Dielectric properties of exfoliated graphite reinforced flouroelastomer composites

Dielectric relaxation behavior of nano graphite reinforced flouroelastomer composites has been studied as a function of variation in filler in the frequency range of 0.01–10⁵ Hz. The effect of variation in filler loadings on the complex and real parts of impedance was distinctly visible which has been explained on the basis of interfacial polarization of fillers in a heterogeneous medium and relaxation dynamics of polymer chains in the vicinity of fillers. The electric modulus formalism has been utilized to further investigate the conductivity and relaxation phenomenon. The frequency dependence of AC conductivity has been investigated by using Percolation theory. The phenomenon of percolation in the composites has been discussed based on the measured changes in electric conductivity and morphology of composites at different concentrations of the filler. The percolation threshold as studied by DC conductivity occurred in the vicinity of 2.5–3.5 phr of filler loading. Scanning electron microscope microphotographs showed agglomeration of the filler above this concentration and formation of a continuous network structure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dielectric relaxation of Ensaco®350G reinforced microcellular EPDM vulcanizates

The dielectric relaxation characteristics of microcellular EPDM vulcanizates has been studied as a function of variation in filler and blowing agent loadings in the frequency range of 100–10⁶ Hz. The dielectric constant ε′ increases with increasing filler loadings at all frequencies. This has been explained on the basis of interfacial polarization of fillers in a heterogeneous medium. The effect of variation in filler and blowing agent loadings on the complex and real parts of impedance was distinctly visible. Which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. The phenomenon of percolation in the composites has been discussed based on the measured changes in electric conductivity and morphology of composites at different concentrations of the filler. The percolation threshold as studied by DC conductivity occurred near 40 phr of filler loading. SEM microphotographs showed agglomeration of the filler above this concentration and formation of a continuous network structure. POLYM. COMPOS., 28: 657–666, 2007. © 2007 Society of Plastics Engineers     

Dielectric and dynamic mechanical relaxation behavior of exfoliated nano graphite reinforced flouroelastomer composites

Dynamic mechanical analysis and dielectric relaxation spectra of exfoliated nano graphite reinforced flouroelastomer composites were used to study their relaxation behavior as a function of temperature (−80°C to +40°C) and frequency (0.01 to 10⁵ Hz). The effect of filler loadings on glass transition temperature was marginal for all the composites and T_g value was in the narrow range of 7.8–8.4°C, which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. Strain‐dependent dynamical parameters were evaluated at dynamic strain amplitudes of 0.01–10%. The nonlinearity in storage modulus has been explained on the concept of filler‐polymer interaction and filler aggregation of the nano graphite platelets. The variation in real and complex part of impedance with frequency has been studied as a function of filler. The percolation of the nano graphite as studied by conductivity measurements is also reported. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Dielectric relaxation of conductive carbon black reinforced chlorosulfonated polyethylene vulcanizates

The frequency dependent dielectric relaxation behavior of conductive carbon black reinforced chlorosulfonated polyethylene (CSM) vulcanizates has been studied for different filler loadings in the frequency range of 10²–10⁶ Hz over a wide range of temperatures (30–120°C). The effects of filler loadings on the dielectric permittivity (ε′), dielectric loss tangent (tan δ), impedance, and electrical conductivity were studied. The variation of the dielectric permittivity with the filler loadings was explained on the basis of interfacial polarization of the filler in the polymer matrix. The frequency dependence of ac conductivity has been investigated using percolation theory. The effect of filler loading on the complex and real parts of impedance was clearly observed, which can be explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. The percolation threshold occurred near 30 phr of filler loading. Scanning electron microphotographs showed the agglomeration of the filler on and above these filler loadings. Additionally, the effect of temperature on dielectric loss tangent, dielectric permittivity, ac conductivity, and Nyquist plot of conductive black reinforced CSM vulcanizates has been studied. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Effect of fillers on the relaxation behavior of chlorobutyl vulcanizates

