INVESTIGATION OF MICROSTRUCTURE AND CONDUCTIVE MECHANISM OF HIGH DENSITY POLYETHYLENE/CARBON BLACK PARTICLE COMPOSITE BY POSITRON ANNIHILATION LIFETIME SPECTROSCOPY

The microstructure and conductive mechanism of high density polyethylene/carbon black (HDPE/CB) compositewere investigated by positron annihilation lifetime spectroscopy (PALS). The PALS were measured in two series of samples,one with various CB contents in the composites and the other with various γ-irradiation doses in HDPE/CB compositecontaining 20 wt% CB. It was found that CB particles distribute in the amorphous regions, the CB critical content value inHDPE/CB composite is about 16.7 wtO/ and the suitable γ-irradiation dose for improving the conductive behavior ofHDPE/CB composite is about 20 Mrad. T'he result observed for the second set of samples suggests that γ-irradiation causesnot only cross-linking in amorphous regions but also destruction of the partial crystalline structure. Therefore, a suitableirradiation dose, about 20 Mrad, can induce sufficient cross-linking in the amorphous regions without enhancing thedecomposition of crystalline structure, so that the positive temperature coefficient (PTC) effect remains while the negativetemperature coefficient (NTC) effect is suppressed. A new interpretation of the conductive mechanism, which might providea more detailed explanation of the PTC effect and the NTC effect has been proposed.     

Electroactive shape memory cyanate/polybutadiene epoxy composites filled with carbon black

Electroactive shape memory composites were synthesized using polybutadiene epoxy(PBEP) and bisphenol A type cyanate ester(BACE) filled with different contents of carbon black(CB). Dynamic mechanical analysis(DMA), scanning electron microscopy(SEM), electrical performance and electroactive shape memory behavior were systematically investigated. It is found that the volume resistivity decreased due to excellent electrical conductivity of CB, in turn resulting in good electroactive shape memory properties. The content of CB and applied voltage had significant influence on electroactive shape memory effect of developed BACE/PBEP/CB composites. Shape recovery can be observed within a few seconds with the CB content of 5 wt% and voltage of 60 V. Shape recovery time decreased with increasing content of CB and voltage. The infrared thermometer revealed that the temperature rises above the glass transition temperature faster with the increase of voltage and the decrease of resistance.     

Electrical Percolation of Carbon Black Filled Poly （ethylene oxide） Composites in Relation to the Matrix Morphology

The present work studies the electrical conduction performance of carbon blaak (CB) filled poly(ethylene oxide) (PEO) composites. The addition of CB leads to reduced matrix crystallinity as the fillers which are partly situated inside the lamellae and hinder the growth of PEO crystallites. As a result, the electrical percolation behavior is related with the matrix morphology.     

Resistivity-Temperature Behavior of CB-Filled HDPE Foaming Composites

High-density polyethylene/carbon black foaming conductive composites were prepared from acetylene black（ACEY） and super conductive carbon black（HG-1P） as conductive filler, low-density polyethylene（LDPE） as the second component, ethylene-vinyl acetate（EVA） and ethylene propylene rubber（EPR） as the third component, azobisformamide（AC） as foamer, and dicumyl peroxide（DCP） as cross-linker. The structure and resistivity-temperature behavior of high-density polyethylene（HDPE）/CB foaming conductive composites were investigated. Influences of carbon black, LDPE, EVA, EPR, AC, and DCP on the foaming performance and resistivity-temperature behavior of HDPE/CB foaming conductive composites were also studied. The results reveal that HDPE/CB foaming conductive composite exhibits better switching characteristic; ACET-filled HDPE foaming conductive composite displays better positive temperature coefficient（PYC） effect; whereas super conductive carbon black（HG-1P）-filled HDPE foaming conductive composite shows better negative temperature coefficient（NTC） effect.     

