Nanograin nucleation at the growth front in melt crystallization of syndiotactic polystyrene

Melt-crystallization of syndiotactic polystyrene (sPS) is studied using simultaneous small/wide angle X-ray scattering (SAXS/WAXS). Emergence, intensification, and saturation of WAXS reflections within 120 s at isothermal crystallization temperature Tc = 250 °C after quenching from 300 °C illustrate crystallinity development through successive nucleation of instantaneously stabilized crystallites of lateral (hk0) coherence length Λ ≈ 75 nm. The corresponding SAXS profiles exhibit increased density heterogeneity due to formation of nanograins; fitting of time-resolved SAXS data with a model of arrayed disks reveals slightly thickened (lc = 7.4–8.4 nm) disks of radius R ≈ 9 nm and long period L ≈ 19 nm with polydisperse stacking number slowly enhanced from an average of 1.2 to 2.4. The moderate ratio of Λ/2R ≈ 4 indicates imperfect coalescence of nanograins in the lamellar assembly process. More importantly, with successively increased Tc from 250 to 260 °C the development of density heterogeneity of SAXS invariant Qinv is found to precede that of the WAXS-determined crystallinity Xc increasingly more, suggesting a precursor mesophase with non-crystalline nanograins. Avrami analysis for the developments of Xc and Qinv further reveals the same Avrami exponent n ≈ 3, consistent with heterogeneous nucleation of crystallites; the corresponding Avrami rate constant κ1/n(Tc) extracted from Xc is correlated to the crystal growth rates G(Tc) described by the Hoffman-Lauritzen theory with a common surface-nucleation rate constant Kg. A lateral surface energy σ ≈ 17 mJ m−2 can be deduced on the basis of Kg using previously determined fold surface energy σe ≈ 27 mJ m−2. Correspondingly, κ1/n(Tc) extracted from Qinv is described by a mesophase model proposed by Strobl with a zero-growth temperature of the nanograin mesophase ca. 30 K below the β-crystal melting point of sPS. Together, these results suggest that sPS melt-crystallization proceeds with nucleation of non-crystalline nanograins (SAXS-before-WAXS regime) at the crystal growth front, followed by crystallization of the nanograins with similar kinetics to sustain the growth front. Branching/twisting can occur at the lamellar growth front due to frustrated nanograin alignment, favoring the microscopically observed sheaf-like crystal morphology.