Resistivity and Thermal Reproducibility of High‐Density Polyethylene Heaters Filled With Carbon Black

Summary: Various output heaters were extruded with CB‐filled HDPE composites. The effects of crystallinity on the PTC and thermal reproducibility of the quenched, annealed, and E‐beam crosslinked heaters were examined during heating and cooling cycles at an applied voltage of 220 V. Conductor resisitivity and PTC effect of the heaters increased as crystallinity of composites increased. During the thermal cycling test, significant changes in heater‐output and resistivity for annealed and quenched heaters were observed. However, for quenched/E‐beam radiated and annealed/E‐beam radiated heaters no significant difference was found. These results indicate that the annealing process did not affect the thermal and electrical reproducibility of HDPE/CB heaters significantly.

Acetylene black aggregates in polyethylene matrix.     

Resistivity and thermal reproducibility of carbon black and metallic powder filled silicone rubber heaters

Flexible heaters were prepared by extruding platinum‐catalyzed silicone rubber composites with conductive carbon black (CB) and metallic fillers. The conductor resistivity of the extruded heaters decreased in order of conductive titanium dioxide (TiO₂) > aluminum powder ≈ zinc powder > copper powder. Thermoelectric switching phenomena were investigated for the silicone rubber/CB/metallic powder systems. The positive temperature coefficient effect was dependent mainly on the CB content rather than on the content of the metallic powders. Resistivity and thermal reproducibility of the extruded heaters were also investigated by periodically applying AC voltage of 110 V. The heaters containing copper and TiO₂ powders exhibited excellent electrical reproducibility. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1122–1128, 2005     

Effects of thermal aging on morphology,resistivity, and thermal properties of extruded high‐density polyethylene/carbon black heating elements

Various output heating elements were extruded with carbon black (CB)‐filled high‐density polyethylene (HDPE) composites. After thermal aging near melting point of HDPE, the effects of thermal aging on the morphology, resistivity, and thermal properties of the extruded and electron beam (EB)‐irradiated heating elements were examined using scanning electron microscopy (SEM) megohmmeter and differential scanning calorimetry, respectively. The heating element was insulated with a polytetrafluoroethylene tape wrap. The SEM image of HDPE is covered with microvoids that leave a dimple‐like structure on the surface. As the percolation threshold is achieved, CB aggregates are usually located in oval cavities larger than the particles themselves. During the resistivity–temperature cycling test, significant change in resistivity was observed for extruded and EB‐irradiated heaters. In case of thermal‐aged samples at 140°C for 120 h, both heaters showed good stability without pronounced changes in resistivity after resistivity–temperature cycling test. After thermal aged at 140°C for 120 h, the Heater02‐EB composite recovered the oval cavity structure, whereas for Heater02, the amorphous region became narrower and formed a more electroconductive pathway. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Influence of radiation structures on positive‐temperature‐coefficient and negative‐temperature‐coefficient effects of irradiated low‐density polyethylene/carbon black composites

The electrical‐resistivity/temperature behaviors of low‐density polyethylene (LDPE)/carbon black (CB) composites irradiated with ⁶⁰Co γ rays were studied. The experimental results showed that the irradiated composites could be separated into insoluble crosslinking networks with CB (gel) and soluble components (sol) by solvent‐extraction techniques. When the sol of an irradiated LDPE/CB composite was extracted, the electrical conductivity of the system increased. The positive‐temperature‐coefficient (PTC) and negative‐temperature‐coefficient (NTC) intensities of the gels of the irradiated composites became extremely small and independent of the radiation dose. The sols and gels of the irradiated LDPE/CB composites, which had different thermal behaviors, played important roles in the appearances of the PTC and NTC effects. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 700–704, 2005     

Electrical resistivity of carbon black filled high‐density polyethylene composites

The electrical resistivity of high‐density polyethylene (HDPE) loaded with carbon black (CB) blends was evaluated as a function of the blending time and the melt index of HDPE. The relationship between the positive temperature coefficient effect and the room temperature volume resistivity was investigated. The positive temperature coefficient effect and reproducibility were improved significantly when the blending time of HDPE and CB was comparatively long. The effects of ⁶⁰Co γ‐ray and electron beam irradiation on the positive and negative temperature coefficient behavior of the blends were studied. The effect of thermal aging on the volume resistivity was studied to ascertain the structural stability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2440–2446, 2002     

Electrical properties of carbon black filled crosslinked polyethylene

The electrical resistivity of peroxide and radiation crosslinked polyethylene/carbon black compounds was studied as a function of black concentration and, temperature in heating/cooling cycles. Different carbon blacks in compounds with polyethylene responded differently, regarding electrical resistivity, to the effect of crosslinking. In one case (fine black) the resistivity and PTC (positive temperature coefficient) effect did not significantly change, whereas in another case (coarse black) the effect of crosslinking-was to significantly increase the resistivity and reduce the PTC effect. The main advantages of crosslinking were to give compounds having good electrical reproducibility and to practically eliminate the NTC (negative temperature coefficient) effect in compounds containing fine, coarse, or mixtures of carbon blacks. Crosslinked compounds containing mixtures of carbon blacks have shown good conductivity, electrical reproducibility, and switching properties.     

