Influences of compatibilization and compounding process on electrical conduction and thermal stabilities of carbon black‐filled immiscible polypropylene/polystyrene blends

The influences of styrene–butadiene–styrene (SBS) copolymer compatibilizer and compounding process on the electrical conduction and thermal stabilities of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) (1/1) blends were investigated. The immiscible CB/PP/PS composite with CB homogeneously located in the PS phase exhibited the highest resistivity and the fastest variation amplitudes of electrical resistivity (ρ) and rheological parameters upon annealing. An optimal content of 5 vol% SBS could significantly lower ρ of the composites by partially trapping CB particles in the PP/PS interfacial region and by reducing the phase size. The compatibilizer markedly slowed down the variation amplitudes of ρ and rheological parameters and the phase coalescence of the composites submitted to thermal annealing. The (SBS/CB)/PP/PS composite with CB located at the PP/PS interface and in the PP phase prepared by blending a (SBS/CB) masterbatch with PP and PS exhibited lower ρ and better thermal stability in comparison with the CB/SBS/PP/PS composite with CB mainly within the PS phase and partially at the PP/PS interface prepared by direct blending. Spreading and wetting coefficients were used to explain the CB distribution and the phase morphology of the composites. © 2012 Society of Chemical Industry     

Carbon black‐filled immiscible polypropylene/epoxy blends

Carbon black‐ (CB) filled immiscible thermoplastic/thermosetting polymer blends consisting of polypropylene (PP) and epoxy resin were reported in this paper. The PP/epoxy/CB blends with varied compositions and different processing sequences were prepared by melt‐mixing method. The CB distribution and the relationship between morphology and electrical properties of the PP/epoxy/CB blends were investigated. Scanning electron microscopy (SEM), optical microscopy, and extraction experimental results showed that in PP/epoxy blends CB particles preferentially localized in the epoxy phase, indicating that CB has a good affinity with epoxy resin. The incorporation of CB changed the spherical particles of the dispersed epoxy phase into elongated structure. With increasing epoxy content, the elongation deformation of epoxy phase became more obvious and eventually the blends developed into cocontinuous structure. When CB was initially blended with PP and followed by the addition of epoxy resin, the partial migration of CB from PP to the epoxy phase was observed. When the PP/epoxy ratio was 40/60, the percolation threshold was reduced to about 4 phr CB, which is half of the percolation threshold of the PP/CB composite. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 461–471, 2006     

Crystallization behavior of carbon black‐filled polypropylene and polypropylene/epoxy composites

The crystallization behavior of polypropylene (PP)/carbon black (CB) and PP/epoxy/CB composites was studied with differential scanning calorimetry (DSC). The effects of compatibilizer MAH‐g‐PP and dynamic cure on the crystallization behavior are investigated. The nonisothermal crystallization parameters analysis showed that CB particles in the PP/CB composites and the dispersed epoxy particles in the PP/epoxy composites could act as nucleating agents, accelerating the crystallization of the composites. Morphological studies indicated that the incorporation of CB into PP/epoxy resulted in its preferential localization in the epoxy resin phase, changing the spherical epoxy particles into elongated structure, and thus reduced the nucleation effect of epoxy particles. Addition of MAH‐g‐PP significantly decreased the average diameter of epoxy particles in the PP/epoxy and PP/epoxy/CB composites, promoting the crystallization of PP more effectively. The isothermal crystallization kinetics and thermodynamics of the PP/CB and PP/epoxy/CB composites were studied with the Avrami equation and Hoffman theory, respectively. The Avrami exponent and the crystallization rate of the PP/CB composites were higher than those of PP, and the free energy of chain folding for PP crystallization decreased with increasing CB content. Addition of MAH‐g‐PP into the PP/epoxy and PP/epoxy/CB composites increased the crystallization rate of the composites and decreased the chain folding energy significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 104–118, 2006     

