Elastomeric conductive composites based on conducting polymer–modified carbon black

Thermally stable elastomeric composites were prepared via melt processing from poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS) and conducting polymer-modified carbon black (CPMCB) additives. CPMCB additives represent a novel thermally stable conductive compound made via “in-situ” deposition of polyaniline or polypyrrole on carbon black particles. Incorporating CPMCB is advantageous to the melt processing of composites, as it reduces the melt viscosity in comparison to the use of pure carbon black. Thermogravimetric analyses (TGA) showed that the composites are thermally stable with no appreciable degradation at temperatures as high as 300°C. In addition, the electrical conductivity of the composites was found to be very stable at high temperatures. Polym. Compos. 25:617–621, 2004. © 2004 Society of Plastics Engineers.     

In situ melt grafting in carbon black/polyolefin composites and its influence on conductive performance

To improve the conductive properties of carbon‐black‐filled low‐density polyethylene, in situ grafting of certain monomers was applied during the melt compounding process. The experimental data obtained demonstrated that chemical bonding could thus be established between the fillers and the matrix polymer. The degree of enhancement of the filler/matrix interfacial interactions in the composites prepared in this way depends on the species of the grafting monomers being employed. When compared with the untreated carbon black composites, the composites manufactured through in situ melt grafting exhibited reduced room temperature resistivities and greatly increased positive temperature coefficient intensities, as well as favorable performance reproducibility. This proposed technical route has several advantages, including simplicity, low cost and easy control. Copyright © 2004 Society of Chemical Industry     

Melt spinning of β‐phase poly(vinylidene fluoride) yarns with and without a conductive core

When poly(vinylidene fluoride) (PVDF) is to be used as a piezoelectric material, the processing must include the formation of polar β‐phase crystallites, as well as the application of electrically conducting charge collectors, that is, electrodes. In this article, results from the melt spinning of PVDF yarns and a novel bicomponent PVDF‐yarn with a conductive carbon black/polypropylene (CB/PP) core are presented. Melt spinning has been done under conditions typical for industrial large‐scale fiber production. The effects on the resulting crystalline structure of varying the spinning velocity, draw rate, and draw temperature are discussed. The results show that, for maximum α‐to‐β phase transformation, cold drawing should take place at a temperature between 70 and 90°C, and both the draw ratio and the draw rate should be as high as possible. It was observed that the cold drawing necessary to form β‐phase crystallinity simultaneously leads to a decrease in the core conductivity of the bicomponent yarns. In this work, the melt spinning of bicomponent fibers with high‐β‐phase PVDF in the sheath and a CB/PP core was successfully accomplished. The core material remained electrically conductive, paving the way for the use of a CB‐polymer compound as inner electrode in the melt spinning of piezoelectric bicomponent fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A new approach for conductive network formation in electrospun poly(vinylidene fluoride) nanofibers

Conductive nanofibers of poly(vinylidene fluoride) (PVDF) filled with polyaniline (PANi)‐coated multi‐wall carbon nanotubes (MWCNTs) were fabricated using the electrospinning technique. PANi is an intrinsically conductive polymer. The addition of PANi‐coated MWCNTs to PVDF created short conductive strands on the surface of the nanofibers, facilitating the formation of a conductive network in the transverse direction of the nanofibers. Piezoelectricity along with electric conductivity makes these PVDF nanofibers promising for applications such as sensors and actuators. Electrospun PVDF nanofiber mats had higher piezoelectricity than melt‐processed samples produced using traditional polymer processing techniques, such as compression molding. Spectroscopic imaging techniques were employed to study the effects of the filler and processing conditions on the nanofiber structure. X‐ray diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry results indicated a large increase in the β‐phase crystals of the PVDF nanofibers. This higher content of β‐phase crystals enhanced the piezoelectricity of the nanofibers. © 2015 Society of Chemical Industry     

Low‐Temperature Sintering of β‐Spodumene Ceramics Using Li2O–GeO2 as a Sintering Additive

Low‐temperature sintering of β‐spodumene ceramics with low coefficient of thermal expansion (CTE) was attained using Li₂O–GeO₂ sintering additive. Single‐phase β‐spodumene ceramics could be synthesized by heat treatment at 1000°C using highly pure and fine amorphous silica, α‐alumina, and lithium carbonate powders mixture via the solid‐state reaction route. The mixture was calcined at 950°C, finely pulverized, compacted, and finally sintered with or without the sintering additive at 800°C–1400°C for 2 h. The relative density reached 98% for the sample sintered with 3 mass% Li₂O–GeO₂ additive at 1000°C. Its Young's modulus was 167 GPa and flexural strength was 115 MPa. Its CTE (from R.T. to 800°C) was 0.7 × 10^?6 K^?1 and dielectric constant was 6.8 with loss tangent of 0.9% at 5 MHz. These properties were excellent or comparative compared with those previously reported for the samples sintered at around 1300°C–1400°C via melt‐quenching routes. As a result, β‐spodumene ceramics with single phase and sufficient properties were obtained at about 300°C lower sintering temperature by adding Li₂O–GeO₂ sintering additive via the conventional solid‐state reaction route. These results suggest that β‐spodumene ceramics sintered with Li₂O–GeO₂ sintering additive has a potential use as LTCC for multichip modules.     

