Effect of some service conditions on the electrical resistivity of conductive styrene–butadiene rubber–carbon black composites

Conductive polymer composites were prepared using vulcanized styrene–butadiene rubber as a matrix and conductive carbon black as a filler. The filler loading was varied from 10 to 60 phr. The volume resistivity was measured against the loading of the carbon black to verify the percolation limit. The electrical conductivity of filled polymer composites is attributed to the formation of some continuous conductive networks in the polymer matrix. These conductive networks involve specific arrangements of conductive elements (carbon black aggregates) so that the electrical paths are formed for free movement of electrons. The effects of temperature and pressure on the volume resistivity of the composites were studied. The volume resistivity of all the composites increased with increase in temperature, and the rate of increase in the resistivity against temperature depended on the loading of carbon black. The change in volume resistivity during the heating and cooling cycle did not follow the same route, leading to the phenomena of electrical hysteresis and electrical set. It was found that the composites with 40 and 60 phr carbon black become more conductive after undergoing the heat treatment. Generally, all the composites showed a positive temperature coefficient of resistivity. The volume resistivity of all the composites decreased with increase in pressure. The relaxation characteristic of the volume resistivity of the composites was studied with respect to time under a constant load. It was found that the volume resistivity of the compressed specimen of the composites decreased exponentially with time. It was observed that initially a faster relaxation process and later a slower relaxation process occurred in these composites. Some mechanical properties of these composites were also measured to confirm the efficacy of these composites for practical applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2179–2188, 2004     

Electrical conductivity of carbon blacks under compression

A study was made of the electrical conductivity of six commercial carbon blacks under compression. The influence of the applied pressure, sample volume, mechanical work, and density of the carbons was investigated. The conductivity was measured at room temperature by impedance spectroscopy over the frequency range 20-10⁶ Hz with a voltage of 1 V. The decrease in volume under compression depended significantly on each particular carbon and on the applied pressure, and for a larger number of carbons it was only important at low pressures. The patterns of variation of the conductivity with pressure and mechanical work were similar. Of the pressure and volume effects comprised in the influence of mechanical work on the conductivity, that of the pressure appeared to predominate. The increase in conductivity with decreasing sample volume was greater for the carbons in which the volume under compression was smaller. The total increase in conductivity was greater for the densest carbons and least for the lightest one. Both the conductivity and its variation under compression were positively related to the density of the carbons.     

A study of the mechanical and electrical properties of a polymer/carbon black binder system used in battery electrodes

The effects of carbon black content and crosslinking on the mechanical and electrical properties of a fluorinated elastomer, FC2178 (Dyneon Corp., Oakdale, MN), poly(vinylidene fluoride‐co‐hexafluoropropylene), were investigated and compared to those of poly(vinylidene fluoride) (PVDF). Attention was given to changes in mechanical and electrical properties of the polymers when under cyclic deformation. To describe the mechanical properties of the carbon‐filled polymers in a way that is independent of the chemical details, two mechanical models were used to fit cyclic stress–strain experiments. The linear model was used to determine the effect of crosslinking on the mechanical properties of crosslinked FC2178 films. However, when carbon black was added to the polymer films, the linear model no longer fit the data well. In particular, the cyclic stress–strain curves for carbon‐filled polymers showed non‐linear regions and displayed the characteristic of ‘memory.’ A non‐linear element was added in parallel with the existing elements of the linear model to successfully describe the effects of the added carbon black. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1891–1899, 2003     