The effect of addition of fillers (carbon black (CB), carbon silica dual phase filler (CSDPF), and nanoclays) on the relaxation behavior of chlorobutyl vulcanizates has been studied. The primary relaxation (α‐transition, the glass transition) was studied by dynamic mechanical analysis as a function of temperature (?60 to +100°C) and positron annihilation life time spectroscopy (?70 to +110°C). Irrespective of the filler and its loading, all the composites showed the glass transition temperature in the range of –29 to –33°C, which was explained on the basis of relaxation chain dynamics of polyisobutylene in the vicinity of fillers. The secondary relaxation (α* or β relaxation) was studied using dielectric relaxation spectra in the frequency range of 100–10⁶ Hz. Nanoclays had a profound influence on the secondary relaxation, whereas CSDPF and CB had a marginal effect. The nonlinear strain dependent dynamical parameters were also evaluated at double strain amplitudes of 0.07–5%. The nonlinearity in tan δ and storage modulus has been explained on the concept of filler–polymer interactions and the interaggregate attraction (filler networking). The “percolation limit” of the fillers in the composites has been studied by DC conductivity measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3161–3173, 2006     

Influence of carbon‐based nanofillers on the electrical and dielectric properties of ethylene vinyl acetate nanocomposites

A comparative study of ethylene vinyl acetate nanocomposites based on expanded graphite, multiwalled carbon nanotubes, and carbon nanofibers has been carried out to investigate the effect of different carbon nanofillers on the electrical properties of the corresponding composites. The composites were prepared by ultrasonic dispersion of fillers in ethylene vinyl acetate solution, followed by casting and compression molding. The dependence of AC conductivity and dielectric constant on the frequency and filler concentration was investigated. Carbon nanofibers provided maximum conductivity as well as lowest percolation threshold (8.2 vol%) compared to expanded graphite and multiwalled carbon nanotubes filled composites. The improvement in both electrical conductivity and dielectric constant was attributed to the high filler aspect ratio and the formation of conducting networks. The relationship of dielectric constant with filler volume fraction for all the composite systems is estimated using a power law. The pressure sensing capability of the composites at respective percolation thresholds was also compared. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

AC conductivity and positive temperature coefficient effect in microcellular EPDM vulcanizates

Dielectric relaxation spectra of conductive carbon black reinforced microcellular EPDM vulcanizates were used to study their relaxation behavior in the frequency range of 0.01–10⁵ Hz over a wide range of temperature from 30 to 120°C. The effect of variation in filler loading and blowing agent loading (density) on dielectric characteristics such as impedance, dielectric constant, and conductivity has been studied. The experimental results show that the relative dielectric permittivity of the composites depends strongly on the extent of carbon black and blowing agent concentrations. The frequency dependence of AC conductivity has been investigated by using Percolation theory. The permittivity and conductivity of the microcellular composites have been analyzed based on scaling theory at increasing temperatures. The applicability of Lichtenecker‐Rother's “rule of mixture” to describe the complex permittivity of the composite has also been investigated. Irrespective of the blowing agent loading and temperature, the percolation threshold as studied by DC conductivity was found to be at 40 phr loading of the filler. Scanning electron microphotographs showed agglomeration of the filler above this concentration and formation of a continuous network structure. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Dielectric relaxation behavior of conducting carbon black reinforced ethylene acrylic elastomer vulcanizates

The dielectric relaxation characteristics of conductive carbon black (CCB) reinforced ethylene acrylic elastomer (AEM) vulcanizates have been studied as a function of frequency (10¹–10⁶ Hz) at different filler loading over a wide range of temperatures (30–120°C). The effect of filler loadings on the dielectric permittivity (ε′), loss tangent (tan δ), complex impedance (Z*), and electrical conductivity (σ_ac) were studied. The variation of ε′ with filler loading has been explained based on the interfacial polarization of the fillers within a heterogeneous system. The effect of filler loading on the imaginary (Z″) and real (Z′) part of Z* were distinctly visible, which may be due to the relaxation dynamics of polymer chains at the polymer–filler interface. The frequency dependency of σ_ac has been investigated using percolation theory. The phenomenon of percolation in the composites has been discussed in terms of σ_ac. The percolation threshold (?_crit) occurred in the range of 20–30 phr (parts per hundred) of filler loading. The effect of temperature on tan δ, ε′, σ_ac, and Nyquist plots of CCB‐based AEM vulcanizates has been investigated. The CCB was uniformly dispersed within the AEM matrix as studied from the transmission electron microscope (TEM) photomicrographs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Relaxation behavior of conductive carbon black reinforced EPDM microcellular vulcanizates