Thermal reproducibility and voltage stability of carbon black/multiwalled carbon nanotube and carbon black/SnO2‐Sb coated titanium dioxide filled silicone rubber heaters

Flexible heaters were prepared by extruding platinum‐catalyzed silicone rubber (SR) compound with carbon black (CB)/multiwalled carbon nanotube (MWNT) and CB/SnO₂‐Sb coated titanium dioxide (TiO₂). MWNT with average particle length of 20 μm and acicular shaped TiO₂ with average particle length of 1.7 μm were selected. Thermal aging and mechanical deformation stability were compared for SR/CB, SR/CB/MWNT, and SR/CB/TiO₂ composites system. During thermal aging, conductor resistivity decreased because of the toughening effect of SR matrix. When 1 wt % of MWNT and TiO₂ were added into SR/CB compound, the deformation stability increased significantly. Thermal reproducibility and voltage stability of the extruded heaters were also investigated by applying AC voltage of 220 V. The heaters containing MWNT exhibited poor thermal reproducibility and voltage stability compared with heater containing TiO₂ or unfilled. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation of multi‐walled carbon nanotube‐reinforced high‐density polyethylene/carbon black nanocomposites using electrical,DSC and positron lifetime spectroscopy techniques

BACKGROUND: The positive temperature coefficient (PTC) effect on material properties has attracted much attention in recent years due to the prospects of many applications like temperature sensors, thermistors, self‐regulating heaters, etc. It has been suggested that incorporation of multi‐walled carbon nanotubes (MWNTs) into carbon black (CB)‐filled polymers could improve the electrical properties of composites due to high conductivity and network structure and significantly reduce the required CB loading. RESULTS: We observed no change in melting temperature and crystalline transition temperature on addition of MWNTs. However, the heat of fusion decreases as the amount of conducting carboxylated MWNT (c‐MWNT) filler increases and the resistivity of the composite decreases. The free volume shows an increase up to 1.5 wt% of c‐MWNT content and then decreases. CONCLUSION: Well‐developed crystals could not be formed due to restricted chain mobility as filler content increases. This results in minimum intermolecular interactions, and thus a decreased heat of fusion. A composite with c‐MWNT content of 0.5 wt% showed the highest PTC and higher resistivity at 150 °C possibly due to the formation of flocculated structures at elevated temperature. For filler content greater than 1.5 wt%, the decrease in free volume may be due to restricted chain mobility. Copyright © 2009 Society of Chemical Industry     

Resistivity–volume expansion characteristics of carbon black‐loaded polyethylene

The resistivity and volume expansion of carbon black (CB)/high‐density polyethylene (HDPE) composite with different CB volume fractions at different temperatures were measured simultaneously. A model based on Meyer's theory is proposed to explain the positive temperature coefficient resistance (PTCR) effect. The relationship between resistivity and volume expansion was determined. It was found that the phase change is the main cause of the PTC effect in the crystalline polymer PTC materials. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 53–58, 2000     

Resistivity‐temperature behavior of carbon fiber filled semicrystalline composites

Carbon fiber (CF) filled low‐density polyethylene (LDPE) composites were prepared by the conventional melt‐mixing method. The distribution of CF in the composite was studied by wide‐angle X‐ray diffraction (WAXD) and scanning electron microscope (SEM) observations. A phenomenological model was proposed to illustrate the resistivity‐temperature behavior of CF‐filled semicrystalline composites. The effects of the content and aspect ratio of CF on the positive temperature coefficient (PTC) and the room temperature resistivity were elucidated. A balance between the PTC intensity and the room‐temperature resistivity can be achieved by using a mixture of CFs with low and high aspect ratios. The negative temperature coefficient (NTC) phenomenon can be effectively eliminated by crosslinking under γ‐ray radiation, and the crosslinked composite exhibits a higher PTC intensity and PTC transition temperature than the noncrosslinked counterpart. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1222–1228, 2004     

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     

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     

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.     

