DC and AC electrical conductivity of bionanocomposites based on the immiscible polymer blend poly(epsilon-caprolactone)/polylactide (PCL/PLA, w/w 70/30), loaded with multiwall carbon nanotubes (CNT), were studied in a wide frequency range, 10(-3) < or = f < or = 10(7) Hz from 143 to 313 K. The nanofiller concentration ranged from 0 to 4 wt % and it was shown to be selectively located in the PCL phase. The PCL crystallinity degree was not affected by the presence of CNT. The variation of the DC conductivity allowed the determination of the percolation threshold, p(c) = 0.98 wt %, and the critical exponent t = 2.2 of the scaling law. The linear dependence of log (sigma(DC)) versus p(-1/3) showed the existence of tunneling conduction among CNT not yet in physical contact. The temperature independent results indicated a conventional tunnel effect. The AC conductivity of the nanocomposites followed the predictions of the universal dynamic response and the s exponents were determined at low concentrations. Master curves are presented showing the length and temperature-time superpositions.
Polycarbonate/poly( -caprolactone) (PC/PCL) blends are found to be miscible when extruded samples are studied without any further thermal treatment. PCL crystallizes in blends containing 60% or less polycarbonate, a component that remains amorphous for all blend compositions under these conditions. Single, broad calorimetric glass transitions together with distinct component dynamics determined by thermally stimulated depolarization current experiments indicate the miscibility of the blends and the existence of different average local compositions. The Lodge-McLeish model is applied to the compositional variation of the two effective glass transition temperatures. Quantitative agreement is obtained for both components by adjusting the self-concentration values to best fit the experimental points. The relevant length for PCL is very close to its Kuhn length, whereas for PC the best fit leads to a slightly shorter characteristic length. It is shown that upon annealing at sufficiently high-temperature PC undergoes crystallization and thereby induces phase segregation in the otherwise amorphous regions of the blends.
Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b-poly(epsilon-caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the alpha mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large T(g) contrast.
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