RESUMEN
Tailoring the distribution of nanoparticles and further constructing effective microcapacitors in polymer blends are important issues for developing high-performance polymer dielectric nanocomposites. The common method to control the selective localization of nanoparticles in an immiscible polymer blend is relatively difficult and it easily results in the accumulation of nanoparticles in one component, which usually leads to a dramatic increase of the dielectric loss in the nanocomposites. In this work, a novel strategy based on step-by-step crystallization has been proposed to tailor the refined distribution and dispersion of carbon nanotubes (CNTs) in a melt-miscible blend poly(butylene succinate)/poly(vinylidene fluoride) (PBS/PVDF) through the crystallization-induced phase separation and the engineered interfacial affinity between CNTs and polymer components to acquire high dielectric constant and low dielectric loss. The results reveal that PBS is excluded along the growth front of PVDF spherulites and locates in the margin areas of PVDF spherulites during the step-by-step crystallization process. Moreover, because of the higher interfacial interaction between CNTs and PBS, CNTs are located in the PBS-rich domain, resulting in a high concentration of CNTs in the interspherulites of PVDF. Thus, the dielectric constants of the nanocomposites are greatly improved by nearly 5-24 times compared with the nanocomposites achieved by quick cooling and, simultaneously, the dielectric loss of the nanocomposites is still maintained at a low level. This work shows that the step-by-step crystallization method can be used to fabricate the nanocomposites with a synergistic increase in the dielectric performance due to the formation of a refined microcapacitor assembly. To the best of our knowledge, this is the first report to show that the dielectric constant of the nanocomposites can be greatly enhanced just through the crystallization-optimized distribution and dispersion of CNTs in immiscible polymer blends, and it possibly gives a new technical route for the fabrication of advanced dielectric composites.
RESUMEN
We examined the composition and molecular weight dependence of the glass transition temperature in detail for two types of hydrogen bonding miscible blends: poly (2-vinyl pyridine)/poly (vinyl phenol) (2VPy/VPh) and poly (4-vinyl pyridine)/poly (vinyl phenol) (4VPy/VPh). Regarding the functional form of the glass transition temperature, Tg, as a function of the weight fraction, we found a weak deviation from the Kwei equation for 2VPy/VPh blends. In contrast, such a deviation was not observed for the 4VPy/VPh blend. By relating the difference in the functional forms of Tg between the two blend systems to the difference in hydrogen bonding ability, we proposed a modified version of the Kwei equation. As for the interaction parameter, q in the Kwei equation, clear molecular weight dependence was observed for 2VPy/VPh blends: the lower the VPh molecular weight in the oligomer level, the higher the q values, suggesting the higher hydrogen bonding formability near the polymer chain ends than the middle part of a polymer chain.
RESUMEN
Miscible polymer blends with different glass transition temperatures (Tg) are known to create confined interphases between glassy and mobile chains. Here, we show that nanoparticles adsorbed with a high-Tg polymer, poly(methyl methacrylate), and dispersed in a low-Tg matrix polymer, poly(ethylene oxide), exhibit a liquid-to-solid transition at temperatures above Tg's of both polymers. The mechanical adaptivity of nanocomposites to temperature underlies the existence of dynamically asymmetric bound layers on nanoparticles and more importantly reveals their impact on macroscopic mechanical response of composites. The unusual reversible stiffening behavior sets these materials apart from conventional polymer composites that soften upon heating. The presented stiffening mechanism in polymer nanocomposites can be used in applications for flexible electronics or mechanically induced actuators responding to environmental changes like temperature or magnetic fields.