Carbon nanocapsules-reinforced syndiotactic polystyrene nanocomposites: Crystallization and morphological features

Syndiotactic polystyrene (sPS) composites filled with well-dispersed carbon nanocapsules (CNC) were prepared through solution blending along with ultrasonication. Several analytic techniques, including DSC, FTIR, PLM, WAXD, TEM, and TGA were performed to reveal the CNC effects on the crystallization, morphology and the thermal degradation of the as-prepared sPS/CNC composites. Addition of CNC was found to favor the crystalline modification of β-form sPS and depress the α-form ones. For the dynamic crystallization, a gradual reduction of cold-crystallization temperature of the α-form sPS was observed by increasing the CNC content although the glass transition temperature remained unchanged (∼96 °C). In contrast, the melt-crystallization temperature of the β-form sPS was elevated from 238 °C for the neat sPS to 251 °C for the 99/5 composite in spite of the fact that the equilibrium melting temperature (∼290 °C) determined from the linear Hoffman-Weeks plot was irrelevant with CNC concentrations. The former was attributable to the formation of an effective heat-conduction path to trigger an earlier overall crystallization. On the other hand, the latter resulted from the enhanced nucleation sites due to the presence of uniformly dispersed CNCs. Results of the isothermal crystallization of the β-form sPS concluded that the presence of 1% CNCs led to a significant increase in the crystallization rate as much as an order of magnitude. Moreover, the Avrami exponent changed to ∼2.0 from a value of 2.8 for the neat sPS, suggesting a different crystallization mechanism involved. At a given crystallization temperature, PLM results showed a negligible variation in the crystal growth rates and a decrease in spherulitic sizes, indicating that nucleation played the key role in enhancing the crystallization rate. For samples isothermally crystallized at 260 °C, the lamellar thickness was constant to be ∼7.2 nm regardless of the CNC content. Due to the enhanced nucleation, however, lamellar stacks were more randomly oriented and its lateral dimensions became shorter with increasing CNC contents. For composites with more than 1 wt% CNC, the crystallizability of sPS chains was reduced and the annealing peak located ca. 4 °C higher than the crystallization temperature became more evident, suggesting the plausible formation of micro-crystals in between the lamellar stacks. The TGA results illustrated that a better thermal stability was reached for the CNC-filled sPS composites.