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     

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     

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     

Investigation of electrically conductive acrylonitrile‐butadiene rubber

Electrically conductive acrylonitrile‐butadiene rubbers (NBRs) containing carbon black (CB) as conductive filler were prepared in order to investigate their electrical and mechanical properties. The effects of conductive CB loading, temperature, acrylonitrile content, crosslinking density of vulcanizates, and plasticizer on conductivity were studied. The change in electrical conductivity of NBRs with different amounts of CB showed that there is a certain critical point (percolation threshold) where a significant decrease in electrical resistivity (increase in conductivity) is observed. Mechanical properties such as tensile strength, elongation to break, and surface hardness of vulcanized NBRs were measured. It was found that the percolation threshold was 5 phr of CB for the NBR/CB composites. J. VINYL ADDIT. TECHNOL., 13:71–75, 2007. © 2007 Society of Plastics Engineers.     

Improved stability of volume resistivity in carbon black/ethylene-vinyl acetate copolymer composites by employing multi-walled carbon nanotubes as second filler

Semiconductive polymer shielding layers of power cable require stable volume resistivity to protect the insulation layer from stress enhancements when carbon black (CB)/polymer composite undergoes thermal cycles. For the CB-filled polymer composites, CB would often re-aggregate when temperature is close to the melting point of polymer matrix, so that the conductive network would be destroyed. Re-distribution of CB and re-formation of conductive CB network under thermal cycles might be the main reason for the instability of volume resistivity. In this work, the re-aggregation of CB in the CB/polymer composites was disclosed. Besides, a small amount of multi-walled carbon nanotubes (MWNTs) was employed as cofiller with CB to improve the stability of volume resistivity of the polymer composites under thermal cycles. The total weight fraction of conductive fillers (CB or CB cofilled with MWNTs) was set as 35 wt%. Compared with the polymer composites loaded with CB solely, the volume resistivity of the composites filled with CB-MWNTs was much more stable with changing temperature. This can be attributed to the enhancement of conductive networks when the MWNTs are employed as second conductive filler.     

Effect of axial stretching on electrical resistivity of short carbon fibre and carbon black filled conductive rubber composites

The variation of electrical resistivity of carbon black and short carbon fibre (SCF) filled rubber composites was studied against the degree of strain at constant strain rate. It was found that both the degree of strain and strain rate affect the electrical resistivity of the composites. The change in resistivity against the strain and strain rate depends both on the concentration and the type of conductive filler. The incorporation of short carbon fibres (SCF) imparts higher conductivity to the composite than carbon black at the same level of loading. Composites filled with carbon black exhibit better mechanical properties than SCF filled composites. Electrical setting, ie a permanent change in electrical resistivity, was observed during extension–retraction cycles. A good correlation was found between the mechanical response and the electrical response towards strain sensitivity. The results of different experiments are discussed in the light of breakdown and formation of conductive networks in the filled rubber composites. © 2002 Society of Chemical Industry     

Effect of strain on the properties of an ethylene–octene elastomer with conductive carbon fillers

Composites that incorporate a conductive filler into an ethylene–octene (EO) elastomer matrix were evaluated for DC electrical and mechanical properties. Comparing three types of fillers (carbon fiber, low structure carbon black, and high structure carbon black), it was found that the composite with high structure carbon black exhibited a combination of properties not generally achievable with this type of filler in an elastomeric matrix. A decrease in resistivity at low strains is unusual and has only been reported previously in a few instances. Reversibility in the resistivity upon cyclic deformation is a particularly unusual feature of EO with high structure carbon black. The mechanical and electrical performance of the high structure carbon black composites at high strains was also impressive. Mechanical reinforcement in accordance with the Guth model attested to good particle–matrix adhesion. The EO matrix also produced composites that retained the inherent high elongation of the unfilled elastomer even with the maximum amount of filler (30% by volume). The EO matrix with other conducting fillers did not exhibit the exceptional properties of EO with high structure carbon black. Composites with carbon fiber and low structure carbon black did not maintain good mechanical properties, generally exhibited an increase in resistivity with strain, and exhibited irreversible changes in both mechanical and electrical properties after extension to even low strains. An explanation of the unusual properties of EO with high structure carbon black required unique features of both filler and the matrix. The proposed model incorporates the multifunctional physical crosslinks of the EO matrix and dynamic filler–matrix bonds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 894–905, 2000     