The correlativity of positive temperature coefficient effects in conductive silicone rubber

A thorough study on the positive temperature coefficient (PTC) effects of conductive silicone rubber was made. Various conductive silicone rubbers with apparent differences in PTC anomalies (defined as the ratio of peak resistivity to room temperature resistivity) were chosen. The correlation between the size of the PTC anomaly and both the thermal expansion coefficient of conductive silicone rubber and the interaction between silicone rubber and carbon black (CB) were found. The effects of cross‐linking on the temperature effect of resistivity of conductive silicone rubber were also studied. The results testify the important role of the interaction between silicone rubber and CBs in the temperature effect of resistivity of conductive silicone rubber. Copyright © 2005 Society of Chemical Industry     

Effect of nanoclay on positive temperature coefficient to resistivity characteristics of high density polyethylene/silver‐coated glass bead composites

Positive temperature coefficient to resistivity characteristics of high density polyethylene (HDPE)/silver (Ag)‐coated glass bead (45 wt%) composites, without and with nanoclay, has been investigated with reference to HDPE/carbon black (CB) (10 wt%) composites. Plot of resistivity versus temperature of HDPE/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈128°C, close to the melting temperature (T_m) of HDPE. However, for HDPE/Ag coated glass bead (45 wt%) composites, the PTC trip temperature (≈88°C) appeared well below the T_m of HDPE. Addition of 1 phr clay in the composites resulted in an increase in PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites, whereas no significant effect of clay on PTC trip temperature was evident in HDPE/CB/clay composites. We proposed that the PTC trip temperature in HDPE/Ag‐coated glass bead composites was governed by the difference in coefficient of thermal expansion of HDPE and Ag‐coated glass beads. The room temperature resistivity and PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites were found to be very stable on thermal cycling. Dynamic mechanical analyzer results showed higher storage modulus of HDPE/Ag‐coated glass bead (45 wt%) composites compared with the HDPE/CB (10 wt%) composites. Thermal stability of HDPE/Ag‐coated glass bead (45 wt%) composites was also improved compared with that of HDPE/CB (10 wt%) composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

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     

The electrical behavior of thermosetting polymer composites containing metal plated ceramic filler

This paper describes the electrical behavior of a thermosetting system, based on epoxy resin, containing metal plated fillers. Ceramic fillers such as chopped glass fibers and mica flakes were coated with copper by electroless plating and incorporated into an epoxy resin based on di‐glycidyl ether of bisphenol A (DGEBA) with tri‐ethylenetetramine (TETA) curing agent. The percolation threshold in these systems is obtained at very low copper contents of 0.11–0.44 vol%. The epoxy/copper coated mica system is characterized by an extremely large positive temperature coefficient (PTC) effect, which is not followed by a negative temperature coefficient (NTC) effect. Increasing the copper coated mica concentration raises the PTC temperature of the first temperature cycle, and exposing the material to continuous heating‐cooling cycles results in a decrease in the PTC temperature and an increase of its room temperature resistivity. Inverse relations were found between the coefficient of thermal expansion and the PTC temperature. Accordingly, the mechanism governing the PTC effect in the epoxy/copper coated mica composite is based on a larger thermal expansion coefficient of the matrix compared with the ceramic filler. POLYM. COMPOS., 26:12–19, 2005. © 2004 Society of Plastics Engineers.     

制备工艺对PTC复合材料阻温特性的影响

研究了密炼工艺对聚乙烯／炭黑复合材料室温电阻率及ＰＴＣ强度的影响,针对一定配方找到了最佳密炼工艺条件。电子束辐照交联能有效消除ＮＴＣ现象和提高材料的电性能循环稳定性,有助于制备低电阻率、高ＰＴＣ强度并具有较好电性能循环稳定及热敏开关特性和电路保护元件。     

Resistivity and Thermal Reproducibility of the Carbon Black and SnO2/Sb Coated Titanium Dioxide Filled Silicone Rubber Heaters

Summary: Flexible heaters were prepared by extruding platinum‐catalyzed silicone rubber compound with electroconductive carbon black (CB) and SnO₂/Sb coated titanium dioxide (TiO₂). Two types of acicular‐shaped TiO₂ with average particle sizes of 1.7 and 5.2 µm, and two types of spherical‐shaped TiO₂ with average particle sizes of 0.3 and 2.5 µm were selected. Thermoelectric switching phenomena were investigated for the silicone rubber/CB/TiO₂ system. Positive temperature coefficient (PTC) was significant when the acicular filler was added rather than spherical ones. Resistivity change and thermal reproducibility of the extruded heaters were also investigated by applying periodically AC voltage of 220 V. The heaters containing acicular‐shaped TiO₂ exhibited excellent electrical reproducibility.

Scanning electron micrograph of the fractured surface of the extruded composites.     

Positive temperature coefficient effect and interaction based on low‐density polyethylene/graphite powder composites

In this article, the positive temperature coefficient (PTC) and interaction based on low‐density polyethylene (LDPE) filled with the loading of graphite (G) powder have been investigated. The dependence of the room temperature resistivity on filler content showed the significant decrease. The PTC behavior enhanced with increasing graphite content but this was not always the case. The maximum PTC effect was observed in LDPE/G composites (G, 45 wt %) with the relatively low room temperature resistivity. The thermal behavior was measured by differential scanning calorimetry (DSC). The structure characteristic for LDPE/G composites was examined by X‐ray diffraction (XRD), field‐emission scanning electron microscopy (SEM), and stress–strain test. The fact was revealed that the slight interaction between LDPE matrix and graphite may lead to change the thermal‐electric properties of the PTC materials. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012