Dynamic mechanical analysis and dielectric relaxation spectra of conductive carbon black reinforced microcellular EPDM vulcanizates were used to study the relaxation behavior as a function of temperature (−90 to +100°C) and frequency (0.01–10⁵ Hz). The effect of filler and blowing agent loadings on dynamic mechanical and dielectric relaxation characteristics has been investigated. The effect of filler and blowing agent loadings on glass transition temperature was marginal for all the composites (T_g value was in the range of −39 to −35°C), which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. Strain-dependent dynamical parameters were evaluated at dynamic strain amplitudes of 0.07–5%. The nonlinearity in storage modulus has been explained based on the concept of filler–polymer interaction and interaggregate attraction (filler networking) of carbon black. The variation in real and complex part of impedance with frequency has been studied as a function of filler and blowing agent loading. Additionally, the effect of crosslinking on the dielectric relaxation has also been reported. POLYM. ENG. SCI., 47:984–995, 2007. © 2007 Society of Plastics Engineers     

Dielectric relaxation of conductive carbon black reinforced ethylene‐octene copolymer vulcanizates

The dielectric relaxation behavior of different conducting carbon black‐filled ethylene‐octene copolymer (EOC) vulcanizates prepared by melt‐mixing method has been studied as a function of frequency (100 Hz–5 MHz) over a wide range of temperatures (25–100°C). The effect of filler loading and frequency on AC conductivity, dielectric permittivity, impedance, and dielectric loss tangent (tanδ) has been studied. The nature of variation of the dielectric permittivity with the filler loadings was explained on the basis of interfacial polarization of the filler in the polymer matrix. The effect of filler loading on the real and complex part of the impedance was explained by the relaxation dynamics of the polymer chains in the vicinity of the fillers. The effect of filler and temperature on dielectric loss tangent, dielectric permittivity, AC conductivity, and Nyquist plot was also reported. The bound rubber (BR) value increases with increase in filler loading suggesting the formation of strong interphase, which is correlated with dielectric loss. Thermal activation energy (E_a) was found to be decreasing with the temperature, which follows the Arrhenius relation: τ_b = τ₀ exp(−E_a/K_BT) where τ_b is the relaxation time for the bulk material. From the plot of lnτ_b versus inverse of absolute temperature (1/T), the activation energies (E_a) were found to be 0.37 and 0.44eV, respectively. The percolation threshold was observed with 40 phr carbon black loading. POLYM. COMPOS., 37:342–352, 2016. © 2014 Society of Plastics Engineers     

Measurement of AC conductivity and dielectric properties of flexible conductive styrene–butadiene rubber‐carbon black composites

Flexible conductive polymer composites were prepared using styrene–butadiene rubber (SBR) as a matrix and conductive carbon black as filler. The filler loading was varied from 10 to 60 phr. The effect of frequency, filler loading, temperature, and applied pressure on the AC conductivity, permittivity, and loss factor of the composites was studied. The AC conductivity of low and high loaded composites was found to be frequency dependent and independent respectively. The permittivity and the loss factor were continuously decreasing with increasing frequency. The increase in filler loading increased the AC conductivity, dielectric constant, and loss factor of the composites. Increase in temperature imposed increase in conductivity and permittivity of the composites. With increasing applied pressure the properties showed exponential increase. The effect of time under a constant compressive stress was studied and dielectric relaxation times were evaluated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 986–995, 2007     

Electric‐field induced filler association dynamics and resulting improvements in the electrical conductivity of polyester/multiwall carbon nanotube composites

The effects of electric fields on the filler response dynamics and electrical percolation of poly(ethylene succinate)/multiwall carbon nanotube (MWCNT) composites are studied. When subjected to AC electric fields in their melt state, PESu/MWCNT composites exhibit dramatic improvements in their transverse electrical conductivity. More importantly, the elevated conductivity values are preserved after matrix solidification. Overall, the experimental results show that the electrified composites exhibit the same electrical conductivity levels as their non‐electrified counterparts at approximately threefold less filler content. The dynamics of the insulator‐to‐conductor transition under an electric field also are studied for these composites and correlate reasonably well with operating parameters, such as electric field intensity, matrix viscosity, and filler content through a relatively simple model. Such a model can serve as an enabling tool in the determination of process conditions for the manufacturing of electrically conducting MWCNT/polymer composites. POLYM. COMPOS., 38:1571–1578, 2017. © 2015 Society of Plastics Engineers     