Electrical properties and morphology of carbon black‐filled HDPE/EVA composites

The sensitive effect of weight ratio of the high‐density polyethylene (HDPE)/ethylene‐vinylacetate copolymer (EVA) on the electrical properties of HDPE/EVA/carbon black (CB) composites was investigated. With the EVA content increasing from 0 wt % to 100 wt %, an obvious change of positive temperature coefficient (PTC) curve was observed, and a U‐shaped insulator‐conductor‐insulator transition in HDPE/EVA/CB composites with a CB concentration nearby the percolation threshold was found. The selective location of CB particles in HDPE/EVA blend was analyzed by means of theoretical method and scanning electron micrograph (SEM) in order to explain the U‐shaped insulator‐conductor‐insulator transition, a phenomenon different from double percolation in this composite. The first significant change of the resistivity, an insulator‐conductor transition, occurred when the conductive networks diffused into the whole matrix due to the forming of the conductive networks and the continuous EVA phase. The second time significant change of the resistivity, a conductor‐insulator transition, appeared when the amorphous phase is too large for CB particles to form the conductive networks throughout the whole matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Experimental analysis of viscoelastic properties in carbon black‐filled natural rubber compounds

Processability and viscoelastic properties of natural rubber (NR) compounds filled with different carbon black loadings and types were investigated with the use of a steady shear rheometer, namely, the Mooney viscometer, and an oscillatory rheometer, namely, the Rubber Process Analyser (RPA2000). It was found that the type and amount of carbon black strongly influence the viscoelastic properties of rubber compounds. Both the dilution effect and filler transient network are responsible for the viscoelastic properties, depending on the vulcanization state. In the case of uncured compounds, the damping factor of the uncured NR decreases with increasing black loading. This is attributed to the reduction of mobilized rubber content in the compound (or the dilution effect). However, in the case of the cured NR vulcanizates, the filler transient network is the dominant factor governing the damping factor of the vulcanizate. With increasing black loading, the damping factor of the vulcanizate clearly increases. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2197–2203, 2005     

Carbon black‐filled PET/HDPE blends: Effect of the CB structure on rheological and electric properties

The rheological and electric properties of blends of poly(ethylene terephthalate) (PET) and high‐density polyethylene (HDPE) filled with various types of carbon black (CB) were analyzed in detail in this project. Four types of CB samples with available values of surface area, particle size, porosity, density, and maximum packing fraction were considered. Blends were prepared using an internal mixing chamber at two different rotational speeds, prior to mold compression of the samples. The rheological properties of the blends with varying polymer composition and a constant amount of CB were recorded in terms of torque variation with time for two shear rates (in terms of rotational speed). Rheological data were related to the resistivity of blends. Results show that the CB structure (porosity, surface area, apparent bulk density, and particle size) largely determine the resulting equilibrium torque and electrical properties. Furthermore, since CB is preferentially located in the HDPE phase, higher conductivity is observed as the PET content decreases, since the relative CB content in this phase increases. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 562–569, 2001     

Manipulating the conductivity of carbon‐black‐filled immiscible polymer composites by insulating nanoparticles

The conductivity of an immiscible polymer blend system, microfibrillar conductive poly(ethylene terephthalate) (PET)/polyethylene (PE) composite (MCPC) containing carbon black (CB), was changed by the addition of insulating CaCO₃ nanoparticles. In MCPC, the PET forms microfibrils during processing and PE forms the matrix. The CB particles are selectively localized in the PET microfibrils. When the insulating CaCO₃ nanoparticles are added, they substitute for some of the conductive CB particles and obstruct the electron paths. As a result, the resistivity of the MCPC can be tailored depending on the insulating filler content. The resistivity‐insulating filler content curve displays a sluggish postpercolation region (the region immediately following the percolation region and in front of the equilibrium flat of the resistivity‐filler content curve), suggesting that the MCPC in the postpercolation region possesses an enhanced manufacturing reproducibility and a widened processing window. These features are of crucial importance in making sensor materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Thermodynamically induced self‐assembled electrically conductive networks in carbon‐black‐filled ternary polymer blends

By calculating the surface tensions of the components, composites with innovative thermodynamically induced self‐assembled electrically conductive networks were designed, prepared and investigated. Carbon black (CB) was added into a ternary blend system comprised of poly(methyl methacrylate) (PMMA), ethylene–acrylic acid copolymer (EAA) and polypropylene (PP). Scanning electron microscopy images show that the PMMA/EAA/PP ternary blend forms a tri‐continuous phase structure like a sandwich, in which PMMA and PP form a co‐continuous phase while EAA spreads at the interface of the PMMA and PP phases as a sheath. The micrographs and resistivity–temperature characteristic curve results indicate that CB fillers are selectively located at the interface of the PMMA and PP phases, namely the EAA phase. The percolation threshold of PMMA/EAA‐CB/PP composites is 0.2 vol%, which is only one‐fifth of that of PP/CB composites. Copyright © 2011 Society of Chemical Industry     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Time dependences of conduction and self‐heating in acetylene carbon black‐filled high‐density polyethylene composites