Poly(ethylene terephthalate)/carbon black composite fibers prepared by electrospinning

Poly(ethylene terephthalate)(PET)/carbon black(CB) composite fibers with improved mechanical properties in tensile modulus and tensile strength are prepared by eletrospinning. Stable dispersions suitable for electrospinning are obtained by dispersing melt pre-compounded PET/CB composites in hexafluoroisopropanol. The fiber morphology and CB dispersion are investigated by FESEM and TEM. The addition of CB has no obvious effect on fiber diameter, and the average fiber diameters for all the samples are around 2-3 μm. CB in the fibers is in the form of submicron-sized clusters. The thermal properties of the PET/CB composite fibers are evaluated by DSC, showing almost unchanged melting temperature and crystallinity. Uniaxial tensile tests are used to measure the mechanical properties of the PET/CB composite fiber mats. The fiber mats containing 1 wt%-8.5 wt% CB have significantly improved tensile modulus compared to neat PET fiber mat, showing reinforcing effect of CB. The electrical conductivity of the fiber mats has also been tested.     

Electrical properties of conductive polymer composites prepared by an innovational method

<正>An innovational method that poly(styrene-co-maleic anhydride)(SMA),a compatibilizer of immiscible nylon6/polystyrene(PA6/PS) blends,was first reacted with carbon black(CB) and then blended with PA6/PS,has been employed to prepare the PA6/PS/(SMA-CB) composites of which CB localized at the interface.In PA6/PS/CB blends,CB was found to preferentially localize in the PA6 phase.However,in the PA6/PS/(SMA-CB) blends,it was found that CB particles can be induced by SMA to localize at the interface.The electrical porperties of PA6/PS/(SMA-CB) composites were investigated.The results showed that the composites exhibited distinct triple percolation behavior,i.e.the percolation is governed by the percolation of CB in SMA phase,the continuity of SMA-CB at the interface and the continuity of PA6/PS interface.The percolation threshold of PA6/PS/(SMA-CB) was only 0.15 wt%,which is much lower than that of PA6/PS/CB.Moreover,the PTC(positive temperature coefficient) intensity of PA6/PS/(SMA-CB) composites was stronger than that of PA6/PS/CB and the negative temperature coefficient(NTC) effect was eliminated.The electrical properties of PA6/PS/(SMA-CB) were explained in terms of its special interface morphology:SMA and CB localize at interphase to form the conductive pathways.     

Influence of Liquid Isoprene Rubber on Strain Softening of Carbon Black Filled Isoprene Rubber Nanocomposites

The reinforcement of rubbers by nanoparticles is always accompanied with enhanced dissipation of mechanical energy upon large deformations. Methods for solving the contradiction between improving reinforcement and reducing energy dissipation for rubber nanocomposites have not been well developed. Herein carbon black(CB) filled isoprene rubber(IR)/liquid isoprene rubber(LR) blend nanocomposites with similar crosslink density(ν_e) are prepared and influence of LR on the strain softening behaviors including Payne effect under large amplitude shear deformation and Mullins effect under cyclic uniaxial deformation is investigated. The introduction of LR could improve the frequency sensitivity of loss modulus and reduce critical strain amplitude for Payne effect and loss modulus at the low amplitudes.Meanwhile, tuning ν_e and LR content allows reducing mechanical hysteresis in Mullins effect without significant impact on the mechanical performances. The investigation is illuminating for manufacturing nanocomposite vulcanizates with balanced mechanical hysteresis and reinforcement effect.     

Formation of Network by Carbon Black，Silica and Their Mixing Fillers in Isoprene Rubber北大核心CSCD

The network formed by fillers has great influence on the mechanical properties of rubber materials. To understand the formation of network by carbon black,silica,and carbon black/silica mixing fillers in rubber and its influence on the properties of rubber,isoprene rubber/filler composites with different filler loadings are prepared and their micromorphology,rheological and tensile properties are investigated. It is found that the dispersion of fillers is better in rubber after cure than that in rubber before cure for all three rubber systems,and the filler size of silica is smaller than that of carbon black,but the aggregation is more severe in silica filled rubber system. In mixed filler system,the two fillers tend to aggregate separately, leading to the low modulus at small strain than that in single filler system. With the increase of the filler loading,the tensile strength increases first and then decreases,the elongation at break decreases,and the temperature rise in compression flexometer tests increases. Moreover,the temperature rise in mixed filler system is higher than that in single filler system at high filler loading. © 2022, Science Press (China). All rights reserved.     

