Prepare Poly(methyl methacrylate)‐Grafted Carbon Nanotubes and Its Effect on Poly(vinylidene fluoride)–Carbon Nanotube Composite Properties

Poly(methyl methacrylate)‐grafted carbon nanotubes (PMMA@MWCNTs) are nondestructively prepared via the integration of mussel‐inspired polydopamine (PDA) chemistry and the surface‐initiated atom transfer radical polymerization (ATRP) method. The structures and properties of the poly(vinylidene fluoride)‐based (PVDF‐based) nanocomposites filled with pristine MWCNTs and PMMA@MWCNTs are investigated. The results show that the encapsulation of PMMA on the MWCNTs surface not only improves the dispersibility of MWCNTs in the PVDF matrix but also enhances the interfacial interaction between MWCNTs and PVDF. The addition of PMMA@MWCNTs nanofillers to PVDF can effectively induce the crystal structure of PVDF to transform from the α‐phase to the β/γ ‐phase, and nearly 100% β/γ ‐phase PVDF formed when the nanofiller loading is higher than 5 wt%. Compared with the MWCNTs/PVDF composites, the PMMA@MWCNTs/PVDF composites exhibit obvious improvement in the percolation threshold because the PMMA shells hinder the direct contact of the MWCNTs. Moreover, the loss tangent of the PMMA@MWCNTs/PVDF composites is effectively suppressed due to the reduced leakage current in the composites and the enhanced interfacial strength between the nanofiller and the matrix.     

Fabrication and dielectric properties of poly(ether ether ketone)/polyimide blends with selectively distributed multi‐walled carbon nanotubes

The distribution and contents of conductive fillers have a decisive influence on the dielectric properties of polymer/conductive filler composites. Herein, we clarified how the phase morphology and filler contents affect the dielectric properties of poly(ether ether ketone) (PEEK)/polyimide (TPI)/multi‐walled carbon nanotubes (MWCNTs) composites, in which MWCNTs were selectively located in the TPI phase. Firstly, PEEK/TPI/MWCNTs composites with identical MWCNTs content but different PEEK/TPI ratios were prepared. The composites with co‐continuous phase structure exhibited much better dielectric properties than those with sea–island structure. Then, PEEK/TPI/MWCNTs composites with the same PEEK/TPI ratio but various MWCNTs contents were prepared. The dielectric constant of the composite with 2 wt% MWCNTs reached 11306, which is because the formation of a co‐continuous phase structure benefited the mini‐capacitor network. Our results provide an effective method to develop high‐dielectric‐constant composites using the concept of double percolation. © 2015 Society of Chemical Industry     

High-dielectric constant percolative composite of P(VDF-TrFE) and modified multi-walled carbon-nanotubes

To develop a high-dielectric constant composite of poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] and multi-walled carbon-nanotubes (MWCNTs) with desirable homogeneity, MWCNTs were treated with a nitro-sulfuric acid by ultrasonication. The chemically modified MWCNTs (a-MWCNTs) were characterized by Fourier transform infrared spectroscopy and a back-titration procedure. Improvement of the dispersibility of a-MWCNTs in polymer matrix, in comparison with unmodified MWCNTs in P(VDF-TrFE), was confirmed by field emission scanning electron microscopy. Electric behavior of the composites with different volume fraction of dispersed carbon nanotubes can be described by percolation theory, as well as the Maxwell–Wagner–Sillars mechanism. The percolation threshold (f _c ) of composites with a-MWCNTs (f _c  = 0.0308) is larger than that of composites with MWCNTs (f _c  = 0.0216) due to better dispersion of a-MWCNTs in matrix and the reduction of aspect ratio of a-MWCNTs occurred in the modification procedure. The composite with 2.98 vol% (close to the percolation threshold) of a-MWCNTs has a dielectric constant of 592 at 100 Hz and room temperature.     

