Crystallization in Microdomains of a Block Copolymer Comprising Semicrystalline Block Observed by Simultaneous Measurement of SAXS and WAXS with H_v‐SALS or DSC

Abstract

Semicrystalline block copolymers provide us with a fascinating model for studying the kinetics of crystallization. We performed the simultaneous measurement of small‐ (SAXS) and wide‐angle (WAXS) x‐ray scattering (SWAXS) with differential scanning calorimetry (DSC), or SWAXS with small‐angle light scattering (H _v‐SALS). The specimen used was polyethylene‐b‐poly(ethylene propylene) (PE‐b‐PEP) with the molecular weight of 44,200. The PE block has the melting point (T _m) at 108°C. We observed the time evolution of crystallization in the lamellar microdomains of PE‐b‐PEP after a temperature drop from 180°C (≫T _m) to a variety of temperatures slightly below T _m. The exothermic signal was observed by DSC right after the temperature drop, while the four‐leaf‐clover pattern of H _v‐SALS and the SAXS peaks due to the lamellar microdomains were observed several minutes after the temperature equilibration. The WAXS peaks of (110) and (200) reflection were almost simultaneously detected with the H _v‐SALS and the SAXS peaks at crystallization temperature of 100°C. With the crystallization temperature closer to T _m, the WAXS crystalline signals showed up with longer time lag after the H _v‐SALS and the SAXS peaks began to appear. Interestingly, these phenomena are interpreted as that long‐range order of density fluctuation up to the order of micrometers was generated prior to the formation of crystals with partially ordered phase rather than the instantaneous crystalline nucleation.

Keywords:

• Microdomains
• Crystallization
• Small‐angle x‐ray scattering
• Wide‐angle x‐ray scattering

Acknowledgments

We thank Dr. Kotaro Satoh and Mr. Hiromichi Nakata (Tsukuba Research Laboratories, Kuraray Co., Ltd.) for their help in dynamic mechanical measurements. The SAXS/WAXD/DSC and SAXS/WAXD/H _v‐SALS measurements were performed under approval of the Photon Factory Program Advisory Committee, KEK (Proposal No. 2001G269 and 2001G275). This work was financially supported in part by the Tatematsu Foundation, a grant for the Research Foundation for the Electrotechnology of Chubu for K. Y. (E‐14114), 2002, and by the Ministry of Education, Culture, Sports, Science and Technology, Grant‐in‐aid for Encouragement of Young Scientists for S.O. (13750829), 2001, and Grant‐in‐aid for Priority Areas ‘strongly correlated soft materials’ for S. S. (14045248), 2002, and by the Foundation for High‐Energy Accelerator Science for S. O., 2002.