High‐density polyethylene/carbon black conductive composites. II. Effect of electron beam irradiation on relationship between resistivity–temperature behavior and volume expansion

A study on the contribution of thermal volume expansion to electrical properties is carried out for high‐density polyethylene (HDPE)/carbon black (CB) composites irradiated by an electron beam. The results show that the volume expansion obviously generates the positive temperature coefficient (PTC) characteristic of resistivity for unirradiated HDPE/CB composites, but the contribution of volume expansion is decreased for crosslinked HDPE in the composites by electron beam irradiation. A higher degree of crosslinking produced by irradiation in the molten state limits the movability of HDPE chains and CB particles so effectively that it decreases the PTC intensity, which is compared with that irradiated at room temperature. It is suggested that the differences in the resistivity–temperature behavior are not explained satisfactorily on only the basis of the thermal volume expansion, and the decreased movability of HDPE chains and CB particles are believed to be the most fatal factors in lowering the PTC effect. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3117–3122, 2002; DOI 10.1002/app.10050     

LDPE/carbon black conductive composites: Influence of radiation crosslinking on PTC and NTC properties

The electrical resistivity of low‐density polyethylene/carbon black composites irradiated by ⁶⁰Co γ‐rays was investigated as a function of temperature. The experimental results obtained by scanning electron microscopy, solvent extraction techniques, and pressure‐specific volume‐temperature analysis techniques showed that the positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effects of the composites were influenced by the irradiation dose, network forming (gel), and soluble fractions (sol). The NTC effect was effectively eliminated when the radiation dose reached 400 kGy. The results showed that the elimination of the NTC effect was related to the difference in the thermal expansion of the gel and sol regions. The thermal expansion of the sol played an important role in both increasing the PTC intensity and decreasing the NTC intensity at 400 kGy. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2742–2749, 2002     

Effect of electron‐beam irradiation on ethylene–methyl acrylate copolymer

Ethylene–methyl acrylate copolymer (Elvaloy 1330) was irradiated by an electron beam at different levels of radiation both in the presence and absence of a trimethylolpropane trimethacrylate sensitizer at various dosages of incorporation. The mechanical, thermal, and electrical properties of these samples were compared. The mechanical properties were observed to reach an optimum maximum around 6 Mrad of irradiation and 1 phr of sensitizer incorporation. Furthermore, an increase in either the radiation dose or the sensitizer level helped very little to further modify the properties. The thermal properties as determined by the thermogravimetric analysis and differential scanning calorimetry studies were quite supportive of the observation made during the study of the mechanical properties. The thermal stability of the irradiated samples underwent an increase with increasing electron‐beam dosage. In a manner similar to those of the mechanical properties, the increase in thermal stability was found to reach a maximum at a particular level of treatment and sensitizer incorporation, beyond which there was marginal or no effect at all. The α transition temperature underwent a substantial increase with increasing crosslink density, as evidenced by the increase in gel content with increasing proportion of electron‐beam radiation dose. The other glass‐transition temperature, however, appeared to remain unaffected. The electrical properties, as described by the dielectric constant, volume resistivity, and breakdown voltage, appeared to be affected very little by the electron‐beam radiation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and conductive properties of polycaprolactone‐grafted carbon black nanocomposites

Polycaprolactone‐grafted carbon black (CB‐g‐PCL) nanocomposites were prepared by surface‐initiated ring‐opening polymerization of ε‐caprolactone on the surface of CB. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), atomic force microscope (AFM), X‐ray diffraction (XRD), and polarizing optical microscope (POM) method were employed to characterize the resultant CB‐g‐PCL. The effect of temperature on resistivity of polycaprolactone‐grafted CB (CB‐g‐PCL) nanocomposites was investigated and compared with that of mixture of CB and PCL. It was found that CB‐g‐PCL nanocomposites exhibited positive temperature coefficient (PTC) phenomena between 48 and 51°C, and negative temperature coefficient (NTC) phenomena and between 51 and 54°C. The prepared CB‐g‐PCL nanocomposites have the potential to be temperature‐dependent switch materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Electron‐beam curing of hydrogenated acrylonitrile–butadiene rubber