Hot‐melt adhesives based on co‐polyamide and multiwalled carbon nanotubes

Composites of two hot melt adhesives based on co‐polyamides, one high viscosity (coPA_A), the other low viscosity (coPA_B), and multiwalled carbon nanotubes (MWCNTs) were prepared using twin‐screw extrusion via dilution of masterbatches. Examination of these composites across the length scales confirmed that the MWCNTs were uniformly dispersed and distributed in the polymer matrices, although some micron size agglomerations were also observed. A rheological percolation was determined from oscillatory rheology measurements at a mass fraction of MWCNTs below 0.01 for coPA_B and, between 0.01 and 0.02 for coPA_A. Significant increases in complex viscosity and storage modulus confirmed the “pseudo‐solid” like behavior of the composite materials. Electrical percolation, determined from dielectric spectroscopy was, found to be at 0.03 and 0.01 MWCNT mass fraction for coPA_A and coPA_B based composites, respectively. Addition of MWCNTs resulted in heterogeneous nucleation and altered the crystallization kinetics of both copolymers. Indirect evidence from contact angle measurements and surface energy calculations confirmed that MWCNT addition enhanced the adhesive properties of coPA_B to a level similar to coPA_A. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45999.     

Ultra‐high dielectric constant of poly(vinylidene fluoride) composites filled with hydroxyl modified graphite powders

We provide a one‐step hydrothermal reaction to modify graphite powders (GPs) and prepare hydroxyl modified GPs/poly(vinylidene fluoride) (PVDF) composites which have excellent dielectric properties using high conductivity, low cost GPs as raw material. Fourier transform infrared spectroscopy (FT‐IR) and X‐ray photoelectron spectroscopy (XPS) showed that hydroxyl groups had been introduced to the surface of GPs. Scanning electron microscopy (SEM) showed that the hydroxyl modified GPs had better dispersion in the polymer matrix than the GPs. An ultra‐high dielectric constant of more than 5.1 × 10³ (dielectric loss is about 3.0) was obtained for the hydroxyl modified GPs/PVDF near the percolation threshold at 1 kHz. The hydroxyl modified GPs/PVDF composites exhibited better dielectric properties than most carbon/polymer composites. POLYM. COMPOS., 37:327–333, 2016. © 2014 Society of Plastics Engineers     

Preparation of high‐k composites with low dielectric loss based on the double‐layer coaxial structure of inorganic/polymer

This study presents a novel and simple modification of cladding multiwalled carbon nanotubes (MWCNTs) using organic polymer and inorganic nanoparticles to synthesize a product, which has a double‐cladding coaxial structure and can be applied as filler in the dielectric field. The first layer of MWCNTs was coated with polyaniline (PANI) through the oxidation–reduction reaction mechanism using Ce(NH₄)₂(NO₃)₆ as oxidizing agent and metal precursor of cerium oxide. Cerium ions on the second cladding layer of MWCNTs were directly deposited from the solution to the surface of the PANI layer forming the double‐cladding hybrid (CeO₂/PANI@MWCNTs). The external inorganic layer provides an insulating shell, which can prevent the contact between the conductive particles and hinder the migration of electrons between the MWCNTs. The intermediate layer of PANI provides the bonding between CeO₂ and the conductive core of MWCNTs, which also shows lower conductivity than carbon nanotubes. The CeO₂/PANI@MWCNTs were compounded with epoxy (EP) resin and formed a dielectric material with the advantage of reducing dielectric loss while ensuring high dielectric constant. The dielectric constant of the coated MWCNTs/EP composites was 194.90 at 10³ Hz with the content of fillers reaching 30 wt %, which is 28 times that of the pure EP. Accordingly, the dielectric loss of 30 wt % coated MWCNTs/EP composites was only 0.09 at 10³ Hz, which is only 2.25 times that of the pure EP. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46299.     