AC and DC dielectric properties of some polypropylene/calcium carbonate composites

AC dielectric properties and thermally stimulated polarization (TSP) and depolarization (TSD) currents were studied in a series of CaCO₃-filled polypropylene composites. The filler content (0 to 50 weight percent) and the average particle size (3.0 to 16.1 μm) at constant filler content (30 weight percent) were varied in separate groups of samples. In a third group of samples the filler (20 to 40 weight percent) was surface treated with stearates. The AC dielectric behavior of composites containing untreated fillers is largely determined by a small amount of adsorbed water. Upon heating, the dielectric properties show maxima (increasing with decreasing frequency) which disappear on cooling. In the case of stearate-treated fillers the dielectric loss level is higher, the dispersion and loss curves on heating reflect a combination of dipolar and protonic processes with water desorption. In the dry state the onset of an audio frequency relaxation process is observed in the pre-melting zone. The thermally stimulated currents of the composites containing treated and untreated fillers are also different. In the case of the untreated fillers the TSP curves show maxima indicating water desorption which are increasingly intense and roughly exponential with filler content. The high temperature conductivity and the intensity of the pre-melting depolarization peak pass through a minimum as a function of filler content. Above 20 weight percent filler content the activation energy of high temperature conductivity decreases. In the case of the surface treated samples, the thermally stimulated response is different for “wet” and dried samples. The dry samples exhibit a relaxation between the amorphous and crystalline transitions of the matrix polymer which is probably due to interfacial relaxation caused by the enhanced surface conductivity of the stearate-treated fillers.     

AC conductivity of carbon fiber–polymer matrix composites at the percolation threshold

This paper reports results on experimental investigation of the conductivity behavior of carbon fiber filled polymer composites at the percolation threshold. Two types of carbon fiber‐epoxy matrix composites have been studied and comparison of the measured data has been made. These two types of composites differ in the surface modification of carbon fibers (in one case the surface of carbon fibers is covered with polymer beads using the microencapsulation technology, in the other their surface stayed unmodified). Experimental data reveal that surface modification of carbon fibers influences greatly the DC conductivity (percolation threshold moves to higher concentrations) but does not influence the AC electrical properties. From the frequency dependence of conductivity upon fiber concentration it becomes clear that it is not possible to predict the high frequency conductivity (electromagnetic interference shielding properties) based on the DC conductivity. Percolation behavior of conductivity as a function of conductive filler concentration is typical only for DC or low frequency AC conductivity. The percolation threshold gradually vanishes for high frequencies of electromagnetic field. The temperature dependence of electrical properties has also been studied. Composites with concentration near the percolation threshold show the switch‐off effect (at the specific temperature the DC conductivity drops by several orders of magnitude). This switch‐off effect does not occur for high frequency AC conductivity.     

Relaxation behavior of conductive carbon black reinforced chlorosulfonated polyethylene composites

Dynamic mechanical analysis and dielectric relaxation spectra of conductive carbon black reinforced chlorosulfonated polyethylene (CSM) composites were used to study their relaxation behavior as a function of temperature and frequency, respectively. A marginal increase in glass transition temperature has been observed upto 30 phr carbon black filled polymer composite, beyond which it decreases, which has been explained on the basis of aggregation of filler particles in the polymer matrix. The strain dependent dynamical parameters were evaluated at dynamic strain amplitudes of 0.1–200%. The nonlinearity in storage modulus increases with increase in filler loading. It can be explained on the basis of filler–polymer interaction and aggregation of the filler particulates. The frequency dependent dynamical mechanical analysis has also been studied at frequency range of 0.1–100 Hz. The variation in real and complex part of impedance with frequency has been studied as a function of filler loading. The effect of filler loading on ac conductivity has been observed as a function of frequency. An increase in conductivity value has been observed with increase in filler loading. This can be explained on the basis of formation of conducting paths between filler particulates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Piezoresistivity of silicone‐rubber/carbon black composites excited by Ac electrical field