The time dependences of electrical conduction and self‐heating behaviors in high‐density polyethylene filled with acetylene carbon black of 0.082 in volume fraction are studied in relation to voltage and ambient temperature. The characteristic decay current constant τ_i, and the exponential growth time constant for self‐heating τ_g are determined for the samples under voltages U above the critical value U_c for the onset of self‐heating. The influences of voltage and ambient temperature on τ_i and τ_g as well as the amplitude of the low‐resistance to high‐resistance switching are discussed on the basis of the random resistor network (RRN) model and the relationship between U_c and the intrinsic resistivity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1124–1131, 2006     

Continuous ultrasonic devulcanization of carbon black‐filled NR vulcanizates

The continuous ultrasonic devulcanization of natural rubber (NR) filled with various concentrations of carbon black (CB) indicated a minimum of crosslink density and gel fraction at an intermediate amplitude, which is independent of CB content. An attempt was made to improve the efficiency of devulcanization by use of various chemicals (1,3 Diphenylguanidine, 2‐Mercaptobenzothiazole, Thianaphthene). However, these experiments did not indicate any improvement in comparison with devulcanization without chemicals. An idea of adding fresh CB into devulcanized compound, which has been shown to improve mechanical properties in the case of styrene–butadiene rubber (SBR), was tested in the present study for CB filled NR compound. The obtained result indicated that an addition of fresh CB to devulcanized CB‐filled NR did not lead to an improvement in mechanical properties upon revulcanization. The revulcanization recipe was optimized to improve the mechanical properties of revulcanized CB‐filled NR vulcanizates. It was found that CB‐filled NR upon revulcanization retained its strain‐induced cystallizability with the tensile strength and elongation at break at about 50 and 70% level of the virgin vulcanizates. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2340–2348, 2001     

Heat treatment‐induced multiple melting behavior of carbon black‐filled polymer blends in relation to the conductive performance stabilization

Polymer blend‐based electrical conductive composites are provided with more possibilities for tailoring the performance in comparison with single polymer systems. To find an optimum heat treatment temperature of the composites, which is critical to practical applications, detailed thermal analyses of the related materials were carried out as a function of different annealing conditions. Based on the discussion of the morphological variation during treatment in terms of multiple melting behavior, it was found that an annealing temperature of 75°C is able to stabilize the resistivity of the composites within a reasonable period of time, as only solid‐state crystallization of LDPE and uniformization of EVA crystalline size are involved. In contrast to treatment at a temperature higher than 75°C, the ultimate equilibrium resistivity resulting from the above annealing procedure approaches the resistivity of the composites as‐manufactured. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1267–1273, 2001     

不同粒径炭黑填充的氯化聚乙烯/氯丁橡胶共混胶的性能

采用不同粒径的炭黑填充氯化聚乙烯/氯丁二烯(CM/CR)共混胶,研究了炭黑粒径对其分散性、共混胶硫化特性、物理机械性能、动态力学性能和耐油性的影响。结果表明,随炭黑粒径的增大,CM/CR共混胶的门尼黏度减小,正硫化时间延长;粒径太小或太大均不利于炭黑在共混胶中的分散;不同粒径炭黑的填充胶均表现出Payne效应,粒径越小的炭黑对共混胶的增强效果越好,填充胶的耐油性越好,但Payne效应也最明显。     

Electrical behavior and structure of polypropylene/ultrahigh molecular weight polyethylene/carbon black immiscible blends

This study investigates the electrical behavior, which is the positive temperature coefficient/negative temperature coefficient (PTC/NTC), and structure of polypropylene (PP)/ultrahigh molecular weight polyethylene (UHMWPE)/carbon black (CB) and PP/γ irradiated UHMWPE (XL‐UHMWPE)/CB blends. As‐received UHMWPE or XL‐UHMWPE particles are chosen as the dispersed phase because of their unusual structural and rheological properties (extremely high viscosity), which practically prevent CB particles penetration. Because of their stronger affinity to PE, CB particles initially form conductive networks in the UHMWPE phase, followed by distribution in the PP matrix, thus interconnecting the CB‐covered UHMWPE particles. This unusual CB distribution results in a reduced electrical percolation threshold and also a double‐PTC effect. The blends are also investigated as filaments for the effect of shear rate and processing temperature on their electrical properties using a capillary rheometer. Because of the different morphologies of the as‐received and XL‐UHMWPE particles in the filaments, the UHMWPE containing blends exhibit unpredictable resistivities with increasing shear rates, while their XL‐UHMWPE containing counterparts depict more stable trends. The different electrical properties of the produced filaments are also related to differences in the rheological behavior of PP/UHMWPE/CB and PP/XL‐UHMWPE/CB blends. Although the flow mechanism of the former blend is attributed to polymer viscous flow, the latter is attributed to particle slippage effects. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 104–115, 2001     