Nanocomposite films of poly(vinylidene fluoride) filled with polyvinylpyrrolidone‐coated multiwalled carbon nanotubes: Enhancement of β‐polymorph formation and tensile properties

To improve interactions between carbon nanotubes (CNTs) and poly(vinylidene fluoride) (PVDF) matrix, multiwalled CNTs (MWCNTs) were successfully coated with amphiphilic polyvinylpyrrolidone (PVP) using an ultrasonication treatment performed in aqueous solution. It was found that PVP chains could be attached noncovalently onto the nanotubes' surface, enabling a stable dispersion of MWCNTs in both water and N,N‐dimethylformamide. PVP‐coated MWCNTs/PVDF nanocomposite films were prepared by a solution casting method. The strong specific dipolar interaction between the PVP's carbonyl group (C?O) and the PVDF's fluorine group C?F₂ results in high compatibility between PVP and PVDF, helping PVP‐coated MWCNTs to be homogenously dispersed within PVDF. Fourier transform infrared and X‐ray diffraction characterization revealed that the as‐prepared nanocomposite PVDF films exhibit a purely β‐polymorph even at a very low content of PVP‐wrapped MWCNTs (0.1 wt%) while this phase is totally absent in the corresponding unmodified MWCNTs/PVDF nanocomposites. A possible mechanism of β‐phase formation in PVP‐coated MWCNTs/PVDF nanocomposites has been discussed. Furthermore, the tensile properties of PVDF nanocomposites as function of the content in PVP‐coated MWCNTs were also studied. Results shows that the addition of 2.0 wt% of PVP‐coated MWCNTs lead to a 168% increase in Young's modulus and a 120% in tensile strength. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

PTCR characteristics of poly(styrene‐co‐acrylonitrile) copolymer/stainless steel powder composites

Positive temperature coefficient of resistivity (PTCR) characteristics of poly(styrene‐co‐acrylonitrile) copolymer (SAN)/stainless steel (SS) powder (80 wt %) composites prepared by melt‐mixing method has been investigated with reference to SAN/carbon black (CB) composites. The SAN/CB (10 wt %) composites showed a sudden rise in resistivity (PTC trip) at 125°C, above the glass transition temperature (T_g) of SAN (T_g ≈ 107°C). However, the PTC trip temperature of SAN/SS (80 wt %) composites appeared at 94°C, well below the T_g of SAN. Addition of 1 phr of nanoclay increased the PTC trip temperature of SAN/CB (10 wt %) composites to 130°C, while SAN/SS (80 wt %)/clay (1 phr) nanocomposites showed the PTC trip at 101°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between SAN and SS played a key role that led to a disruption in continuous network structure of SS even at a temperature below the T_g of SAN. The dielectric properties study of SAN/SS (80 wt %) composites indicated possible use of the PTC composites as dielectric material. DMA results showed higher storage modulus of SAN/SS composites than the SAN/CB composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of multi‐walled carbon nanotubes and conductive carbon black on electrical,dielectric, and mechanical properties of epoxidized natural rubber composites

The influence of multi‐walled carbon nanotubes (MWCNTs) and conductive carbon black (CCB) on cure, electrical, dielectric, and mechanical properties of epoxidized natural rubber (ENR) composites was investigated. It was found that short MWCNTs (S‐MWCNTs) with low loading significantly affected the cure characteristics in a way similar to high loading of CCB. Moreover, the ENR/S‐MWCNTs composites exhibited high AC conductivity, dielectric constant, and dielectric loss tangent (tan δ ) compared to the ENR/CCB and ENR/L‐MWCNTs (long MWCNTs) composites. In addition, the S‐MWCNTs composites showed the lowest percolation threshold concentration, defined as the lowest loading to form conductive paths in the insulating ENR matrix. This might be attributed to the comparatively high interfacial polarization, with good dispersion and distribution, of the S‐MWCNTs in ENR matrix. These characteristics were confirmed by TEM imaging and by a high bound rubber content, corroborating strong filler–rubber interactions in the ENR/S‐MWCNTs composites. However, the L‐MWCNTs composites showed the lowest electrical and other related properties, despite the highest aspect ratio and specific surface area of this filler. This might be because of the flocculation of nanotubes by mutual entanglement, leading to a poor uneven distribution in the ENR matrix. POLYM. COMPOS., 38:1031–1042, 2017. © 2015 Society of Plastics Engineers     

Investigation of electrical,mechanical, and thermal properties of functionalized multiwalled carbon nanotubes‐reduced graphene Oxide/PMMA hybrid nanocomposites

