Carbon black–filled immiscible blends of poly(vinylidene fluoride) and high density polyethylene: The relationship between morphology and positive and negative temperature coefficient effects

Conductive polymer composites were prepared by melt-mixing of an immiscible blend of poly(vinylidene fluoride) (PVDF), high density polyethylene (HDPE), and carbon black (CB). Three major factors—the carbon black content, the carbon black type, and the composite morphology—were shown to have remarkable effects on the positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effect of the composites. The relationship between the morphology and the PTC and NTC effects of the composites was investigated using optical microscopy (OM) and scanning electron microscopy (SEM). The OM micrographs indicated that CB was selectively located in the HDPE phase and the SEM micrographs showed that there were some gaps between the two phases. The PTC effect of the composites is caused by the thermal expansion as a result of the melting of the HDPE crystallites. The morphology of the composites greatly affects the PTC and NTC behaviors of the composites. When the CB-filled HDPE formed a continuous phase and the PVDF formed a dispersed phase, the PTC and NTC behaviors of the composites were similar to those of CB-filled neat HDPE composite without crosslinking. When the composite exhibited an interlocking structure, a normal PTC effect could also be observed, but the NTC effect was delayed to higher temperatures. A mechanism was proposed to explain this new physical phenomenon, and the mechanism was verified by another CB-filled polymer blend comprising an alternating copolymer of tetrafluoroethylene-ethylene and HDPE.     

Temperature dependence of electrical resistivity for carbon black filled ultra-high molecular weight polyethylene composites prepared by hot compaction

In this article, the temperature dependence of electrical resistivity is studied for carbon black (CB)/ultra-high molecular weight polyethylene (UHMWPE) composites. A new positive temperature coefficient (PTC) material with a very low percolation threshold is produced by the hot compaction method. The very low percolation threshold can be attributed to the segregation of CB in the interfacial regions of UHMWPE particles. The percolation threshold decreases with the increase of the molecular weight of UHMWPE, and with the decrease of the particle size of CB. For CB filled lower molecular weight UHMWPE (145M) composites, the PTC temperature, at which a sharp increase in the resistivity of the composite occurs, decreases with the increase of CB size. However, for a higher molecular weight UHMWPE (630M) filled with CB, the second PTC effect is observed and the negative temperature coefficient (NTC) effect is eliminated. A mechanism is proposed to explain these phenomena based on the optical microscopy and TEM observations. It can be concluded that the degree of the intermixing between CB and UHMWPE particles plays an important role in determining the electrical properties of the composites.     

超高分子量聚乙烯对有机PTC复合材料的超强稳定作用研究

利用传统的熔融 混合方法制备碳黑填充的聚丙烯 (PP) /超高分子量聚乙烯 (UHMWPE)复合物。当PP/UHMWPE混合比大于 3 / 7,碳黑填充PP/UHMWPE复合物的PTC和NTC效应类似于碳黑填充的纯净PP聚合物。然而当重量比等于或小于 3 / 7时 ,复合物所表现的PTC效应非常相似于碳黑填充的纯净的UHMWPE聚合物。在复合物中应用粘度非常高的聚合物作为一种组分可以有效消除NTC效应     

UHMWPE对有机PTC复合材料的稳定作用

利用传统的熔融－混合方法制备碳黑填充的聚丙烯（PP）／超高分子质量聚乙烯（UHMWPE）复合材料,当P／UHMWPE质量比大于3／7时,碳黑填充PP／UHMWPE复合物的正温度系数（PTC）和负温度系数（NTC）效应类似于碳黑填充的纯PP聚合物,但当质量比等于或小于3／7时,复合物所表现的PTC效应非常相似于碳黑填充充的纯UHMWPE聚合物,在复合物中采用粘度非常高的聚合物作为一种组分可以有效消除NTC效应。     

Study of electrical phenomena in carbon black–filled HDPE composite

Percolation, positive temperature coefficient (PTC), and negative temperature co-efficient (NTC) in carbon black-filled HDPE composites, were studied by measuring AC electrical properties. An equivalent single parallel circuit model, which consists of a resistor and a capacitor, was adapted to explain the distribution of carbon black in composite. The electrical conductivity and admittance and phase angle were characterized by measuring the distribution of carbon black aggregates with an impedance analyzer. It was concluded that PTC is due to the deagglomeration or the breakage of the conduction networks caused by thermal expansion and/or crystalline melting of the matrix polymer, and NTC is due to the reagglomeration of the network of carbon black aggregates.     

