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.     

Improvement of conductive network quality in carbon black‐filled polymer blends

Heat treatment of polymer‐based composites is critical for the enhancement of both stability and long‐term service life, especially when the materials function under an inconstant temperature environment. The present article discusses the effect of heat‐treatment conditions on the electrically conductive properties of carbon black (CB)‐filled low‐density polyethylene (LDPE) and ethylene–vinyl acetate copolymer (EVA) composites, which are candidates for positive temperature coefficient (PTC) materials. It was found that the dispersion mode of CB particles changes as a function of the matrix morphology. When the composites are irradiated to form crosslinked networks in the matrix for the elimination of negative temperature coefficient (NTC) behavior, some of the produced free radicals are also entrapped for quite a long time after the irradiation treatment. These residual radicals further enhance the interaction between CB and the matrix and further induce the crosslinking of the matrix so that the composites' conductivity changes with time as a result of the continuous variation in the contacts between the conductive fillers. To improve the quality of the conduction paths in the composites, appropriate post‐heat treatment should be carried out, which speeds up the formation of the above‐mentioned two kinds of crosslinked structures within a limited time. Annealing at 75°C for more than 10 h is believed to be an effective way. After the treatment, a balanced performance characterized by reduced room‐temperature resistivity and improved PTC intensity was obtained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2768–2775, 2002     

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     

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     

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     

Room temperature resistance relaxation behavior for carbon black filled conductive polymer composites

Room temperature resistance relaxation was studied with respect to carbon black (CB) volume fraction, the type of polymer matrix, and the environment. It was found that resistance of CB filled poly(methylvinylsiloxane) and polypropylene (PP) conductive composites changed at room temperature with different directions and amplitudes, depending on the filler volume fraction and the environment. The room temperature resistance relaxation was ascribed to the local Joule heat at the tunneling junction or the swelling effect of the solvents. On the other hand, CB filled immiscible PP/Nylon 1212 blends exhibited a stable electrical conduction due to the selective distribution of CB aggregates along the interface between polymer matrices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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‐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     

Novel flexible electrically conductive adhesives from functional epoxy,flexibilizers, micro‐silver flakes and nano‐silver spheres for electronic packaging

In this study, five different flexibilizers were added into a matrix resin to improve the flexibility of electrically conductive adhesives (ECAs). The flexible ECAs were fabricated from the matrix resin and electrically conductive fillers. Their curing was fixed at 150 °C for 30 min. Of the five flexibilizers, 1,3‐propanediol bis(4‐aminobenzoate) (PBA) had the best effect on the electrical, mechanical and thermal properties of the ECAs. During curing, PBA reacted with the functional epoxy in the matrix resin. The soft ether segments in PBA were grafted into the crosslinked epoxy network to form an orderly spaced mesh structure. This led to high‐temperature stability, with the pyrolysis temperature being above 350 °C. Flexible ECAs with a 10% weight ratio of PBA in the matrix resin had the best properties. Their viscosity and bulk resistivity were the lowest. Their flexibility and electrical conductivity were the highest. They also had low storage modulus which could effectively dissipate or reduce the residual shear stress generated by the mismatch of thermal expansion coefficient between chip and substrate. Their impact strength was the lowest, and the toughening effect was so significant that the improvement was about 48% compared to ECAs. © 2013 Society of Chemical Industry     

Characterization of carbon black‐filled immiscible polypropylene/polystyrene blends

The electrical and rheological behaviors of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) blends were investigated. The compounding sequence influences the phase morphology of the ternary CB/PP/PS composites and the distribution of CB aggregates. Simultaneous measurements of resistance and dynamic modulus were carried out to monitor the phase coalescence of the ternary composites and CB migration and agglomeration in the PS phase during annealing at temperatures above the melting point of PP. The variation of resistivity is mainly attributed to CB agglomeration in the PS phase and the interfacial region, while the variation of dynamic modulus is regarded as the superimposition of the phase coalescence and CB agglomeration in the PS phase. The ternary composites with the majority of CB particles distributed in the interfacial region show the lowest conductive percolation threshold and the most stable resistivity–temperature performance during heating–cooling cycles. Copyright © 2011 Society of Chemical Industry     

Multiple percolation in a carbon‐filled polymer composites via foaming

This article describes an investigation into the effects of foaming on the electrical conductivity for a carbon‐filled cyclic olefin copolymer (COC) composite incorporating both chopped carbon fibers (cCF) and carbon black (CB). Foamed and solid samples were injection molded and then analyzed for cell size, fiber length, fiber orientation, and electrical conductivity. Foamed samples exhibited higher electrical conductivity in the through‐plane direction for materials containing only CB or composites containing both filler types, and reduced electrical conductivity in the cCF‐filled composites. The increased electrical property gained by foaming was attributed to multiple percolation with CB aggregates forming more effective conductive clusters and networks in the continuous polymer phase during growth of the gas domains. A mechanism for the phenomenon was proposed based on these experimental observations. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

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     

Temperature and time dependence of electrical resistivity in an anisotropically conductive polymer composite with in situ conductive microfibrils

An anisotropically conductive polymer composite (ACPC) based on conductive carbon black (CB) and binary polymer blend of polyethylene (PE) and polyethylene terephthalate (PET) was successfully fabricated under shear and elongational flow fields. The PET phase formed in situ the aligned conductive microfibrils whose surfaces were coated by CB particles. This ACPC material exhibited a strong electrical anisotropy within a broad temperature range. When the ACPC samples were subjected to isothermal treatment (IT), they showed anomalous variations of the positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects. The PTC intensity was attenuated gradually with the increase of the IT time, and the NTC intensity was nearly eliminated after IT of 8 or 16 h. Beyond 16 h, the resistivity in the NTC region rose anomalously with the temperature after the elimination of NTC effect, which was the result of much transformation from the potential pathways to the intrinsic pathways due to the disordering of oriented conductive microfibrils. When the amount of potential pathways was very small, the effect of the intrinsic pathway separation surmounts that of the potential pathways, leading to the anomalous resistivity increase in the NTC region. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electric self‐heating behavior of acetylene carbon black filled high‐density polyethylene composites