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     

Electrical conductivity of carbon black and carbon fibre filled silicone rubber composites

Electrically conductive silicone rubber composites have been prepared through incorporation of conductive acetylene black and short carbon fibre (SCF). The percolation limit for the attainment of high conductivity is found to be relatively less for silicone rubber based composites compared to EPDM or NBR based composites reported earlier. Percolation limit is found to be lower for SCF-filled systems (7.5 phr) compared to black-filled ones (14 phr). Both black- and SCF-filled systems exhibit an increase in resistivity with the increase in temperature (PCT effect). This PCT effect may be explained in terms of differences in the thermal expansion between the rubber matrix and the conductive filler. However, resistivity-versus-temperature plots are not identical during the heating-cooling cycle, leading to some hysteresis and electrical set. The current-voltage relationship is linear (Ohmic in nature) at room temperature but becomes non-linear (non-Ohmic) at elevated temperatures. The resistivity of these composites is measured under different conditions such as on applying pressure and being subjected to different mechanical stress and strain over the specimens. An effort has been made to correlate the effect of different parameters on electrical resistivity with the change in the conductive network structure under different conditions.     

Mechanical,electrical, and dielectric properties of polyvinylidene fluoride/short carbon fiber composites with low‐electrical percolation threshold

In this investigation, polyvinylidene fluoride (PVDF)/short carbon fiber (SCF) composites have been prepared by solution casting technique to enhance electrical and dielectric properties with very low‐electrical percolation threshold (0.5 phr SCF). The effect of SCF content on mechanical, thermal and morphological properties of the composites have also been investigated. The mechanical properties of the composites are found to reduce compared to neat PVDF due to poor polymer–filler interaction which can be concluded from FESEM micrographs showing poor bonding between PVDF and SCF. The PVDF/SCF composites exhibit either positive temperature coefficient effect of resistivity or negative temperature coefficient effect of resistivity depending on the loading of SCF in the polymer matrix. The change in conductivity during heating–cooling cycle for these composites shows electrical hysteresis along with electrical set. The melting point of the composites marginally increases with the increase in fiber loading in PVDF matrix as evidenced from DSC thermograms. X‐ray diffraction analysis reveals the crystallinity of PVDF decreases with the increase in SCF loading in matrix polymer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39866.     

炭黑填充复合型导电聚合物的研究进展

在聚合物基体中添加导电炭黑以降低聚合物的电阻率,是目前最为常用的制备导电聚合物的方法。综述了炭黑填充复合型导电聚合物的研究进展。对影响复合材料导电性能及渗滤阈值的因素进行了讨论。重点介绍了使用共混聚合物作基体,并利用炭黑在共混基体中的非均相分布来降低炭黑用量的研究。     

Resistive viscoelasticity of silicone rubber/carbon black composite

Electrical conductive polymer composites are shown as prospective flexible pressure and stretch sensors for detecting the dangerous deformations and for sensing the pressure with minimal intrusion. To better understand the piezoresistive mechanism and improve the performance of this type of sensor, a series of experiments were conducted to investigate the resistive viscoelasticity of silicone rubber/carbon black composite film. First, the flexible conductive composite film was composed with liquid silicone rubber as the matrix and conductive carbon black as the filler. The filler loading was fixed at 5 phr in mass ratio. Then, the resistive viscoelasticity of the composite film was studied as a function of frequency in the range from DC to 1 MHz, including resistive creep, resistive relaxation, and resistive recovery, although in a standard experiment, one‐step stress or one‐step strain was loaded in transient time and the resistance responses were measured. Result from the experiment shows that the creep of resistance is composed of two distinct segments. One is coincident with the strain creep of a typical viscoelastic material, while the other is quite different. Both the relaxation and the recovery of resistance exhibit strong frequency dependence. The relaxation speed becomes slower with the increase of exciting frequency except DC, and the relaxation speed is marginal when excited by DC electrical field. The recovery time becomes shorter with the increase of the exciting frequency. POLYM. COMPOS., 32:29–35, 2011. © 2010 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     