炭黑粒子偶联处理的HDPE复合材料PTC性能研究

研究了以HDPE为基体,工业炭黑（CB）为导电粒子的高分子复合材料的PTC（正温度系数）导电行为。考察了炭黑及偶联剂种类、用量对高分子PTC导电材料性能的影响,并探讨了偶联接枝机理,从理论上对改性效果进行了分析。结果表明,对炭黑,尤其是槽法炭黑 表面处理可显著提高复合材料的电导率及减小NTC（负温度系数）效应;钛酸酯偶联剂具有最佳改性效果,可明显改善炭黑粒子分散状态,增强材料的PTC效应,其最佳用量为1％质量份。     

Study on filler content dependence of the onset of positive temperature coefficient (PTC) effect of electrical resistivity for UHMWPE/LDPE/CF composites based on their DC and AC electrical behaviors

Composites of carbon fibers (CF) filled with ultrahigh molecule weight polyethylene/low density polyethylene blend matrix (UHMWPE/LDPE) were prepared by kneading method. The positive temperature coefficient (PTC) effect of electrical resistivity of UHMWPE/LDPE/CF composites was investigated by direct current (DC) and alternating current (AC) measurements over the frequency range of 10⁰–10^6.5 Hz from 30 to 150 °C. The onsets of PTC effect were found to be strongly depended upon the CF content even the melting behaviors were almost same for all composites. To interpret this phenomenon, a master curve of temperature–frequency–resistivity superposition was constructed for composites with different CF contents based on the AC resistivity. The CF content dependence of correlation length was related to the onset of PTC effect. The transitions of conductor–insulator were studied quantitatively by complex planes of AC impedance, and the calculated capacitances and resistances showed a similar PTC effect under DC. Based on the analysis of AC capacitance, the average distances between CFs were calculated using a plane capacitance model which varied with CF concentration and temperature, and the tendency was consistent to the PTC effect.     

接枝炭黑/聚乙烯导电复合材料正电阻温度系数(PTC)效应研究

用接枝炭黑作导电粒子研究了在聚乙烯基材中的正 (电阻 )温度系数 (PTC)效应。结果发现 ,甲基丙烯酸甲酯接枝的炭黑在高密度聚乙烯中能表现出较好的 PTC效应。从实验现象分析 ,接枝炭黑的 PTC效应是结晶熔融和体积膨胀双重变化共同作用的结果。     

HDPE/CB复合体系PTC行为的工艺研究

采用高结构导电炭黑(CB)Vxc—72与半晶聚合物高密度聚乙烯(HDPE)进行熔融共混，制备复合型导电高分子材料。研究了该复合体系中偶联处理、混炼时间、辐射及退火处理等工艺因素对其PTC(电阻—温度效应)性能的影响。结果表明，当辐照剂量为140—160kGy、炭黑非均匀分散且进行退火处理时复合体系具有最佳的PTC性能，但混炼时间过长、偶联处理均会使复合体系PTC强度降低。     

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     

Electrical properties of polyethylene and carbon black particle blends prepared by gelation/crystallization from solution

Composite materials based on low molecular weight polyethylene (LMWPE), ultra-high molecular weight polyethylene (UHMWPE) and carbon black (CB) particles were prepared by gelation/crystallization from solution. The positive temperature coefficient (PTC) intensity for the 90/10 (LMWPE/UHMWPE) composition exceeded five orders of magnitude for the specimens heat-treated at a suitable temperature, which was almost equal to that observed with LMWPE-CB blends prepared by a kneading method. In comparison with LMWPE-CB blends, much promoted reproducibility of PTC effect and inhibition of the negative temperature coefficient (NTC) effect were achieved.     

