Relaxation behavior of conductive carbon black reinforced EPDM microcellular vulcanizates

Dynamic mechanical analysis and dielectric relaxation spectra of conductive carbon black reinforced microcellular EPDM vulcanizates were used to study the relaxation behavior as a function of temperature (−90 to +100°C) and frequency (0.01–10⁵ Hz). The effect of filler and blowing agent loadings on dynamic mechanical and dielectric relaxation characteristics has been investigated. The effect of filler and blowing agent loadings on glass transition temperature was marginal for all the composites (T_g value was in the range of −39 to −35°C), which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. Strain-dependent dynamical parameters were evaluated at dynamic strain amplitudes of 0.07–5%. The nonlinearity in storage modulus has been explained based on the concept of filler–polymer interaction and interaggregate attraction (filler networking) of carbon black. The variation in real and complex part of impedance with frequency has been studied as a function of filler and blowing agent loading. Additionally, the effect of crosslinking on the dielectric relaxation has also been reported. POLYM. ENG. SCI., 47:984–995, 2007. © 2007 Society of Plastics Engineers     

Dielectric relaxation of Ensaco®350G reinforced microcellular EPDM vulcanizates

The dielectric relaxation characteristics of microcellular EPDM vulcanizates has been studied as a function of variation in filler and blowing agent loadings in the frequency range of 100–10⁶ Hz. The dielectric constant ε′ increases with increasing filler loadings at all frequencies. This has been explained on the basis of interfacial polarization of fillers in a heterogeneous medium. The effect of variation in filler and blowing agent loadings on the complex and real parts of impedance was distinctly visible. Which has been explained on the basis of relaxation dynamics of polymer chains in the vicinity of fillers. The phenomenon of percolation in the composites has been discussed based on the measured changes in electric conductivity and morphology of composites at different concentrations of the filler. The percolation threshold as studied by DC conductivity occurred near 40 phr of filler loading. SEM microphotographs showed agglomeration of the filler above this concentration and formation of a continuous network structure. POLYM. COMPOS., 28: 657–666, 2007. © 2007 Society of Plastics Engineers     

Impedance analysis and electromagnetic interference shielding effectiveness of conductive carbon black reinforced microcellular EPDM rubber vulcanizates

The effect of processing variables (filler and blowing agent loadings) and operating variables (frequency and sample thickness) on the impedance and electromagnetic interference (EMI) shielding effectiveness of excess conductive carbon black reinforced solid and microcellular EPDM vulcanizates has been investigated. Increasing frequency showed a decrease in real part of complex impedance for both filler and blowing agent loadings, whereas the imaginary part showed a slight peak in the range of 9–10 GHz followed by a subsequent decrease. The measured impedance values were plotted as Nyquist plots (Argand diagrams) and a Resistor–Capacitance model was assumed. Increasing blowing agent loadings showed a marginal increase in the bulk resistivity, whereas increasing filler loadings had a significant decrease. The EMI shielding effectiveness increased monotonically with filler loading and showed a maximum of around 75 dB at 60 phr loadings, thus making them suitable for shielding applications. Increasing blowing agent loadings showed an increase in shielding effectiveness at low loadings (2 phr) whereas further increase showed a rapid decrease. This has been explained on the basis of formation of voids in the composite, which affect the absorbance capacity of the microcellular vulcanizates. However, the microcellular composites showed sufficiently high values in the range of 50–60 Db, thus making Vulcan XC 72 reinforced microcellular EPDM vulcanizates as ideal packaging material for EMI shielding applications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Deformation and energy-absorption characteristics of microcellular EPDM rubber

Compressive stress–strain properties of closed-cell microcellular EPDM rubber vulcanizates with and without a filler were studied with the variation of density. For filler variation studies, silica and carbon black (N330) were used. With a decrease in density, the stress–strain curve for microcellular EPDM behaves differently from that for the solid vulcanizates: The curve rises steeply when cell breakdown occurs. The compressive stress–strain properties are found to depend on the strain rate. The compression set at constant stress increases with decreasing density. The energy-absorption behavior was studied from the compressive stress–strain properties. The efficiency, E, and ideality, I, parameters were also determined as they are useful for the evaluation of closed-cell microcellular rubber as a cushioning and packaging material. These parameters were plotted against stress to find the maximum efficiency and maximum ideality region which will make these materials suitable for cushioning or packaging applications. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:263–269, 1998     