Electrical, mechanical, and thermal properties of the poly(methyl methacrylate) (PMMA) composites containing functionalized multiwalled carbon nanotubes (f‐MWCNTs) and reduced graphene oxide (rGO) hybrid nanofillers have been investigated. The observed electrical percolation threshold of FHC is 0.8 wt% with maximum conductivity of 1.21 × 10^?3 S/cm at 4 wt% of f‐MWCNTs. The electrical transport mechanism and magneto resistance studied of hybrid composites have also been investigated. Progressive addition of f‐MWCNTs in rGO/PMMA composite results increase in mechanical (tensile strength and Young's modulus) and thermal (thermal stability) properties of f‐MWCNTs‐rGO/PMMA hybrid nanocomposites (FHC). The increased mechanical properties are due to the efficient load transfer from PMMA matrix to f‐MWCNTs and rGO through better chemical interaction. The strong interaction between PMMA and f‐MWCNTs‐rGO in FHC is the main cause for improved thermal stability. POLYM. ENG. SCI., 59:1075–1083, 2019. © 2019 Society of Plastics Engineers     

Effect of heat treatment on the electrical properties of lead zirconate titanate/poly (vinylidene fluoride) composites

Ceramic/polymer composites are attracting increasing interest in materials research and practical applications due to the combination of excellent electric properties of piezoelectric ceramics and good flexibility of polymer matrices. In this case, the crystallization of the polymer has a significant effect on the electric properties of ceramic/polymer composites. Based on different heat treatment methods, the crystallization of poly(vinylidene fluoride) (PVDF) in composites of lead zirconate titanate (PZT) and PVDF can be controlled effectively. PZT/PVDF composites with various PVDF crystallizations exhibit distinctive dielectric and piezoelectric properties. When the crystallization of PVDF is 21%, the PZT/PVDF composites show a high dielectric constant (ε) of 165 and a low dielectric loss (tan δ) of 0.03 at 10³ Hz, and when the crystallization of PVDF reaches 34%, the piezoelectric coefficient (d₃₃) of PZT/PVDF composites can be up to ca 100 pC N^?1. By controlling the crystallization of PVDF, PZT/PVDF composites with excellent dielectric and piezoelectric properties were obtained, which can be employed as promising candidates in high‐efficiency capacitors and as novel piezoelectric materials. Copyright © 2010 Society of Chemical Industry     

Novel dielectric behaviors in PVDF‐based semiconductor composites

Composites of polyvinylidene fluoride (PVDF) filled with different conductive fillers as carbon black (CB), nickel (Ni), zinc (Zn), and tungsten (W), respectively, were prepared at same processing condition. The temperature dependence of dielectric behaviors of composites was studied at wide filler concentration and wide frequency ranges. Results show that there are giant dielectric constants as the concentration of filler is near the percolation threshold. The dielectric constants of all studied composites decrease slowly with increasing of frequency and rise gradually with increasing filler contents in the composites. Two relaxation peak regions of dielectric constant are observed from ?30 to 40°C and from 100 to 150°C, which can be attributed to the contribution of polar effect of PVDF. The CB filled PVDF (CB/PVDF) composites present a lower percolation threshold than other metallic‐filler filled PVDF composites. The maximal dielectric constant was found in the Ni filled PVDF (Ni/PVDF) composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tailored dielectric and mechanical properties of noncovalently functionalized carbon nanotube/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) nanocomposites

The preparation of high‐dielectric poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) composites containing functionalized single‐walled carbon nanotubes (f‐SWCNTs) noncovalently appended with dibutyltindilaurate are reported herein. Transmission electron microscopy and X‐ray photoelectron and Raman spectroscopy confirmed the noncovalent functionalization of the SWCNTs. The SEBS‐f‐SWCNT composites exhibited enhanced mechanical properties as well as a stable and high dielectric constant of approximately 1000 at 1 Hz with rather low dielectric loss at 2 wt% filler content. The significantly enhanced dielectric property originates from the noncovalent functionalization of the SWCNTs that ensures good dispersion of the f‐SWCNTs in the polymer matrix. The f‐SWCNTs also acted as a reinforcing filler, thereby enhancing the mechanical properties of the composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.