Preparation and properties of β‐phase graphene oxide/PVDF composite films

We report preparation of graphene oxide (GO) from expanded graphite (EG) via a modified Hummers method. GO/PVDF composites films were obtained using solvent N, N‐Dimethylformamide (DMF) and cosolvent comprising deionized water/DMF combination. X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses revealed that the main crystal structure of the composite films is β‐phase, and use cosolvent method tends to favor the formation of β‐phase. Scanning electron microscopy (SEM) was used to investigate the microstructure of composite films. Storage modulus and loss modulus were measured by Dynamic mechanical analysis (DMA). Broadband dielectric spectrum tests showed an increase in the dielectric constant of the GO/PVDF composite films with the rising content of GO, and by cosolvent method could improve the dielectric constant while reducing the dielectric loss. Our method that uses GO as an additive and deionized water/DMF as the cosolvent provides a promising and low‐cost pathway to obtain high dielectric materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41577.     

Investigation of the physico‐mechanical properties of electrospun PVDF/cellulose (nano)fibers

The electro‐activity and mechanical properties of PVDF depends mainly on the β‐phase content and degree of crystallinity. In this study, cellulose fibers were used to improve these characteristics. This could be achieved because the hydroxyl groups on cellulose would force the fluorine atoms in PVDF to be in the trans‐conformation, and the cellulose particles could act as nucleation centers. Electrospinning was used to prepare the PVDF/cellulose (nano)fibrous films, and this improved the total crystallinity and the formation of β‐crystals. However, the presence and amount of cellulose in PVDF were found to have little influence on the β‐phase content and on the total crystallinity of PVDF. Improvements in the extent of crystallinity and the β‐phase content were primarily brought about by the chain‐ and crystal orientation as a result of electrospinning. The thermal stability of PVDF in the composites slightly increased with increasing cellulose content in the composites up to 1.0 wt %, while the modulus and tensile strength significantly increased up to the same filler level. The dielectric storage permittivity also increased with increasing cellulose content, but the presence of cellulose had no influence on the dynamics of the γ‐ and β‐relaxations of the PVDF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43594.     

Effect of unfunctionalized and HNO3‐functionalized MWCNT on the mechanical and electrical performances of PEMFC bipolar plates

This study aims at developing lightweight and high performance electrically conductive nanocomposites for proton exchange membrane fuel cell (PEMFC) bipolar plates (BPPs). These composites were made from an optimized co‐continuous mixture of Polyethylene terephthalate (PET) and polyvinylidene fluoride (PVDF) reinforced with highly conductive carbon additives composed of carbon black (CB) and synthetic graphite (GR). Multiwall carbon nanotubes (MWCNT) were functionalized then used to improve BPPs electrical conductivity and their mechanical properties, such as flexural and impact strengths. It was observed that the best BPP prototype was obtained using nitric acid (HNO₃)‐functionalized MWCNT. The latter led to the smothest BPP surface, the lowest through‐plane resitivity (0.12 Ω cm) and the highest impact and flexural strengths. These results are attributed to the improved dispersion of the functionalized MWCNT, a result of their best compatibilization with the (PET/PVDF) polymeric phase. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43624.     

Effect of flow history on poly(vinylidine fluoride) crystalline phase transformation

This study was devoted to the effect of extensional flow during film extrusion on the formation of the β‐crystalline phase and on the piezoelectric properties of the extruded poly(vinylidine fluoride) (PVDF) films after cold drawing. The PVDF films were extruded at different draw ratios with two different dies, a conventional slit die and a two‐channel die, of which the latter was capable of applying high extensional flow to the PVDF melt. The PVDF films prepared with the two‐channel die were drawn at different temperatures, strain rates, and strains. The optimum stretching conditions for the achievement of the maximum β‐phase content were determined as follows: temperature = 90°C, strain = 500%, and strain rate = 0.083 s^?1. The samples prepared from the dies were then drawn under optimum stretching conditions, and their β‐phase content and piezoelectric strain coefficient (d₃₃) values were compared at equal draw ratios. Measured by the Fourier transform infrared technique, a maximum of 82% β‐phase content was obtained for the samples prepared with the two‐channel die, which was 7% higher than that of the samples prepared by the slit die. The d₃₃ value of the two‐channel die was 35 pC/N, which was also 5 pC/N higher than that of the samples prepared with the slit die. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Conductive poly(vinylidene fluoride)/polyethylene/graphene blend‐nanocomposites: Relationship between rheology,morphology, and electrical conductivity

