Effect of small amount of poly(ethylene naphthalate) on isothermal crystallization and spherulitic morphology of poly(trimethylene terephthalate)

Abstract

The effect of a small amount of poly(ethylene naphthalate) (PEN) in its blends with poly(trimethylene terephthalate) (PTT) on isothermal melt-crystallization kinetics and spherulitic morphology of the blends was thoroughly investigated. The maximum PEN content in the blends was 9 wt%. Due to the single composition-dependent glass transition temperature ( T g) that was observed for each blend, these blends appeared to be miscible in the amorphous state. After isothermal crystallization from the melt state, the neat PTT and its blends with PEN exhibited either double or triple melting endotherms. The triple endothermic peaks were observed in both the neat PTT and the blends when being crystallized at crystallization temperatures ( T c) of less than or equal to ∼195 °C. The equilibrium melting temperature ( T m 0 ) for the neat PTT was determined based on the linear Hoffman–Weeks extrapolative method to be ∼248 °C. Such values for the blends were found to decrease with the addition and increasing amount of PEN. Both the neat PTT and the blends were isothermally crystallized over the T c range of 190–205 °C. At a given T c, the 97PTT/3PEN blend exhibited a half-time of crystallization ( t 0.5) value that was lower, while it exhibited reciprocal half-time ( t 0.5 - 1 ), Avrami rate constant ( K A), and spherulitic growth rate ( G) values that were greater, than those of the neat PTT. With further increase in the PEN content, the t 0.5 value increased, while the t 0.5 - 1 , K A, and G values decreased. Analysis of the G values based on the Lauritzen–Hoffman's (LH) secondary nucleation theory showed that the neat PTT and the 91PTT/9PEN blend exhibited a regime II→III transition at ∼194 °C (∼467.2 K), while no regime transition was observed for the other two blends. The lateral and the fold surface free energies ( σ and σ e) and the work of chain folding ( q) for the neat PTT and the blends were 19.4, 30.2–46.3 erg cm −2, and 2.4–3.6 kcal mol −1, respectively. Lastly, the effect of both the T c and the PEN content on morphology and texture of the PTT spherulites was also investigated and the results showed that the texture of the spherulites became coarser with increasing T c and PEN content.