The electron‐beam‐induced crosslinking of hydrogenated acrylonitrile–butadiene rubber (HNBR) was investigated. HNBR sheets were exposed to electron‐beam irradiation in air at a room temperature of 25 ± 2°C over a dose range of 0–20 Mrad. An attempt was made to correlate the structure of the irradiated rubber with the properties. The ratio of chain scission to crosslinking and the gelation dose were determined by a method proposed elsewhere. The gel content and dynamic storage modulus increased with the radiation dose. Fourier transform infrared studies revealed the formation of double bonds and carbonyl and ether groups. These observations were further supported by a thermogravimetric analysis of the carbonaceous residue of irradiated HNBR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 648–651, 2005     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and properties of closed‐cell foam prepared from irradiation crosslinked silicone rubber

Silicone rubber foam was prepared through crosslinking with electron beam irradiation and foaming by the decomposing of blowing agent azobisformamide (AC) in hot air. The crosslinking and foaming of silicone rubber was carried out separately, which was different from the conventional method of chemical crosslinking and foaming. After foaming, the silicone rubber foam was irradiated again to stabilize the foam structure and further improve its mechanical properties. The effects of irradiation dose before and after foaming, and the amount of blowing agents on the structure and properties of silicone rubber foam were studied. The experimental results show that with the increase of AC content, the average cell diameter of silicone rubber foam increases a little, the foam density decreases to a minimum value when AC content is 10 phr. With the increase of irradiation dose before foaming from 10 to 17.5 kGy, the cell nucleation density of silicone rubber foam increases, the average cell diameter decreases, and the foam density increases. With the increase of irradiation before foaming, the tensile strength, tensile modulus, and the elongation at break of the silicone rubber foam increase. Through irradiation crosslinking again after foaming, the foam density is decreased and the mechanical properties of silicone foam are further improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of γ‐aminopropyltriethoxylsilane on morphological characteristics of hybrid nylon‐66‐based membranes before electron beam irradiation

Nylon‐66 is a typical semicrystalline polymer that can be crosslinked using crosslinking agents and electron beam irradiation. Hybrid nylon‐66‐based membranes are more porous but denser compared to the pure nylon‐66 membrane. Besides that, hybrid nylon‐66 membranes exhibit higher water uptake and severe swelling in water. Si/nylon‐66 membranes were prepared by adding γ‐aminopropyltriethoxylsilane (APTEOS). Crosslinked silica in nylon‐66 membranes is confirmed with high gel content and Fourier transform infrared peaks, but XRD results showed that there is a low crystalline degree in these membranes. The thermal stability of hybrid nylon‐66 membranes is also less affected by APTEOS. The crosslinking agent only improves storage modulus in hybrid nylon‐66 membranes. After irradiation, it is learned that APTEOS improves separation performance of nylon‐66 membranes. However, excessive APTEOS causes the ratio of effective thickness over porosity (Δx/A_k) reduces significantly resulting a lower permeability membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

炭黑/环氧树脂复合材料的制备及电性能研究

介绍了以二氧化硅为分散剂的炭黑/二氧化硅/环氧树脂基复合材料的组成、制备、导电机理,渗流阈值及PTC效应。分析了影响其PTC效应的因素,包括炭黑粒子、聚合物基体以及材料的加工工艺等。     

Correlation between current–voltage (I–V) characteristic in the electric–thermal equilibrium state and resistivity‐temperature behavior of electro‐conductive silicone rubber

In the electric–thermal equilibrium state the current–voltage (I–V) characteristics of conductive silicone rubbers above the percolation threshold are found to be nonlinear. A mathematic model as I = a₁U ± (a₂U² + C) has been built for the nonlinear I–V relations. Constant C and quadratic term a₂U² can be considered as deviation from Ohm's law. For the first time, a correlation is found for conductive silicone rubber between the I–V characteristic in the electric–thermal equilibrium state and the resistivity–temperature characteristic. Samples with positive temperature coefficient (PTC) resistivity effect exhibit negative deviation from linearity, with an I–V relation as I = a₁U ? (a₂U² + C). Samples with negative temperature coefficient (NTC) resistivity effect exhibit positive deviation, with an I–V relation as I = a₁U + (a₂U² + C). The higher the loaded voltage, the more pronounced the deviation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Radiation grafting/crosslinking of silk using electron‐beam irradiation