Relationship between rheology, morphology, and electrical conductivity of the poly(vinylidene fluoride)/polyethylene/graphene nano‐platelets ternary system (PVDF/PE/GnP) were investigated. All the blend nanocomposites were prepared via a two‐step melt mixing method. GnP (0.75 and 1.5 wt %) was first compounded with PVDF and then the resulted premixtuers were melt mixed with PE to achieve the desired compositions. The corresponding reference nanocomposites and filler‐less blends were also prepared. Effect of an interfacial agent (PEMA; maleic anhydride grafted polyethylene) was also studied in this work. The results of rheological analysis in conjunction with the Raman spectroscopy experiments revealed that GnP had higher affinity to PVDF than PE, which in turn led to creation of conductive networks of GnP (1.5 wt %) in PVDF matrix exhibiting the electrical conductivity of about 10^?2 (S/cm). Double percolated micro‐structure was predicted for the PE/PVDF 40/60 (wt/wt) blend containing low GnP content (0.9 wt %) and confirmed via direct electron microscopy and conductivity analysis. Using 5 wt % of the PEMA reduced the conductivity to 10^?5 (S/cm) and further increase in PEMA content to 10 wt % led to non‐conductive characteristics. The latter was attributed to the migration of GnP from the PVDF phase to PE/PEMA phase and hence disturbance of double percolated micro‐structure. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46333.     

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     

Time–temperature dependence of the electrical resistivity of high‐density polyethylene/carbon black composites

Several carbon blacks with surface areas from 105 to 1353 m²/g were used to produce composites through melt compounding with a high‐density polyethylene matrix. The electrical behavior of the obtained composites was investigated by the measurement of their resistivity as a function of the carbon black content and type at various temperatures and times during isothermal annealing treatments. The percolation threshold markedly decreased as the carbon black surface area increased, reaching a minimum value of 1.8 vol % for the carbon black with a surface area of 1353 m²/g. The resistivity passed through a maximum as the test temperature increased. Moreover, the analysis of the experimental data evidenced that the host high‐density polyethylene matrix and the conductive carbon black network rearranged during the isothermal thermal treatments, causing a resistivity decrease. This rearrangement became less and less important as the carbon black surface area increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Enhanced electroactive β phase in three phase PVDF/CaCO3/nanoclay composites: Effect of micro‐CaCO3 and uniaxial stretching

In this study, electroactive polar phase transformation and crystallinity of poly(vinylidene fluoride) (PVDF)‐based composites, such as PVDF/CaCO₃/nanoclay, is explored as a function of micro‐CaCO₃ fraction and draw ratio (R) of uniaxial stretching. Composites including PVDF/clay, PVDF/CaCO₃ and most importantly PVDF/CaCO₃/clay with varying fraction of micro‐CaCO₃ were extruded into homogenous and flexible cast films. Characterization via Fourier transform infrared spectroscopy, X‐ray diffraction, and differential scanning calorimetry (DSC) confirmed the presence of β phase in all the composites incorporated with micro‐CaCO₃ and nanoclay either individually (i.e., PVDF/CaCO₃ and PVDF/clay films, respectively) or together (i.e., PVDF/CaCO₃/nanoclay composites). Interestingly, a gradual but significant improvement in this electroactive phase (β phase) was obtained with successive increment in CaCO₃ content into a fixed composition of PVDF and nanoclay (PVDF/CaCO₃/clay composites). Further increment in β phase content was obtained via uniaxial stretching to different draw ratios and at a temperature of 90 °C, where for PVDF/CaCO₃/clay (especially, 100–35‐3 and 100–40‐3) samples almost no α phase was observed irrespective of R. Conversely, the crystallinity of melt extruded samples decreased gradually all the way with CaCO₃ concentration in PVDF/CaCO₃/clay composites compared to the neat PVDF while increased gradually with increasing draw ratio. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44940.     

Coaxial electrospun nanofibers of poly(vinylidene fluoride)/polyaniline filled with multi‐walled carbon nanotubes

Core‐shell nanofibers of poly (vinylidene fluoride)/polyaniline/multi‐walled carbon nanotubes (PVDF/PANi/MWCNTs) have been produced using the coaxial electrospinning technique. The nanofibers were semiconductive and had better piezoelectric properties than pure PVDF nanofibers. Piezoelectric PVDF nanofibers are capable of converting mechanical energy into electrical energy, which can be stored in charge storage devices. However, PVDF is not conductive and therefore, a conductive associate material is needed to transfer accumulated static charges into the capacitor. Fourier Transform Infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) were carried out to study the crystalline β‐phase of PVDF. There was an increase in β‐phase in the electrospun PVDF nanofibers filled with MWCNTs as compared with compression molded samples of neat PVDF. Incorporation of PANi as an intrinsically conductive polymer (ICP) and MWCNTs as conductive nanofiller helps the movement of static charges. Core‐shell nanofibers had conductivities of about seven orders of magnitude higher than simple electrospun nanofibers. POLYM. COMPOS., 35:1198–1203, 2014. © 2013 Society of Plastics Engineers     

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.     