Flexible conductive composites were prepared using liquid silicone rubber as a matrix and conductive carbon black (CCB) as a filler, and the filler loading was varied from 1 to 15 phr in mass ratio. The surface conductivity was studied as a function of CCB concentration (1, 5, 10, 15 wt %), frequency in the range from DC to 1 MHz. The AC resistivity of the composites with low CCB concentration was found to be frequency dependent, whereas the composites with high CCB concentration was almost frequency independent. The resistance/impedance drift of the composites with time decreases sharply with the increase of frequency of applied electrical field. The piezoresistivity of the composite with 5 wt % CCB concentration (the upper percolation limit) was studied. It is found that the composite exhibits prominent positive piezoresistivity coefficient effect through the measurement frequency, and the sensitivity becomes steeper with the increase of exciting frequency. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

DC and AC conductivity in epoxy resin/multiwall carbon nanotubes percolative system

This study attempts to investigate how the inclusion of Multiwalled Carbon‐NanoTubes (MWCNT) influences the DC and AC conductivity response of standard high performance epoxy systems. Towards this direction, the highly electrical conductive fillers were homogenously dispersed at various weight contents (in the range of 0.1% up to 1.0%) using a well established shear mixing protocol. The DC and AC conductivity of the prepared nanocomposites was measured. AC conductivity was examined in the frequency range from 101 to 106 HZ at ambient temperature. An enhancement of conductivity, in accordance to percolation theory, was evidenced increasing the weight content of the conductive nano‐filler. The AC conductivity was found to be frequency dependent beyond a critical frequency that increased with the nano‐filler content. It is proposed that the critical frequency follows also a percolation type law with the weight fraction of the nanotubes. A deeper analysis of all aforementioned observations highlights the multiparametric reliance of the macroscopic electrical response on the properties of the nanotubes, their electrical network topology, and their interactions with the surrounding polymer and CNTs. POLYM. COMPOS., 31:1874–1880, 2010. © 2010 Society of Plastics Engineers.     

Mechanical, rheological, and thermal behavior assessments in HDPE/PA-6/EVOH ternary blends with variable morphology

Visco-elastic and dielectric spectra of multiwalled carbon-nanotube reinforced silicon elastomer nanocomposites were used to study relaxation behavior. SEM photomicrographs shows well dispersion of MWCNT in elastomer matrix. In visco-elastic analysis primary relaxation was studied as a function of temperature (?100 to 100 °C) at frequency 1Hz and strain 1 %. The effect of MWCNT loadings on storage modulus, loss modulus, and loss tangent has been studied. The non-linearity in loss tangent, storage modulus and loss modulus was explained on the basis of MWCNT-elastomer interaction and the inter-aggregate attraction of MWCNT. The secondary β relaxation was studied using dielectric relaxation spectra in the frequency range of 0.1 Hz to 10⁶ Hz. The effect of MWCNT loadings on the complex and real parts of impedance was distinctly visible which has been explained on the basis of interfacial polarization of fillers in a heterogeneous medium and relaxation dynamics of polymer chains in the vicinity of fillers. The dielectric formalism has been utilized to further investigate the conductivity and relaxation phenomenon. The ‘percolation limit’ of the MWCNT in the silicon elastomer was found to be in the range of 4 phr loading.     

Effect of temperature,pressure, and composition on DC resistivity and AC conductivity of conductive styrene–butadiene rubber–particulate metal alloy nanocomposites

Conductive nanocomposites were prepared using styrene butadiene rubber as the polymer matrix and nanosized powder of copper–nickel (Cu–Ni) alloy as the filler. The filler loading was varied from 0 to 40 phr. The electrical conductivity of filled polymer composites is due to the formation of some continuous conductive networks in the polymer matrix. Atomic force microscopy was used to determine the particle size of the nanofiller and its nature of dispersion in the rubber matrix. The DC volume resistivity was measured against the loading of the nanofiller to check the percolation limit. The effect of temperature, applied pressure, time duration under constant compressive stress on the DC resistivity and AC conductivity of the composites with different filler loading were investigated. The change in DC resistivity and AC conductivity against temperature of these composites exhibited positive coefficient of temperature. With the change in applied pressure and time duration under constant compressive stress the DC resistivity undergoes an exponential decrease. The effect of AC field frequency on the AC conductivity was investigated. POLYM. COMPOS. 28:696–704, 2007. © 2007 Society of Plastics Engineers     

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