Comparison of crystallization kinetics in various nanoconfined geometries

Phase morphological effect on crystallization kinetics in various nanoconfined spaces in a polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer with a PEO volume fraction of 37vol% was investigated. The phase morphology was characterized by small-angle X-ray scattering and transmission electron microscopy techniques. When the sample was cast from chloroform solution and annealed at 150°C, a double gyroid (DG) phase was obtained. After it was subjected to a large-amplitude reciprocating shear, the sample transformed to an oriented hexagonal cylinder (Hex) phase. To obtain a lamellar confined geometry, lamellar single crystals were grown from dilute solutions. The crystallization in the lamellar (Lam) phase was one-dimensionally (1D) confined, while it was two-dimensionally (2D) confined in the DG and Hex phases, although they had different structures. Differential scanning calorimetry (DSC) was employed to study the crystallization kinetics using the Avrami analysis for these three nanoconfined geometries. Heterogeneous nucleation was found in all three samples in the crystallization temperature (T_c) regions studied. DSC results indicated that the crystallization kinetics in the Lam phase was the fastest, and the PEO crystals possessed higher thermodynamic stability than in the DG and Hex phases. For the crystallization kinetics in two 2D-confined phases, at low T_c (<35°C) the PEO crystallization rates in the DG and Hex phases were similar, while at high T_c (>35°C) the PEO crystallization was slower in the DG phase than in the Hex phase. The Avrami exponent n-values for the DG and the Hex samples were similar (∼1.8), yet the values of lnK in the DG phase were smaller than those in the Hex phase. This suggested that the linear growth rate was slower in the DG phase than in the Hex phase due to continuous curved channels in the DG phase.