The radiation grafting of silk with methacrylamide (MAA) was studied using an electron‐beam (EB) irradiation technique. Two irradiation processes, preirradiation and coirradiation, were compared, and some factors affecting the degree of grafting were investigated. The radiation crosslinking of silk with dimethyloldihydroxyethylene urea (DMDHEU) was preliminarily studied. The physical and mechanical properties such as whiteness, breaking strength, and resilience of the radiation‐grafted/crosslinked silk fabrics were examined. The radiation grafting of silk with MAA increases the silk weight, while the radiation crosslinking of silk with DMDHEU imparts improved crease resistance to silk. X‐ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) analysis indicate the formation of peroxy and free‐radical species on the EB‐irradiated silk. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2028–2034, 2004     

Special electrical conductivity of carbon black‐filled two‐phased thermoplastic vulcanizates

The electrical properties of carbon black (CB)‐filled two‐phased thermoplastic vulcanizates (based on ethylene‐propylene‐diene copolymer and polypropylene, TPV) were investigated in this article. The results showed that the composites had a singularity in electrical conductivity compared with CB‐filled polypropylene composites. Both the loading of CB and the concentration of rubber phase in TPV had the remarkable effect on electrical property of composites. The rubber particles in TPV presented unique and competitive effects in constructing CB electrical conducting network, namely exclusion and block effects. The percolation threshold value of composites apparently decreased with rubber phase content. However, percolation behavior of composites was weakened when rubber phase content was very high. The percolation behavior of composites with loading of CB is weakened apparently by rubber particles. When annealing the composites in the melt state, the resistance‐time dependence of composites was strongly affected by the pressure of mold annealing. Although air aging had a negligible effect on the electrical properties, the microstructure of the CB/TPV composites had changed during air aging. CB/TPV composite only exhibited the negative temperature coefficient behavior even though the temperature was in the melting region of polypropylene, which was mainly attributed to the exclusive effect brought by the thermal expansion of rubber particles. The special electrical properties of CB/TPV can find potential application in many fields. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical relaxation of medical grade UHMWPE of different crosslink density as prepared by electron beam irradiation

Dynamic mechanical thermal analysis (DMTA) has been applied on medical grade ultra high molecular weight polyethylene of different crosslink density as prepared by electron beam irradiation to probe for contributions from crosslinking as well as crystallization. The crosslinking proceeds at a crystalline structure with a crystallinity about 50%. With increasing irradiation dose from 0 to 110 kGy, the molar mass between adjacent crosslinks decreases significantly to reach 3170 g/mol at lowest, whereas the crystallite thickness changes and new thin lamellae grow at almost constant degree of crystallinity. From DMTA in the entire temperature range from ?150 to +140°C and the angular frequency range from 0.6 to 135.4 Hz, three relaxation processes γ, β, and α of different temperature position and activation energy are distinguished. The corresponding chain mobility has been discussed as a sensitive discriminator for the coexisting crosslinked and lamellar phases showing the same dimension of a couple of 10 of nanometres. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Preparation of carboxymethyl sago pulp hydrogel from sago waste by electron beam irradiation and swelling behavior in water and various pH media