Electrical properties of carbon black filled polyethylene

Resistivity and dielectric constant of polyethylene/carbon black compounds were measured from room temperature to 140°C. Within the polyethylene melting region a PTC/NTC (positive followed by negative temperature coefficients) phenomenon is observed, whose intensity depends on the type of carbon black, its concentration and other parameters. Reproducibility of the PTC phenomenon in polyethylene compounds containing a single type of carbon black is rather low. However, by using mixtures of carbon blacks differing appreciably in their particle size, remarkable reproducibility improvements can be achieved. Several other aspects are also discussed in the present paper covering current-voltage relationships in these materials, comparison of PTC curves with DSC thermograms upon heating and cooling, and dielectric constant-temperature relations. The carbon black concentration giving the optimum PTC intensity can be predicted approximately from room temperature data.     

Positive temperature coefficient behavior of polymer composites having a high melting temperature

The positive temperature coefficient (PTC) behavior of polymers having a high melting temperature, such as nylon, polyvinylidene fluoride, polyester, and polyacetal, was investigated. Carbon black and nickel powder were used to investigate the influence of their conductive fillers on PTC intensity. The polymer/filler composite was irradiated with gamma rays at dosages of 50, 100, and 150 kGy for the purpose of reducing the negative temperature coefficient (NTC) of a conductive composite. It was found that the PTC temperature depended on the melting point of the polymer matrix. The crosslinking structure enhanced the electrical stability and decreased the NTC effect of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 394–401, 2004     

Effect of incorporating ethylene‐ethylacrylate copolymer on the positive temperature coefficient characteristics of carbon black filled HDPE systems

In order to study the effect of introducing ethylene‐ethylacrylate copolymer (EEA) in carbon black‐HDPE composite systems, two HDPE‐EEA composites prepared by pre‐blending and masterbatch‐blending processes were compared with HDPE and EEA composites in terms of positive temperature coefficient (PTC) characteristics and percolation threshold. The percolation threshold of masterbatch‐blended composites occurred at the lowest carbon black concentration among four kinds of composites. The conduction path in the masterbatch‐blended composite is effectively formed as a result of the localization of carbon black distribution predominantly in the EEA phase, resulting in an increase of conductivity. I_peak values, the resistivity ratio of the peak to 25°C, of two blend composites were lower than those of HDPE composites. The I₈₅ values, the resistivity ratio of 85°C to 25°C, of masterbatch‐blended composites were higher than those of pre‐blended as well as HDPE composites. It is evident that since most carbon black is dispersed in the EEA phase of the masterbatch‐blended composites, the conduction networks are mainly broken by the crystal melting of EEA before the temperature reaches the crystal melting temperature of HDPE.     

Effect of coefficient of thermal expansion on positive temperature coefficient of resistivity behavior of HDPE–Cu composites

Positive temperature coefficient of resistivity (PTCR) characteristics of (high density polyethylene) HDPE–Cu composites has been investigated with reference to the conventional HDPE–CB (carbon black) composites. Plot of resistivity against temperature of HDPE–CB composites showed a sudden rise in resistivity (PTC trip) at 127°C, close to the melting temperature of HDPE. However, the PTC trip temperature (98°C) for HDPE–Cu composites was appeared well below the melting temperature of HDPE. Addition of 1 phr nanoclay in the composites resulted in an increase in PTC trip temperature of HDPE–Cu composites, whereas no significant effect of nanoclay on PTC trip temperature was evident in case of HDPE–CB–clay composites. We proposed that the PTC trip temperature in HDPE–Cu composites was governed by the difference in coefficient of thermal expansion (CTE) of HDPE and Cu. The room temperature resistivity and PTC trip temperature of HDPE–Cu composites were very much stable upon thermal cycling. DMA results showed higher storage modulus of HDPE–Cu composites than the HDPE–CB composites. Thermal stability of HDPE–Cu composites was also improved compared to that of HDPE–CB composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The positive temperature coefficient phenomenon of vinyl polymer/CB composites

In this paper, the results of a systematic study of carbon black (CB)-filled conducting polymer positive and negative temperature coefficient (PTC/NTC) effects are report. The conductivity of the composites jumps by several orders of magnitude at the critical value of carbon black. This critical value, ø_c, decreases with the increase of melt index and degree of crystallinity of the polymer. The crystalline lamellae just “modify” the distribution of carbon black and make the dispersion heterogeneous. Radiation cross-linking enhances the PTC intensity and decreases the NTC effect of the materials. The electrical reproducibility of compounds is improved by the cross-linking structure that reduces the freedom of carbon black movement at high temperature. The NTC phenomenon is related to the carbon black coagulation that facilitates electrical conduction at high temperature. The larger the melt index, the more easily carbon black coagulates. A new model was set up to explain the results successfully. © 1993 John Wiley & Sons, Inc.     