A novel method to prepare high-resistivity polymer composites

A novel method was developed for the preparation of high-resistivity conductive polymer composites reproducibly. The conventional method which involves the simple mixing of a conductive filler and a polymer usually produces a conductive polymer composite having a loading curve with a region in which the resistivity changes rapidly as the filler concentration changes. Hence, it is very difficult to obtain reproducible materials in that region. This newly developed method involves the preparation of a conventional conductive polymer composite, which is prepared by the simple mixing of carbon black and a polymer as the first step. The resulting compound, which is crosslinked by either electron-beam radiation or a chemical-crosslinking agent, is ground into a fine powder (composite filler) with the particle size less than 250 microns. The composite filler is mixed with another polymer to form a conductive particulate composite which has a loading curve showing a more gradual change of resistivity as a function of filler concentration. The modification of the loading curve is controlled by the resistivity, the shape, and the size of the composite filler.     

AC impedance analysis and EMI shielding effectiveness of conductive SBR 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 complex AC impedance and electromagnetic interference shielding effectiveness (EMI SE) of the composites were measured at the microwave frequencies of 7.8–12.4 GHz. The effect of variation in filler concentration and measurement frequency on the AC impedance and EMI SE of the composites were investigated. Equivalent circuits describing the conduction behavior of the composites were determined by means of Nyquist plots. The complex electric modulus of the composites was also determined. Increase in the filler loading increased the capacitive nature of the materials. The composites were better defined by a parallel resistor–capacitor circuit in series with a resistor. The EMI SE was found to pass through a maximum with increase in frequency. However, with the increase in filler loading and sample thickness of the material, the EMI SE was found to increase continuously. POLYM. ENG. SCI., 46:1342–1349, 2006. © 2006 Society of Plastics Engineers.     

VGCF填充PVDF/PMMA复合材料导电性能的研究

以气相生长碳纤维（VGCF）为导电填料，聚偏氟乙烯（PVDF）、聚甲基丙烯酸甲酯（PMMA）为基体制备复合型导电高分子材料。考察了填料用量、基体种类、配比以及PVDF结晶行为对复合材料导电性能的影响。结果表明，VGCF填充PMMA、PVDF、PVDF／PMMA（50／50）体系的渗滤阔值分别为5、4、3phr的填料用量。VGCF的加入会导致PVDF／PMMA体系发生微观相分离，而且VGCF会选择性富集在PVDF的非晶相中，所以PVDF／PMMA／VGCF体系的导电性呈现双重渗滤现象，该体系的体积电阻率不仅取决于富集相中VGCF的含量，而且还与PVDF相的连续性及其结晶行为密切相关。     

The effect of filler concentration on the electrical,thermal, and mechanical properties of carbon particle and carbon fiber‐reinforced poly(styrene‐co‐acrylonitrile) composites

Composite materials of poly (styrene‐co‐acrylonitrile) (luran) matrix with carbon fibers (CF)/carbon particles (CP) were prepared and their properties were evaluated. The mechanical and thermal properties of these composites were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Although, by increasing the filler concentration no significant difference was found in melting and crystallization temperatures of the luran. The storage and tensile modulus of the composites increased linearly with filler concentration up to 40 wt % that was approximately three times higher than that of the virgin luran. There is a shift in glass transition temperature of the composite with increasing the filler concentration and the damping peak became flatter that indicated the effectiveness of the filler–matrix interaction. The volume resistivity and thermal conductivity (TC) of the composites were also measured. At a given carbon filler content the CF–Luran composites have much less volume resistivity as compared to CP–Luran composites. The decreased percolation threshold and volume resistivity in case of CF–Luran composites indicated that conductive paths existed in the composites. The conductive pathways were probably formed through interconnection of the carbon fillers. The volume resistivity was also decreased as a function of temperature. The thermal conductivity was increased linearly as a function of temperature with increasing filler concentration up to 40% of CF and CP. This increase was more profound in case of CF–Luran as compared to CP–Luran composites. This was owing to greater thermal networks of fibers as compared to particles. POLYM. COMPOS., 28:186–197, 2007. © 2007 Society of Plastics Engineers     