The electric self‐heating behavior of carbon black (CB) filled high‐density polyethylene (HDPE) was studied in relation to the time‐dependent current and surface temperature under various voltages and to the voltage‐dependent surface temperature at electric–thermal equilibrium. The resistance increase due to self‐heating restricts the current flow through the sample and thus stabilizes the electric power and the self‐heating temperature to their saturation values, which vary with the voltage. A simple phenomenological model shows that self‐heating at electric‐thermal equilibrium is involved in the initial resistance, the electric field induced positive temperature coefficient (PTC) transition and the heat dissipation. The influences of annealing and irradiation crosslinking on the self‐heating behavior are discussed. Copyright © 2004 Society of Chemical Industry     

Chemical sensing materials based on electrically‐conductive immiscible polymer blends

Two families of electrically‐conductive immiscible polymer blends were studied as liquid sensing materials for an homologous series of alcohols. The systems studied include: multiphase matrices [containing carbon black (CB)] consisting of either polypropylene or high‐impact polystyrene as the major phase and thermoplastic polyurethane as the minor dispersed phase; and polyaniline (PANI) dispersed within a polystyrene matrix. Extruded filaments, produced by a capillary rheometer at various shear‐rate levels were used in the sensing experiments. The electrical resistance of these filaments was selectively sensitive to the various alcohols. Moreover, the responses displayed by these filaments are reproducible and reversible. The sensing behaviour of these blends is determined by the nature of the blend components, the blend composition and the processing conditions. An attempt is made to identify the dominant mechanisms controlling the sensing process in CB‐containing immiscible polymer blends and PANI‐containing blends. In addition, the sensing performances of these blends are compared in the light of their sensing mechanisms. Copyright © 2005 Society of Chemical Industry     

Effect of filler treatment on temperature dependence of resistivity of carbon-black-filled polymer blends

Polyblends prove to be able to provide more possibilities for tailoring conductive polymer composites in comparison with individual polymer systems. Accordingly, ethylene–vinyl acetate—low-density polyethylene (EVA–LDPE) filled with carbon black (CB) was prepared in this study as a candidate for positive temperature coefficient (PTC) material. In consideration of the fact that CB distribution plays the leading role in controlling a composite's conduction behavior, chemical treatment of CB was applied to reveal its influence on percolation and the PTC effect. It was found that titanate coupling agent treatment facilitated sufficient distribution of CB in LDPE phase, leading to lower resistivity and a squarer PTC curve. Composites filled with nitric-acid-treated CB exhibited specific temperature dependence of resistivity as a result of the heterogeneous dispersion of CB at the interface of EVA–LDPE, which might provide the materials with a new function. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 489–494, 1999     

Enhanced electrical properties by tuning the phase morphology of multiwalled carbon nanotube‐filled poly(ether ether ketone)/polyimide composites

A novel high‐performance material with enhanced electrical properties was obtained by tuning the phase morphology of poly(ether ether ketone) (PEEK)/thermoplastic polyimide (TPI)/multiwalled carbon nanotube (MWCNT) composites. MWCNTs were selectively located in the TPI phase due to discrepant affinity of MWCNTs between PEEK and TPI. The dependence of the electrical properties of the PEEK/TPI/MWCNT composites on the phase morphology was investigated by changing the PEEK/TPI ratio, and the maximum conductivity was achieved with a PEEK/TPI ratio of 50/50, which could be explained by the selective location of MWCNTs and the co‐continuous phase morphology of the composites. © 2015 Society of Chemical Industry     

Effects of a quaternary ammonium salt on the properties of carbon‐black‐filled natural rubber compounds

The effects of a quaternary ammonium salt, cetyltrimethylammonium maleate (CTMAM) on the curing characteristics and mechanical properties of carbon‐black‐filled natural rubber compounds are determined. Results indicate that CTMAM increases the rate of vulcanization to a maximum at 1 phr (part per hundred parts of rubber) followed by a decrease as the concentration of CTMAM is further increased. The incorporation of CTMAM also improves mechanical properties such as tensile and tear strengths, tensile modulus, hardness and resilience, whilst elongation at break shows a decreasing trend. CTMAM also improves filler dispersion and increases the extent of crosslinking of carbon‐black‐filled natural rubber compounds. © 2001 Society of Chemical Industry     

Effect of double percolation on the electrical properties and electromagnetic interference shielding effectiveness of carbon‐black‐loaded polystyrene/ethylene vinyl acetate copolymer blends

In this study, the concept of double percolation and selective location of a conducting additive was used to develop conducting polymer composites composed of polystyrene (PS) and ethylene vinyl acetate copolymer (EVA) filled with carbon black (CB). Scanning and transmission electron microscopy suggested that the CB was preferentially located in the EVA phase. By combining a cocontinuous morphology and selective location of CB in the EVA phase, we achieved the highest conductivity values and better electromagnetic interference shielding effectiveness in the X‐band frequency range for the 70:30 w/w PS/EVA blend. Electromagnetic attenuation occurred by both reflection and absorption mechanisms, although the first was predominant for composites with a higher amount of CB. The percolation thresholds of the PS, EVA, and 70:30 w/w PS/EVA blend loaded with CB were estimated from the dependence of the alternating‐current and direct‐current conductivities. The rheological properties were also used to relate the electrical behavior to the microstructure of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43013.