Static and dynamic strain-dependent viscoelastic behavior of black-filled EPDM vulcanizates

The strain dependence of the dynamic mechanical properties of HAF-N330-filled EPDM vulcanizate was studied using a Rheovibron DDV III EP. It is shown that when a dynamic strain is superposed on a static strain, the viscoelastic response of filled rubbers becomes more complex. Under these conditions, dynamic mechanical properties do not correlate with the double strain amplitude. A strain called the “total strain” has been defined in order to interpret the experimental results. It is also shown that the dynamic mechanical properties are displacement velocity dependent, while the comparison is made under identical conditions of strain and frequency. Separability of time and strain effects is observed for the storage modulus, whereas the loss modulus is shown to be a nonseparable function. The elastic and the relaxation components, constituting the mixed function representing the storage modulus are shown to have similar deformation dependence. © 1994 John Wiley & Sons, Inc.     

Dynamic mechanical properties of conductive carbon black‐reinforced closed cell microcellular oil‐extended EPDM rubber vulcanizates: Effect of blowing agent,temperature, frequency,and strain

Dynamic viscoelastic properties of Vulcan XC 72 (excess conductive carbon black)‐reinforced solid‐ and closed‐cell microcellular controlled long chain branching grade oil‐extended EPDM (Keltan 7341A) rubber vulcanizates were studied at four frequencies of 3.5, 11, 35, and 110 Hz, and at a temperature range of ?100 to 160°C.The effect of blowing agent (ADC 21) loading on storage modulus (E′) and loss tangent (tan δ) was studied. The log of storage modulus bears a linear relationship with the log of density for both solid and microcellular rubber. Relative storage modulus (E/E) decreases with decrease in relative density (ρ_f/ρ_s). Both E′ and tan δ were found to be dependent on frequency and temperature. The master curves of the storage modulus versus log temperature‐reduced frequency were formed by superimposing E′ results and by using shift factors calculated by Arrhenius equation. Strain‐dependent isothermal dynamic viscoelastic properties were carried out for dynamic strain amplitude of 0.08–7%. Cole–Cole plots of microcellular vulcanizates show a circular arc with blowing agent (density). Empirical relationship between tan δ versus E′ is found to be linear, whose slope is independent of blowing agent loading or density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1600–1608, 2006     

丙烯酸树脂基导电油墨正/负升温系数协同效应的研究

采用乳液聚合的方法,利用Fox方程进行设计合成了玻璃化温度可控型聚(甲基丙烯酸甲酯-丙烯酸丁酯)[P(MMA-BA)]。借助激光粒度分布仪得到了控制乳液的粒径分布与大小的工艺条件;利用差热扫描量热仪(DSC)测定了聚合物的玻璃化温度(Tg)。实验发现所测的Tg与实验设计值有一定的偏差,为此对Fox公式进行了适用性的修正,理论设计和实测结果达到了很好的吻合。重点探讨了丙烯酸粘结料树脂玻璃化温度与导电填料的配比对电热膜电阻值稳定性的影响。利用扫描电子显微镜观察分析导电网络。结果表明,非晶态丙烯酸高聚物的PTC效应显著,消除了导电填料在温度升高过程中的NTC效应。     

Deformation and energy absorption characteristics of microcellular ethylene‐octene copolymer vulcanizates

Compressive stress‐strain properties of unfilled, CaCO₃, silica and aluminum silicate filled closed‐cell microcellular ethylene‐octene co‐polymer vulcanizates were studied with variation of blowing agent loading (density). With decrease in density, the compressive stress‐strain curves for microcellular vulcanizates behave differently from those of the solid vulcanizates. The stress‐strain properties are found to be strain rate dependent. The log‐log plots of relative compressive moduli versus relative density of the microcellular vulcanizates show a fairly linear correlation. The energy absorption behavior was also studied from the stress‐strain properties. The efficiency, E, and Ideality parameter, I, were evaluated. These parameters were plotted against stress to find the maximum efficiency and maximum ideality region, which will make these materials suitable for cushioning and packaging applications. The cushioning factor, C, for microcellular vulcanizates has also been evaluated for various systems.     

