Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies.

Abstract

We report the dynamic behavior of a sphere-forming poly(styrene)-block-poly(1,4-butadiene) (PS-PB) diblock copolymer comprising 20 vol % PB below the order-disorder transition temperature (TODT = 153 °C) using dynamic mechanical spectroscopy (DMS) and X-ray photon correlation spectroscopy (XPCS). A time-temperature transformation diagram was constructed by monitoring the elasticity of the sample as a function of time following rapid quenches of the disordered melt to various temperatures T < TODT. Isothermal frequency spectra acquired prior to nucleation of the ordered BCC phase were time-temperature superposed, and the shift factors were fit using the Williams-Landel-Ferry (WLF) equation. For comparison, XPCS measurements were used to extract relaxation times from the supercooled liquid as a function of the quench temperature. Alignment of the temperature dependence of the XPCS-based relaxation times with that of the WLF shift factors in the range T = 125-140 °C indicates that both techniques probe the fluctuating mesomorphic micelle dynamics mediated by the relaxation modes of individual chains, including interparticle chain exchange. For deeper quench temperatures, TODT - T ≥ 28 °C, departure of the XPCS time constant from WLF behavior is consistent with a jamming transition, analogous to that encountered in concentrated colloidal systems. We postulate that the dominant relaxation mode in the supercooled disordered liquid transitions from ergodic dynamics governed by chain exchange to a nonergodic regime dominated by local rearrangement of micellar particles at T ≈ Terg, where Terg denotes the ergodicity temperature.