Morphological Confinement on Crystallization in Blends of Poly(oxyethylene-<i>b</i><i>lock</i>-oxybutylene) and Poly(oxybutylene)

Abstract

Three poly(oxyethylene- block -oxybutylene) diblock copolymers, E 76 B 38, E 114 B 56, and E 155 B 76, were blended with poly(oxybutylene) homopolymer, B 14 and B 28, such that lamellae (lam), gyroid (gyr), hexagonally packed cylinders (hex), and body-centered-cubic (bcc) spheres were obtained in the melt. The nonisothermal crystallization on cooling of the blends was investigated with synchrotron small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC). In general, two classes of behavior are observed. In confined crystallization the morphology of the melt is retained, and crystals have limited dimensions. In breakout crystallization the melt morphology is destroyed, and a new lamellar morphology is formed. The morphological state (confinement in or breakout of melt morphology) during crystallization was evaluated by the change of the position of the first-order peak ( q *) in SAXS and the crystallization temperature ( T c ). Breakout of morphology was observed in all E 76 B 38 /B 14 blends and E 114 B 56 /B 28 and E 155 B 76 /B 28 blends with lam morphology, while confined crystallization occurred in E 155 B 76 /B 28 blends with hex and bcc morphologies and E 114 B 56 /B 28 blends with bcc morphology. Confined crystallization was also observed in low E content E 114 B 56 /B 28 blends with hex morphology. These findings lead to two conclusions: (i) the tendency of confined crystallization varies with morphology and decreases in the order bcc > hex > lam, and (ii) confinement on crystallization tends to increase with the extent of segregation between the two blocks. The DSC results show that the crystallization temperature of the blends varies with morphology and chain length of the block copolymers. A much lower T c was observed for the blends exhibiting confined crystallization behavior, and this phenomenon is explained by a homogeneous nucleation mechanism. The morphology over a larger scale was also examined by polarized light microscopy, and spherulite formation was only observed in the blends where the morphology was easily broken out during crystallization.