Reversible electrical behavior with strain for a carbon black‐filled rubber

Most unfilled elastomers exhibit a high electrical resistance. Fillers are usually added to elastomers to enhance their mechanical properties. Frequently the filler type used is an electrically conductive carbon black and the inclusion of such fillers reduces the resistivity of the elastomer compound. Previous work has shown that for elastomers containing high abrasion furnace, carbon black fillers such as N330 (or N300 series) at a volume fraction above the percolation threshold the resistivity changes with strain, the precise resistivity versus strain behavior being nonlinear and irreversible for conventional carbon black fillers. A strain‐measuring device, deriving strain directly from a measure of the resistivity, requires that the behavior be reversible and reproducible from cycle to cycle. This work presents the electrical resistivity behavior of a natural rubber (NR) compound filled with Printex XE2 carbon black. This type of filler has a significantly different morphology to the N300 series blacks examined previously. The Printex was incorporated into the rubber at a volume fraction above its percolation threshold and its behavior is contrasted to that observed with N300 series carbon black‐filled NR. Here, and for the first time, reversible electrical resistivity dependence with strain is reported for an elastomer filled with Printex XE2. This reversible behavior under strain opens up the possibility of applications, such as a flexible load sensor, pressure sensor, or switch. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

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     

Carbon black/polystyrene composites as candidates for gas sensing materials

Amorphous polymer-based composites consisting of polystyrene and carbon black were developed in the current work as candidates for gas sensing materials. With the help of polymerization filling, i.e., in-situ polymerization of styrene in the presence of carbon black, the composites were provided with low percolation threshold. The experimental results indicated that the composites have selective sensitivity as characterized by high electrical responsivity to the vapors of non-polar and low polar solvents, and low responsivity to high polar solvent vapors as well. Besides conductivity of the composites, absorption characteristics of both the matrix and the fillers exert importance influence on the gas sensitivity of the composites. Therefore, composites’ performance can be tailored by changing filler concentration, molecular weight and molecular weight distribution of matrix polymer, etc. In regard to the fact that most conducting polymer composites as vapor sensing materials are based on crystalline polymer matrices, the approach reported by this paper provides another feasible way to develop new candidates.     

Filler-elastomer interactions: influence of oxygen plasma treatment on surface and mechanical properties of carbon black/rubber composites

In this work, the influence of oxygen plasma treatment on the surface and adsorption properties of carbon blacks was investigated using X-ray photoelectron spectroscopy (XPS), ζ-potential, and BET isotherms. Then the mechanical properties [tensile strength and tearing energy (G_IIIC)] of carbon black/acrylonitrile butadiene rubber (NBR) composites were measured. As a result, it was found that oxygen plasma treatment generated oxygen-containing functional groups, such as, carboxyl, hydroxyl, lactone, and carbonyl groups, on the carbon black surfaces, resulting in a decrease in the equilibrium spreading pressure or London dispersive component of surface free energy. The tearing energy of the carbon black/NBR composites improved as the oxygen-containing functional groups on the carbon black surfaces increased. This revealed that there is a relatively high degree of interaction between the polar NBR and the oxygen-functional groups of carbon blacks.     

Effect of processing parameters, applied pressure and temperature on the electrical resistivity of rubber-based conductive composites

Carbon black- and short carbon fibre (SCF)-filled conductive composites were prepared from ethylene vinyl acetate (EVA), ethylene propylene diene (EPDM) rubber and their 50:50 blend. The electrical resistivity of carbon black- and SCF-filled composites were measured under different conditions. The electrical conductivity of filled polymer composites is due to the formation of a continuous conductive network in the polymer matrix. These conductive networks involve specific arrangement of conductive elements so that the electrical paths are formed for free movement of electrons. It was found that electrical conductivity of filled conductive composites depends on different processing parameters like mixing time, rotor speed, mixing temperature, vulcanization time and pressure and service conditions like applied pressure and temperature. The results of different experiments have been discussed in light of break down and formation of the continuous conductive network.     