Dynamic properties of carbon black filled chlorinated polyethylene/hindered phenol blends

Aggregates of carbon black (CB) in a polymer matrix have a tendency to form a CB network. The dynamic mechanical properties of binary systems of chlorinated polyethylene (CPE) and CB or 3,9‐bis{1,1‐dimethyl‐2[β‐(3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl)propionyloxy]ethyl}‐2,4,8,10‐tetraoxaspiro[5,5]‐undecane (AO‐80) and their ternary systems were investigated. It was found that the dynamic mechanical properties of those systems depend on the colloidal properties, surface oxides, and surface modification of CB. For binary systems of CPE and CB, oxidized CB gives a high modulus at low strain amplitude and a large Payne effect compared with untreated CB. In contrast, the reverse effect was observed for their ternary systems. Consequently, a good micro‐dispersion is obtainable by surface modification due to physical adsorption of AO‐80 on oxidized CB particles via hydrogen bonds. © 2003 Society of Chemical Industry     

Electrical characteristics of fluorinated carbon black‐filled poly(vinylidene fluoride) composites

Dispersion and electrical properties of fluorinated carbon black‐filled poly(vinylidene fluoride) (PVDF) composites were studied as a function of the fluorine content. It was found that with increasing the fluorine content carbon particles tend to stick together to form large aggregates. The percolation concentration increases to a high concentration, whereas the percolation process becomes gradual. The temperature dependence of resistivity measurements show that the fluorinated carbon black‐filled PVDF composites exhibit a high PTC intensity and a low NTC effect. These phenomena were discussed in terms of thermodynamic interactions between fluorinated carbon and the PVDF matrix. The dielectric behavior was also investigated in this study. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1063–1070, 2001     

Preparation and characterization of carbon black‐polystyrene composite particles by high‐speed homogenization assisted suspension polymerization

Composite particles of carbon black‐polystyrene with controllable size were successfully prepared using high‐speed homogenization‐assisted suspension polymerization. The carbon black particles were modified by oleic acid to make it more hydrophobic and more compatible with polymers before the encapsulation process. The effects of homogenization speed, homogenization time, agitation speed, pigment concentration, and stabilizer concentration on the properties of complex spheres were investigated in detail. The results of orthogonal experiments proved that the stabilizer concentration plays the most important role in controlling the size of complex particles. The particles were also characterized by FTIR and SEM. SEM photographs proved that the complex particles had good spherical forms with smooth surfaces. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the mold temperature on the electrical properties of carbon-black-loaded polystyrene/SB block copolymer blends

The electrical resistivities of a carbon-black-filled styrene–butadiene block copolymer (SB) and their blends with polystyrene were measured as a function of carbon content for specimens compression-molded at 200 and 250°C. The insulator–conductor point transition was greatly influenced by the mold temperature. This behavior associated to the scanning electronic microscopy investigations suggests the presence of some amount of the filler at the interface. A strong interaction between the filler and the polymer was also observed. The formation of bound rubber and a coherent rubber–filler gel depend on the molding conditions and the carbon black content in the composites. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 825–833, 1998     

Simultaneous measurement of resistance and viscoelastic responses of carbon black‐filled high‐density polyethylene subjected to dynamic torsion

The conduction and viscoelastic responses to temperature are measured simultaneously for carbon black (CB) filled high‐density polyethylene (HDPE) subjected to dynamic torsion. PTC/NTC transition was correlated with the loss tangent peak and the quasi modulus plateau, which was ascribed to the filler network. The bond‐bending model of elastic percolation networks was used to reveal the structural mechanisms for the cyclic resistance changes at different temperatures. The resistance changes at lower temperatures depended on the deformation of the polymer matrix, while the changes in melting state were mainly attributed to the rearrangement of the CB network. A simple scaling law is derived to relate resistance and dynamic storage modulus in the melting region. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008