Triple percolation behavior and positive temperature coefficient effect of conductive polymer composites with especial interface morphology

Selective localization of carbon black (CB) at the interface of polymer blends was achieved by the method that poly(styrene-co-maleic anhydride) (SMA) was first reacted with CB, and then blended with nylon6/polystyrene (PA6/PS). In the PA6/PS blends, CB was localized in PA6 phase and typical double percolation was exhibited. In the PA6/PS/(SMA–CB) blends, TEM results showed that CB particles were induced by SMA to localize at the interface, resulting in the especial interface morphology fabricated by SMA and CB. The especial interface morphology of PA6/PS/(SMA–CB) caused distinct triple percolation behavior and very low percolation threshold. The positive temperature coefficient (PTC) 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 elimination of NTC effect was arisen from the especial interface morphology. A stronger PTC intensity was attributed to the low percolation threshold and the morphology.     

Electrical behavior and positive temperature coefficient effect of graphene/polyvinylidene fluoride composites containing silver nanowires

Polyvinylidene fluoride (PVDF) composites filled with in situ thermally reduced graphene oxide (TRG) and silver nanowire (AgNW) were prepared using solution mixing followed by coagulation and thermal hot pressing. Binary TRG/PVDF nanocomposites exhibited small percolation threshold of 0.12 vol % and low electrical conductivity of approximately 10^-7 S/cm. Hybridization of TRGs with AgNWs led to a significant improvement in electrical conductivity due to their synergistic effect in conductivity. The bulk conductivity of hybrids was higher than a combined total conductivity of TRG/PVDF and AgNW/PVDF composites at the same filler loading. Furthermore, the resistivity of hybrid composites increased with increasing temperature, giving rise to a positive temperature coefficient (PTC) effect at the melting temperature of PVDF. The 0.04 vol % TRG/1 vol % AgNW/PVDF hybrid exhibited pronounced PTC behavior, rendering this composite an attractive material for making current limiting devices and temperature sensors.     

Preparation and properties of carbon black filled EPDM/POE thermaplastic vulcanizates

TPVs filled with different amounts (0–50 phr) of carbon black were prepared via melt mixing by dynamic vulcanization in Haake plasticorder at 150°C and 40rpm and then the properties of them were studied. Torque-time curves showed that the curing degree reached a biggest value at 10 phr and then decreased with the increase of filling content while the curing rate was always rising. Mechanical properties such as tensile strength, tear strength, modulus as well as hardness increased with the increment of carbon black content while the tension set at break was reduced dramatically. Two phase morphology was observed by SEM photographs and the effect of carbon black on curing extent was testified. To illuminate the effect of carbon black, curometer curves and carbon black dispersion pictures were also analyzed. Rubber processing analyzer (RPA) experiments proved that there was a progressive nonlinear behavior, which was more and more clearly expressed with the increment of carbon black content and could be explained via the Payne effect. But the TPVs containing highest carbon black exhibited the fastest drop of G′ with increasing strain amplitude as obtained from the value of G₀′ − G_∞′. The order of tanδ at different carbon black content was tanδ (10 phr) < tanδ (0 phr) < tanδ (30 phr) < tanδ (50 phr) at lower strain amplitude. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology and physical properties of closed-cell microcellular ethylene–propylene–diene terpolymer (EPDM) rubber vulcanizates: Effect of blowing agent and carbon black loading

The morphology of the microcellular ethylene–propylene–diene terpolymer (EPDM) vulcanizes of both an unfilled and filled compound was studied from SEM photomicrographs. Carbon blacks adversely affect the average cell size, maximum cell size, and cell density. Enclosed gas pressure in a closed cell increases the relative modulus at higher strain. Tensile strength decreases more steeply than the expected value obeying the additive rule. At higher temperature, tensile strength, elongation at break, and modulus values decrease. The stress-relaxation behavior is independent of blowing agent loading, i.e., the density of closed-cell microcellular rubber. The elastic nature of the closed cell, i.e., the gas bubble in the microcellular rubber, reduces the hysteresis loss compared to solid rubber vulcanizates. Theoretically calculated flaw sizes are found to be about 3.4 times larger than the maximum cell sizes observed from SEM photomicrographs. It reveals that tear path deviates from the linear front and gives an effective larger depth of the flaws. © 1996 John Wiley & Sons, Inc.     