A Novel Method for Preparing Polyurethane Based Conductive Composites with Low Percolation Threshold

A novel method for preparing conductive carbon black filled polymer composites with low percolation threshold from polyurethane emulsion are reported in this paper. The experimental results indicate that with a rise in carbon black concentration the insulator-conductor transition in the emulsion blended composites occurs at 0.8-1.4vol%. In contrast, the solution blended composites exhibit drastic increase in conductivity at conducting filler fraction as high as 12.3-13.3vol%. It is demonstrated that the composites microstructure rather than chemical structure of the matrix polymer predominantly determines the electrical conduction performance of the composites.     

PTC/NTC Behavior of PVDF Composites Filled with GF and CF

Conductive polyvinylidene fluoride（PVDF）matrix composites filled with graphited fiber（GF）or carbon fiber（CF）were prepared by the melt-mixing method.The breakage and length distribution of the fibers in the polymer matrix were studied by scanning electron microscope（SEM）and optical microscope（OM）observations,respectively. The differences in the positive temperature coefficient（PTC）effects of the composites were mainly attributed to inter-fiber contact ability.The elimination of the negative temperature coefficient（NTC）effect for CF/PVDF composite was because of an increase in the viscosity of the polymer matrix.With the same filler content,CF could be more effective,to eliminate the NTC effect when compared with GF.Addition of 2%CF（mass fraction）in the PVDF composite with 7%GF（mass fraction）could effectively eliminate the NTC phenomenon of the composite.     

Positive‐temperature‐coefficient/negative‐temperature‐coefficient effect of low‐density polyethylene filled with a mixture of carbon black and carbon fiber

Low‐density polyethylene (LDPE) filled with carbon black (CB) and carbon fiber (CF) composites were prepared by a conventional melt‐mixing method. The effects of a mixture of CB and CF on the positive‐temperature‐coefficient (PTC) effect and the negative‐temperature‐coefficient (NTC) effect, as well as the percolation threshold, were examined in detail. A synergy effect between CB and CF occurred, in that continuous conductive pathways formed within the CB/CF‐filled composite. The percolation threshold was moved to a reduced filler content with the addition of CF to an LDPE/CB composite. A model was proposed to explain the difference in the PTC behavior of composites containing CB and CF and composites containing only CB or CF. In addition, the NTC effect was weakened with a mixture of CB and CF, and a relatively small radiation dose was required to eliminate the NTC phenomenon in LDPE/CB/CF composites. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3094–3101, 2003     

Roles of work of adhesion between carbon blacks and thermoplastic polymers on electrical properties of composites

The effect of the work of adhesion between carbon blacks and different thermoplastic polymers on the positive temperature coefficient (PTC) of composites was investigated. Thermoplastic polymers, such as EVA, LDPE, LLDPE, HDPE, and PP, were used with the addition of 30 wt% of carbon blacks. The work of adhesion based on the surface free energy of a composite was studied in the context of two-liquid contact angle measurements using deionized water and diiodomethane. It was observed that the resistivity on PTC behavior was greatly increased near the crystalline melting temperature, due to the thermal expansion of polymeric matrix. It was shown that the PTC intensity defined as the ratio of the maximum resistivity (rho(max)) to the resistivity at room temperature (rho(RT)) had the largest value on CB/HDPE composites. From the experimental results, the decrease in the work of adhesion induced by interactions between carbon black surfaces and polymer chains is an important factor in the fabrication of a PTC composite.     