In‐plane thermal conductivity modeling of carbon‐filled liquid crystal polymer–based resins

Adding conductive carbon fillers to insulating thermoplastic resins increases composite electrical and thermal conductivity. In this study, varying amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid crystal polymer. The in‐plane thermal conductivity of the resulting single filler composites was tested. The results showed that adding synthetic graphite particles caused the largest increase in the in‐plane thermal conductivity of the composite. The composites were modeled using ellipsoidal inclusion problems to predict the effective in‐plane thermal conductivities at varying volume fractions with only physical property data of the constituents. The synthetic graphite and carbon black were modeled using the average field approximation with ellipsoidal inclusions and the model showed good agreement with the experimental data. The carbon fiber polymer composite was modeled using an assemblage of coated ellipsoids and the model showed good agreement with the experimental data. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Nylon 6 induced morphological developments and electrical conductivity improvements of polypropylene/carbon black composites

In this study, a polar conductive filler [carbon black (CB)], a nonpolar polymer [polypropylene (PP)], and a polar polymer [nylon 6 (PA6)] were chosen to fabricate electrically conductive polymer composites by melt blending and compression molding. The morphological developments of these composites were studied. Scanning electron microscopy results showed that in a CB‐filled PP/PA6 (CPA) composite, CB particles were selectively dispersed in PA6 phases and could make the dispersed particles exist as microfiber particles, which could greatly improve the electrical conductivity. The PA6 and CB contents both could affect the morphologies of these composites. The results of electrical resistivity measurements of these composites proved the formation of conductive networks. The resistivity–temperature behaviors of these composites were also studied. For CB‐filled PP (CP) composites, there were apparent positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects and an unrepeatable resistivity–temperature characteristic. However, for CPA composites, there were no PTC or NTC effects from room temperature to 180°C, and the resistivity–temperature behavior showed a repeatable characteristic; this proved that CB particles were selectively dispersed in the PA6 phase from another point of view. All experimental results indicated that the addition of PA6 to a CP composite could lead to an expected morphological structure and improve the electrical conductivity of the CP composite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

An electrical approach to monitor wire and cable thermal oxidation aging condition based on carbon black filled conductive polymer composite

Polymeric materials are widely used as insulation and jacketing materials in wire and cable. When such materials are used for long‐term applications, they undergo thermal oxidation aging in the environment. It is necessary to develop an in situ and nondestructive condition monitoring (CM) method to follow the aging of cable materials. The main objective of this work was to investigate low‐density polyethylene/carbon black (LDPE/CB) conductive polymer composites as potential sensor materials for this purpose. LDPE/CB composites with a carbon black loading below the percolation threshold underwent accelerated thermal oxidation aging experiments. The results indicated that the substantial resistivity decreases of the LDPE/CB composites could be directly related to the increases in volume fraction of the conductive carbon black, which was mainly caused by the mass loss of polymer matrix and sample shrinkage during the thermal oxidation aging process. Compared to existing CM method based on density change, the electrical resistivity is more explicit regarding its absolute changes throughout the thermal oxidation aging. The change in resistivity spanned over four orders of magnitude, whereas the composite density only increased 10%. The results offer strong evidence that resistivity measurements, which reflect property changes under thermal aging conditions, could represent a very useful and nondestructive CM approach as well as a more sensitive method than density CM approach. Crystallinity changes in materials investigated by modulated DSC and TGA measurements indicated deterioration of crystalline regions in polymer during the thermal oxidation aging. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 513–520, 2004