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1. INTRODUCTION
Polymer nanocomposites with better dielectric and electrical insulation properties are slowly emerging as excellent functional materials for dielectric and electrical insulation application and the term nanodielectrics for such material is increasingly becoming popular. Although the technology of addition of additives, agents and fillers are often used for improving dielectric properties has been in existence for several decades [1-3]. The effect of filler size on the dielectric property of the polymer CREDIT understood fully. BE with the advent composites has not been LINE (BELOW) TOIt is INSERTED ON of nanotechnology THE and PAGE OF EACH PAPER leading to the availabilityFIRST commercialization of nanoparticles that polymer nanocomposite technology started to gain momentum.Polymer nanocomposite have
CP1276, International Conference on Advanced Nanomaterials and Nanotechnology (ICANN-2009) edited by P. K. Giri, D. K. Goswami, A. Perumal, and A. Chattopadhyay 2010 American Institute of Physics 978-0-7354-0825-8/10/$30.00
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been found to exhibit enhanced physical, thermal and mechanical properties when compared to the traditional polymer materials and that too at low nanofiller concentration (1-10%) [4-6].The present work looks into two of the dielectric properties in epoxy nanocomposites- dielectric constant and dissipation factor. Dielectric constant determines the charge storage capacity of the materials as well as dictates the dielectric field distribution in a composite insulation system whereas the tan indicates the dielectric losses possible in an insulating material. For many electrical insulation systems, a low tan value is always desired in the dielectric material, whereas the desired r of the material can be higher or lower depending on the end application. Based on these facts, the current experimental investigation attempts to understand the behavior of dielectric properties and loss tangent in epoxy and PP/nylon66 nanocomposites with clay nanofiller at low filler concentration, temperature, frequency (> 1MHz) and sea water ageing.
Table 2. Sample designation and composition of ingredients used in the study Sample Designation Composition by % wt. Epoxy Particulate filler nanoclay A0 100 A2 98 2 A5 95 5 A7 93 7
2.1. Compounding
Before compounding, the polymer granules and fillers were dried at 80 C for 10 hours in an air circulated oven and then dry mixed with nylon66 and other additives. Composition shown in table 3 was mixed and extrudated in a co-rotating twin extruder. The L/D ratio of the screw is 40:1. Mixing speed of 60 rpm was maintained
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for all the compositions. The extrudate from the die were quenched in a tank at 20-30 C and then palletized. For melt blending the temperature profile of the extrusion were Zone 1( 205 oC ) Zone2 ( 235 oC ) Zone 1( 245 oC ) Zone 1( 255 oC ) and Die ( 265 oC ). The extrudate of the composition was palletized in palletizing machine. The rpm of the pelletizer was maintained between the ranges of 60-80 rpm.
Table 3. Materials used in the present study Materials Polyamide-66 (PP) Nylon66 Maleic anhydride grafted PP (MAgPP) Nanoclay Supplier DuPont Co.Ltd IPCL, India. DuPont Co.Ltd Sigma-Aldrich Inc.
Table 4. Sample designation and composition of ingredients used in the study Sample Composition by % wt. Designation PP Nylon 66 Particulate filler nanoclay B 100 B0 50 50 B2 48 50 2 B5 45 50 5 B7 43 50 7
3. MEASUREMENTS
The electrical capacitance (c) and dissipation factor (tan) was measured in the frequency range of 0.1MHz to 30MHz and temperature range of 25 to 180 C at constant ac supply of 1V using HP 4285A multi frequency LCR meter as per ASTM D-150 for all the samples. From the measured value of capacitance, the dielectric constant of the specimen was calculated. The effect of dielectric constant and dissipation factor on sea water ageing of the nanocomposites for the duration of 96 hours were studied
4. RESULTS AND DISCUSSION 4.1. Effect of frequency and filler on dielectric constant
The plot of the dielectric constant as a function of log frequency is shown in figure 2. It is realized that r decreases with increase in frequency. Dielectric constant is a frequency dependent parameter in polymer systems. In a typical epoxy system, based on an epoxy resin cured with an amine hardner as in the present case, the epoxy
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component of dielectric constant is governed by the number of orientable dipoles present in the system and their ability to orient under an applied electric field [7]. Usually, the molecular groups which are attached perpendicular to the longitudinal polymer chain attribute to the dielectric relaxation mechanisms. At lower frequencies of applied voltage, all the free dipolar functional groups in the epoxy chain can orient themselves resulting in a higher r value at these frequencies. As the electric field frequency increases, the bigger dipolar groups find it difficult to orient at the same pace as the alternating field, so the contributions of these dipolar groups to the r goes on reducing resulting in a continuously decreasing r of the matrix system at higher frequencies. Similarly, the inherent dielectric constant of nanoclay particles also decreases with increases in frequency of the applied field [8-9]. This combined decreasing effect of the r for both matrix and filler particles result in a decrease in the effective r of the epoxy and PP/nylon66 composites also when the frequency of the applied field increases. The variation of nanocomposite r in figure 2 shows that there is a significant effect of the matrix type. In PP/nylon66 filled nanoclay composites, a lower permittivity is observed as compared to epoxy filled nanoclay composites. At nanoclay filler loadings of 7% wt. or less, the influence of the filler on the r variations with respect to frequency can be considered to be very minimal, the slope of the r between 103 to 107 Hz is almost the same as that seen for pure epoxy and PP/nylon66 blend. The above observation suggests apart from the influence of filler dielectric constant, there is probably an occurrence of interfacial polarization in the epoxy nanocomposite system.
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Fig. 4. Variation of dielectric constant with sea water ageing in insulating nanocomposites
the electrical conductivity in the epoxy and PP/nylon66 composites. The electrical conductivity in turn depends on the number of charge carriers in the bulk of the material, the relaxation time of the charge carriers and the frequency of the applied electric field. Since the measurement temperatures are maintained constant, their influence on the relaxation times of the charge carriers is neglected. Over the current frequency range of measurement, charge transport will be mainly dominated by lighter electronic species. The effect of filler loading on tan was observed from figure 5. With increasing the filler loading, the tan increases than the unfilled matrix in both the systems. Usually the introduction of inorganic fillers to a polymer matrix enhances the tan values of the composites as there is an enhancement in the sources of charge carriers in the system. The number of nanoparticles causes an increase in the electrical conductivity at this filler loading which in turn influences the tan behaviors [13].
Fig. 7. Variation of dissipation factor with sea water ageing of 96hrs for insulating Nanocomposites.
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Table 6. Diffusion coefficient of pp/nylon 66/clay nanocomposites At 90 C Sample At 30 C At 60 C ( 10-10 cm2/s) (10-10 cm2/s) ( 10-10 cm2/s) B Nylon 66 B0 B2 B5 B7 1.39 3.01 2.68 2.55 2.34 2.17 12.02 23.58 22.98 21.87 20.07 18.61 33.88 66.45 64.72 61.45 56.59 52.48
Where D is the Diffusion coefficient, L is the thickness of the specimen, t is the time of absorption.
5. CONCLUSION
The r and tan of the epoxy and PP/nylon66 nanocomposites shows the inverse relationship with frequency. With increase in nanoclay loading, r and tan of the nanocomposite system increases due to increase in total interfacial area. The epoxy/clay nanocomposite shows slightly higher r and tan as compared with PP/nylon66/clay nanocomposites. The epoxy and PP/nylon66 nanocomposite is hydrophobic in nature with increase in percentage content of nano-filler in the base resin material. Higher the water absorption in epoxy/clay system as compared to PP/nylon66 system.
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