Effect of a carbon black surface treatment on the microwave properties of poly(ethylene terephthalate)/carbon black composites

A surface treatment was applied to carbon black to improve the electrical and microwave properties of poly(ethylene terephthalate) (PET)-based composites. Three different formamide solutions with 1, 2, and 3 wt % concentrations were prepared to modify the surface chemistry of carbon black. Microwave properties such as the absorption loss, return loss, insertion loss, and dielectric constant were measured in the frequency range of 8–12 GHz (X-band range). Composites containing formamide-treated carbon black exhibited enhancements in the electrical conductivity, electromagnetic interference (EMI) shielding effectiveness, and dielectric constant values when compared to composites with untreated carbon black. In addition, increases in the formamide solution concentration and carbon black content of composites resulted in an increase in the electrical conductivity, EMI shielding effectiveness, and dielectric constant values. The percolation threshold concentration of PET composites shifted from a 3 to 1.5 wt % carbon black composition with the surface treatment. The best EMI shielding effectiveness was around 27 dB, which was obtained with the composite containing 8 wt % carbon black treated with a 3 wt % formamide solution. Moreover, this composition gave the lowest electrical resistivity and the highest dielectric constant among the produced composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

炭黑用量对硅橡胶基力敏复合材料性能的影响

以炭黑为导电功能填料制备炭黑/甲基乙烯基硅橡胶(MVQ)力敏复合材料,研究炭黑用量对复合材料硫化特性、拉伸性能、压缩应力松弛性能、电性能和压阻性能的影响.结果表明:炭黑用量为11～16份时,炭黑/MVQ复合材料电性能达到逾渗阈值.随着炭黑用量的增大,炭黑/MVQ复合材料拉伸强度先增大后减小,最后趋于稳定,而压缩松弛率呈减小趋势.炭黑用量为11份时炭黑/MVQ复合材料的压阻重复性较好.适宜的炭黑用量为10～12份.     

炭黑对不饱和聚酯/玻纤复合材料导电性能的影响

在纤维增强不饱和聚酯复合材料中填加不同种类和不同数量的炭黑、ZnO非导电填料及金属导电铝粉进行复合材料电学及力学性能改性研究，通过对体积电阻率和弯曲强度的变化研究，得出乙炔炭黑对材料电学和力学性能综合改性效果较好，非导电填料ZnO用量为15份时改善的导电性能最佳，金属铝粉的填加量在一定范围内既可提高电阻率，又可提高弯曲强度。     

Electrical properties of composites in the vicinity of the percolation threshold

The electrical response of thermoplastic composites composed of carbon black and high‐density polyethylene near the electrical percolation threshold (p_c) has been investigated through the study of the volume resistivity and complex permittivity. The change in conductivity beyond p_c exhibited a critical exponent that was greater than predicted from percolation theory. Composites with carbon black contents slightly larger than p_c exhibited the greatest sensitivity in volume resistivity with temperature variations under the melting point of polyethylene. In addition, percolating composites with low carbon black contents exhibited significant “negative temperature coefficient” (NTC) effects and improvements in conductivity with annealing. Maxwell–Wagner interfacial polarization resulted in moderate increases in both the permittivity (ϵ′) and dielectric loss factor (ϵ″) below p_c, while at percolation, an abrupt and dramatic increase was observed for both components of the complex permittivity. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1573–1582, 1999     

The relationship of carbon black dispersion to electrical resistivity and vulcanizate physical properties

The degree of dispersion of carbon black in rubber is known to be a determining factor in the physical properties of the composite. It is important, therefore, to have a reliable, quantitative technique for assessing carbon black dispersion. It has been known for some time that the degree of dispersion of carbon black is reflected in its electrical resistivity. A resistivity instrument, developed by B. Boonstra, has been redesigned and constructed for use in this study. Factors that influence resistivity (i.e., black type, volume loading, and mixing time) are examined. Physical property and dynamic mechanical measurements are made, and their relationship to black dispersion is investigated. Light microscopy is also used to evaluate dispersion, and these data are compared to the resistivity results.     