Effects of heat treatment on electrical conductivity of HDPE/CB composites

The influence of heat treatment on the electrical conductive behavior of carbon black (CB) filled high density polyethylene (HDPE) composites was investigated. The results showed that the effects of annealing temperature on the resistivity and the PTC intensity of the HDPE/CB composites were significant; the resistivity and the PTC intensity of the composites varied with increasing number of thermal cycles; while the variation became small after the third thermal cycle. Furthermore, the variation of the resistivity was 1.7 times higher than that of the composites without annealing, and the variation of the PTC intensity of the composites was 0.22, which were smaller than those of the specimens without heat treatment. A suitable annealing heat treatment could reduce the resistivity and enhance the PTC intensity of the composites; it was also helpful to improve the stability of the properties of the composites and the repeatability of the PTC effect.     

The stabilization effect of radiation crosslinking on positive temperature coefficient performances of carbon black-polymer composites

In this paper, we report the results of systematic study of effect of radiation crosslinking on PTC/NTC phenomena of carbon black(CB) filled vinyl polymers. We conclude that the effect of radiation crosslinking greatly improves the PTC intensity and electrical reproductivity in thermal cycling.     

HDPE/EPDM/CB复合物的PTC效应

聚合物正温度系数 (PTC)材料 ,是由聚合物基体与炭黑、碳纤维、金属粉末等导电填料共混而成的一种功能导电复合材料 ,其特点是 :当温度升高时 ,在聚合物结晶熔点附近 ,材料的电阻率随温度升高急剧增加 ,可发生几个数量级的突跃 .聚合物 PTC材料可用作自限温加热器、过电流保护器、传感器等 ,有广阔的发展前景 .目前对聚合物 PTC材料的研究主要以聚乙烯 [1～ 5]、乙烯 -醋酸乙烯酯共聚物[6] 、偏氟乙烯 [7] 等单一组分聚合物作为基体材料 .本文研究了以高密度聚乙烯 (HDPE) /三元乙丙胶(EPDM)共混物为基体材料的炭黑 (CB)导电复合材…     

Effects of thermal volume expansion on positive temperature coefficient effect for carbon black filled polymer composites

Polymeric positive temperature coefficient (PTC) materials have been prepared by incorporating carbon black (CB) into two different polymer matrices, crystalline high density polyethylene (HDPE) and amorphous polystyrene (PS). The effects of thermal volume expansion on the electrical properties of conductive polymer composites were studied. The volume fraction of conductive particles behaves like a switch from insulator to conductor in the polymeric PTC composite. Our mathematical model and experimental model have proved that the abrupt resistivity increase at PTC transition range and at the percolation curve close to the critical volume fraction for both polymeric PTC composites have the same conductive mechanism. The thermal expansion is one of the key factors responsible for the PTC effect and can be seen by comparing the PTC transition curves from model predictions and experiment. Furthermore, the model predicts PTC curves of CB/PS composite more successfully than it does for the CB/HDPE composite, and the reasons for this are also discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3078–3083, 2007     

不同粒径炭黑混合对复合型导电材料PTC性能的影响

研究了炭黑分散效果对具有PTC效应的高密度聚乙烯／炭黑导电复合材料性能的影响。实验结果表明，由不同粒度和比表面积的两种炭黑混合后填充的复合材料同由导电性能较好的乙炔炭黑填充复合材料比较，前者具有较低的渗滤阀值、较高的临界温度、优良的PTC特性以及电阻稳定性好的特点．     

Mechanical and rheological properties of poly(ethylene-co-ethyl acrylate) as a function of carbon black content

Carbon black (CB) filled poly(ethylene-co-ethyl acrylate) (EEA-CB) is used as conductive phase in conductive polymer composites (CPC). Electrical conductivity of CPC obtained from blends of immiscible polymers results from CB particles localization within the material, which depends on composition and processing conditions. It is particularly important to control viscosity of such systems as this parameter determines both the phase morphology and conductive pathway structure. The small scale, at which CB particle aggregation/dispersion phenomena occur within CPC, makes direct observations difficult. But the effect of carbon black particles/polymers interactions is clearly visible by means of rheological measurements. A strong reinforcing effect of CB on CPC in both solid and liquid states has been noticed. This phenomenon has been analyzed using classical models as a function of temperature and CB content. The results confirm the necessity of CPC rheology control especially during the process to achieve good reproducibility of electrical properties.