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     

发泡剂AC在EPDM胶料中的热分解研究

研究了硫化剂DCP、发泡剂AC和甲基乙烯基硅橡胶（MVQ）的用量及成型温度对发泡剂AC在EPDM胶料中的分解速率的影响。试验结果表明,发泡剂AC在EPDM胶料中的分解速率随硫化剂DCP用量的增大而减小;随发泡剂AC用量的增大先减小后增大;随MVQ用量的增大而增大;成型温度在160-167℃之间随温度的升高而减小,超过167℃则随温度的升高而增大。     

Dynamic viscoelastic properties of carbon black loaded closed-cell microcellular ethylene-propylene-diene rubber vulcanizates: Effect of blowing agent,temperature frequency,and strain

Dynamic mechanical analysis of carbon black loaded solid and closed-cell microcellular ethylene-propylene-diene (EPDM) vulcanizates was studied at four frequencies of 3.5, 11, 35, and 110 Hz and temperatures from −100 to 150°C. A plot of the log of the storage modulus bears a linear relationship with the log of density for solid as well as closed-cell microcellular rubber. The slope of the line is found to be temperature-dependent. The relative storage modulus decreases with decrease in the relative density. It was also observed that the storage modulus and tan δ are both frequency- and temperature-dependent. The storage modulus results are superposed to form master curves of the modulus vs. Iog temperature-reduced frequency, using shift factors calculated by the Arrhenius equation. Strain-dependent isothermal dynamic mechanical analysis was carried out for DSA varying from 0.07 to 5%. The effect of blowing agent loading on the storage modulus (E′) and loss tangent (tan δ) were also studied. Cole-Cole plots of microcellular rubber shows a circular arc relationship with the density. Plots of tan δ against E′ were found to exhibit a linear relationship. © 1996 John Wiley & Sons, Inc.     

Designs of conductive polymer composites with exceptional reproducibility of positive temperature coefficient effect: A review

Conductive polymer composites with positive temperature coefficient (PTC) effect have gained intensive attention for the potential application in the smart heating field. The PTC reproducibility is significantly essential to guarantee the security and utility of PTC composites. Regrettably, during the repeated temperature cycles, the irreversible self-aggregation of conductive filler and the random reconstruction of conductive network lead to unsatisfactory performance of PTC reproducibility. Extensive efforts have been conducted to address this issue by strategies, including modification of fillers, cross-linking of a polymer matrix, hybrids of fillers, and application of binary polymer matrix. Nevertheless, there are very limited reviews about this issue. In this review, the recent advances in fabricating PTC composites with the enhanced PTC reproducibility have been systematically summarized. Meanwhile, the current challenges and future prospects of PTC composite are also presented. We hope that this review will provide some inspirations for designing PTC materials of long-term performance for commercial applications.     

Preparation and characterization of PPRC/EPDM thermoplastic vulcanizates: A comparative study

Thermoplastic vulcanizates (TPVs) of polypropylene random copolymer (PPRC) with ethylene–propylene diene monomer rubber (EPDM) were prepared through in situ and ex situ compatibilization techniques. Silanized silica as nanofiller was incorporated in the ex situ compatibilized TPVs. Mechanical properties were measured for different formulated TPVs with increasing loading of EPDM from 10 to 30 phr. A comparative data is generated to discuss the effect of two compatibilization techniques and addition of silica filler in the TPVs. The degradation studies were also carried out to check the stability of the blends under harsh ultraviolet environment. The in situ compatibilized TPVs provided better overall mechanical properties. Moreover, it is worth mentioning that the properties of ex situ compatiblized TPVs were enhanced by incorporation of silanized silica filler. Silanized silica filler helped in reducing the die swell significantly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46726.