Transfer function and working principle of a pressure/temperature sensor based on carbon black/silicone rubber composites

Pressure/temperature sensitive silicon rubber (SR) filled with carbon black (CB) was prepared by a liquid mixing method. The transfer function of a pressure/temperature sensor based on CB/SR was derived by general effective media theory. The results show that the transfer functions coincided well with the experimental data, and the negative pressure coefficient of the resistance/positive temperature coefficient of resistance are shown. The working principles of these two kinds of sensors are different. The working principle of the pressure sensor based on CB/SR was related to the volume fraction of CB. With increasing volume fraction of CB, the working principle of this kind of pressure sensor varied from a piezo‐resistive effect to a strain effect. In addition, the working principle of the temperature sensor based on CB/SR was that the resistivity changed with temperature; this was not related to the volume fraction of CB. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42979.     

Carbon black used as a fluidization aid in gas phase elastomer polymerization: I. Carbon black-monomer interactions

The adsorption of butadiene on carbon black is a function of surface properties, high reinforcing, high surface area carbon black adsorbs more butadiene than low reinforcing big particle size carbon black. It is found that the functional groups on modified carbon blacks, oxidized or sulfur modified carbon blacks significantly reduces the butadiene concentration in headspace. Chemisorption of butadiene on the carbon black surface strongly holds butadiene on the surface, which prevents desorption of butadiene from the carbon black surface. These modified carbon blacks result in a very low concentration of butadiene in the headspace, usually 50-100 times lower than unmodified carbon black.     

A comprehensive picture of the electrical phenomena in carbon black-polymer composites

The electrical conductivity of carbon black-polymer composites was found to depend on the structure of the carbon black particles and to deviate from the expectations of classical percolation theory. We have recently proposed a comprehensive percolation-tunneling model that explains semi-quantitatively all these observations. The central observations and the model are reviewed here. Our resistance-noise measurements have shown that, unlike this model, existing alternative models cannot account for the observations.     

Electrical and mechanical behavior of carbon black–filled poly(vinyl acetate) latex–based composites

The electrical and mechanical behaviors of carbon black‐filled. Poly(vinyl acetate) latex‐based polymer composites were examined. These composites were found to exhibit percolation thresholds in electrical conductivity near 2 vol% carbon black due to their segregated microstructures. Storage modulus and ultimate tensile strength (UTS) both exhibited discontinuities at 10 vol% carbon black, corresponding to a critical pigment volume concentration. Drying composites at 60°C rather than room temperature produced a higher percolation threshold and better mechanical properties at carbon black loadings above 10 vol% carbon black. A figure of merit was proposed to assess the balance of electrical conductivity, storage modulus and UTS. The figure of merit exhibited a peak value at 10 vol% for composites dried at room temperature and was shifted to higher carbon black concentrations when composites were dried at 60°C.     

Electrical and dielectric properties of segregated carbon black–polyethylene systems

The electrical and dielectric properties of compression-molded segregated polyethylene-carbon black mixtures are described in the frequency range between 10 and 8000 kHz as a function of frequency, temperature, and carbon black loading. The segregated systems investigated exhibit insulator-conductor transitions in the range 0.25–0.65% (volume/volume) carbon black. The dielectric constant and the dissipation factor of the conductive samples are relatively very high in the frequency range studied. The dielectric constant increased sharply with the carbon black concentration, and then increased moderately beyond the insulator-conductor transition. The dissipation factor-concentration curves for different carbon blacks show maximum values in the vicinity of the critical concentration values. The dielectric properties of these systems are discussed in terms of interfacial Maxwell-Wagner polarization effects.     

Raman scattering in a new carbon material

Samples of a new carbon material, Diamonite-B, were fabricated under high pressure from a commercial carbon black — identified as mixed fullerenes. The new material is neither graphite-like nor diamond-like, but exhibits electrical properties close to graphite and mechanical properties close to diamond. The use of Raman spectroscopy to investigate the vibrational dynamics of this new carbon material and to provide structural characterization of its short-, medium- and long-range order is reported. We also provide the results of investigations of these samples by high resolution electron microscopy and X-ray diffraction. Hardness, electrical conductivity, thermal conductivity and other properties of this new material are compared with synthetic graphite-like and diamond-like materials, two other phases of synthetic bulk carbon.