Solutions of carboxymethyl sago pulp (CMSP) of various degree of substitution were irradiated with electron beam of various radiation doses. The gelation dose (D_g) and p_o/q_o ratio (p_o is degradation density, q_o is crosslinking density) is dependent on CMSP concentration and degree of substitution. In the range of concentrations of 10% to 80% (w/v) CMSP with degree of substitutions of 0.4, 0.6, and 0.8, the p_o/q_o ratio decreases with increasing %CMSP showing that crosslinking processes are dominating and increasing the gel network of the CMSP hydrogel. The fourier transform infrared spectra of CMSP hydrogels of degree of substitutions of 0.4, 0.6, and 0.8 with percentage of gel fractions 25, 35, and ≥ 40 show differences in the intensity of the absorption bands at 1020–1100, 1326, and 1422 cm^?1 with different degree of substitutions and percentage of gel fraction (%GF) that correspond to different extents of chain scission and crosslinking. The swelling behavior in water shows that CMSP hydrogels could absorb 3500–5300% of water by 1 g of CMSP hydrogel. The ability to absorb water increases with the decrease of degree of substitution and %GF of the CMSP hydrogels. It is also observed that the optimum pH for swelling CMSP hydrogel is at pH 7. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Preparation of crosslinked chitosan by electron beam irradiation in the presence of CCl4

In this article, we report the synthesis of crosslinked chitosan using 8 MeV electron beam (EB) irradiation in the presence of carbon tetrachloride. The crosslinked chitosan is characterized by dissolution, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning colorimetry (DSC), and nanoindentation studies. The insolubility of irradiated films in acetic acid indicates that chitosan has undergone crosslinking reaction. FTIR analysis also confirms the crosslinked structure of chitosan. Mechanical properties such as elastic modulus and hardness are calculated from the nanoindentation data. Modulus and hardness of chitosan increase with increase in the irradiation dose due to the increase in the crosslinking. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electron beam irradiation of ethylene‐propylene terpolymer: Evaluation of trimethylol propane trimethacrylate as a crosslink promoter

The effect of electron beam irradiation on ethylene‐propylene terpolymer (EPDM) was investigated. A 50‐part oil‐extended EPDM with high termonomer (ENB) content (iodine number of base polymer) 19, was selected for this study. An increase in irradiation dose from 0 to 200 kGy resulted in increased crosslinking, measured by an increase in gel contents and better swelling resistance. The effect of the multifunctional monomer trimethylol propane trimethacrylate (TMPTMA) as a crosslink promoter was studied using IR spectroscopy. The IR studies revealed enhanced peak absorbances at 1725, 1257, and 1023 cm^?1 as a result of the increased concentration of C = O and C‐O‐C groups and reduced absorbance at 1630 cm^?1 due decreased concentration of C = C groups with TMPTMA level in the irradiated samples. The presence of TMPTMA increased the level of crosslinking at a given irradiation dose, which was manifested by improvement in tensile properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 968–975, 2005     

Thermally induced double‐positive temperature coefficients of electrical resistivity in combined conductive filler–doped polymer composites

Polymer composites of low‐density polyethylene/polypropylene/graphite/vanadium dioxide (LDPE_0.8/PP_0.2/Gr_0.4/VO₂) are prepared by classical melt‐mixing technology and show a notable double positive temperature coefficient of electric resistivity (PTC), which originates from the combined effect of highly conductive Gr and VO₂ with a thermal phase transition. When the weight ratio of VO₂ is 8 wt %, the positive temperature coefficient intensity (PTCI) for the composites reaches 3.85 orders of magnitude. The model system demonstrates the reason for the improvement in the PTC performance of the polymer composites by analyzing the construction of the conductive networks. Therefore, the addition of phase‐transition compounds may be a promising path to improving PTC materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44876.     

Resistivity relaxation behavior of carbon black filled high‐density polyethylene conductive composites

The variation of resistivity for high‐density polyethylene (HDPE) conductive composites filled with carbon black (CB) with time was investigated under the excitation of different temperature field. The movement of CB particles in the HDPE matrix was not a momentary equilibrium process, but a relaxation process. The relaxation of resistivity of the composites was monotonic, and it could be described by an exponential form above melting temperature. However, the relaxation of resistivity was nonmonotonic below melting temperature, herein a parameter t₀ which was the beginning time of the resistivity attenuation could be introduced into the exponential equation. The attenuation of resistivity at constant temperature was limited for the composites with certain content of CB. The resistivity of the composites would incline to a constant value with the prolongation of time no matter what the heat treatment temperature was. Heating rate had influence on the relaxation of resistivity of the composites, and the lower heating velocity resulted in less time to approach to the equilibrium resistivity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013