Influence of morphology on PTC effect for poly (ethylene-co-butyl acrylate)/nylon6 blends with multiwall carbon nanotubes dispersed at interface and in matrix

Multiwall carbon nanotubes (MWCNTs) filled poly (ethylene-co-butyl acrylate)/nylon6 (EBA/PA6) blends were prepared by melt-mixing method. MWCNTs were localized in PA6 phase and the percolation threshold was 6 wt%. A weak PTC (positive temperature coefficient) effect was observed. The method that EBA-g-MAH was first reacted with MWCNTs, and then blended with EBA/PA6 was employed to prepare EBA/PA6/EBA-g-MAH/MWCNTs composites. TEM results showed that MWCNTs were localized both at the interface and in PA6 phase, resulting in the sharp decrease of the percolation threshold. Influence of morphology on the PTC effect of EBA/PA6/EBA-g-MAH/MWCNTs composites was studied. In composites with dispersed PA6 phase, the conductive pathways were fabricated by the contact of dispersed PA6 phase and MWCNTs in PA6 phase. The melt of polyethylene segment crystals in EBA and PA6 phase interrupted the contact of dispersed phases and conductive network formed by MWCNTs in PA6 phase, resulting in the double PTC effect. For composites with dispersed EBA phase, although the conductive pathways were similar with the composites with dispersed PA6 phase, the single PTC effect was observed. And the PTC effect was attributed to the melt of PA6 phase. The conductive pathways of composites with co-continuous morphology were fabricated by MWCNTs at the interface and in continuous PA6 phase. Two strong and a weak PTC effect were observed. PTC effects appeared at the melting temperature of PA6 crystals, polyethylene segment crystals and viscous flow temperature of butyl acrylate units in EBA.     

Effect of high‐energy ball milling on the structure and mechanical properties of ultra‐high molecular weight polyethylene

The structure and properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE) powder after severe deformation processing in a planetary ball mill were studied by means of scanning electron microscopy, differential scanning calorimetry, and X‐ray analysis. We found that the severe deformation processing of UHMWPE changed the morphology of the powder and caused amorphization and partial changes in the structure of the crystalline phase. Monolithic samples were obtained from the pretreated polymer with a hot‐pressing method in a wide range of temperatures. The effect of preliminary deformation processing on the mechanical properties of UHMWPE was studied. It was revealed that during monolitization in its melting temperature range, the mechanical properties of the powder increased, whereas the percentage elongation decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2971–2977, 2013     

Thermo‐electric behavior (PTC) of carbon black–containing PVDF/UHMWPE and PVDF/XL‐UHMWPE blends

This paper describes the structure and electrical performance of PTC/NTC (positive temperature coefficient/negative temperature coefficient) effects and their reproducibility upon healing/cooling cycles. The following three‐component blends were studied: PVDF/UHMWPE/CB, PVDF/XL‐UHMWPE/CB and γ‐irradiated compression molded plaques of these blends. Carbon black (CB) particles are attracted to the UHMWPE (ultra high molecular weight polyethylene) and XL (cross‐linked)UHMWPE particles, which constitute the dispersed phase in the PVDF (polyvinylidene fluoride) matrix, but practically cannot or only very slightly penetrate them because of their extremely high viscosity. A double‐PTC effect was exhibited by all unirradiated samples. Irradiation of compression molded PVDF/UHMWPE/CB plaques does not add to their already outstanding reproducibility, and it results In a wide single‐PTC effect. Irradiation of compression molded PVDF/XL‐UHMV/PE/CB plaque, slabilizes their structure upon heating/cooling cycles and thus makes them reproducible PTC/NTC materials, still exhibiting a double‐PTC effect. The carbon black concentrations studied in this report are extremely low (< 2 phr CB) in comparison to other literature reports.