Kinetic and thermodynamic control in conductive PP/PMMA/EAA carbon black composites

Multiphase polymer blends provide unique morphologies to reduce the percolation concentration and increase conductivity of carbon‐based polymer composites via selective distribution of the conductive filler. In this work, the kinetic and thermodynamic effects on a series of multiphase conductive polymer composites were investigated. The electrical conductivity of carbon black (CB)‐filled conductive polymer blend composites comprising polypropylene, poly(methyl methacrylate), and ethylene–acrylic acid were determined as a function of compounding sequence and annealing time. Kinetic and thermodynamic parameters were found to influence the conductivity. Phase morphology and conductivity at short annealing times were influenced by the compounding sequence where the CB was added after being premixed with one of the polymer components or directly added to the three‐component polymer melt. However, they were thermodynamically driven at longer annealing times; the resistivity was found to decrease by a statistically significant amount to similar levels for all the composite systems with increasing annealing time. The increase in conductivity at longer annealing times was determined to be the result of changes in the phase morphology from sea‐island, dispersed microstructure to a tri‐continuous morphology rather than change in localization of CB, given that the CB was found to be entirely located in the EAA phase even at short annealing times (and independent of compounding sequence), where the conductivity was not measurable. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42134.     

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.     

Facile and effective promotion of β crystalline phase in poly(vinylidene fluoride) via the incorporation of imidazolium ionic liquids

In this study, a facile and efficient protocol to enhance the β‐phase content of poly(vinylidene fluoride) (PVDF) is developed, in which the effect of room temperature ionic liquids (RTILs), including [1‐butyl‐3‐methylimidazolium (bmim)][PF₆], [bmim][BF₄], [bmim][FeCl₄] and [bmim][Cl], on the crystallization behavior of PVDF is investigated. The resulting PVDF/RTIL hybrids are characterized by Fourier transform infrared (FTIR) spectroscopy, XRD, polarized optical microscopy (POM) and DSC. The FTIR spectroscopy and XRD results show that the fraction of β‐phase, F(β), is significantly enhanced by the incorporation of RTILs, specifically from 49.2% for neat PVDF to 92.6% for hybrid filled with 15 wt% [bmim][PF₆]. The analysis of the crystallization behavior based on the DSC tests reveals that the degree of crystallinity increases with incorporation of RTILs, implying that RTILs could act as directing agents to facilitate the crystallization process, which is further evidenced by the POM results. In addition, the non‐isothermal crystallization kinetics of PVDF and PVDF/RTIL composites are investigated by means of DSC and the results indicate that the addition of the RTILs significantly influences the mechanism of nucleation and growth of PVDF crystallites. © 2013 Society of Chemical Industry     

Nickel‐multiwalled carbon nanotubes/polyvinylidene fluoride composites with high dielectric permittivity

Composites with nickel particles coated multiwalled carbon nanotubes (Ni‐MWNTs) embedded into polyvinylidene fluoride (PVDF) were prepared by solution blending and hot‐press processing. The morphology, structure, crystallization behavior, and dielectric properties of composites were studied. The results showed that the crystallization of PVDF was affected by Ni‐MWNTs. With the increment of Ni‐MWNTs, the content of β‐phase in PVDF increased. The dielectric permittivity was as high as 290 at 10³ Hz when the weight fraction of Ni‐MWNTs was 10%. The results can be explained by the space charge polarization at the interfaces between the insulator and the conductor, and the formation of microcapacitance structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3746–3752, 2013     

Effect of composite preparation techniques on electrical and mechanical properties and morphology of nylon 6 based conductive polymer composites

Nylon 6/carbon black conductive composites were prepared using two different methods, masterbatch dilution and melt mixing. Their effect on the size and distribution of carbon black agglomerates in the matrix was studied in terms of electrical and mechanical properties and morphology. The electrical resistivity of composites prepared by both methods decreased with increasing filler composition. The electrical resistivity of the diluted masterbatch composites and the melt mixed composites was reduced from the resistivity of pure nylon 6, 10¹⁵ “ohm, cm”, to 10⁷ “ohm, cm” at 1 and 6 wt % of carbon black, respectively. As the filler content increased, elongation at break and impact strength decreased, but tensile modulus increased. Masterbatch dilution method provided smaller carbon black clusters in composites compared to melt mixing method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2520–2526, 2006