The structure and dynamics of polystyrene (PS)-b-poly(ethylene oxide) block copolymers (BCPs) are studied. The BCPs exhibit microphase-separated cylindrical and lamellar morphologies. Structural dynamics are measured with X-ray photon correlation spectroscopy in the small-angle regime. Morphologies and domain sizes are evaluated using small-angle X-ray scattering (SAXS), scanning electron microscopy, and atomic force microscopy. Different solvent processing conditions are investigated. Grain sizes evaluated using SAXS are found to depend on processing only for the rubbery majority BCP. The structural relaxation times are examined as a function of PS volume fraction, temperature, morphology, and structural sizes. Well above the glass transition temperature (T_g) of PS, all samples exhibit stretched autocorrelation decays and diffusive dynamics. Near T_g of PS, the dynamics of all samples are anomalous with compressed autocorrelation decays and hyperdiffusive dynamics. This transition occurs at 153 °C or 1.13 T_g of PS. In the diffusive regime (at high temperature), structural relaxation times are dependent on the processing method. Near PS T_g (at low temperature), structural relaxation times scale with the PS volume fraction. Structural relaxation times do not correlate with grain size, indicating that the out-of-equilibrium state of PS dominates the structural dynamics of these strongly phase-segregated BCPs.

中文翻译：

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用 X 射线光子相关光谱研究高分子量柱状和层状嵌段共聚物的动力学

研究了聚苯乙烯（PS）-b-聚（环氧乙烷）嵌段共聚物（BCP）的结构和动力学。BCP 表现出微相分离的圆柱形和层状形态。结构动力学通过小角度范围内的 X 射线光子相关光谱进行测量。使用小角 X 射线散射 (SAXS)、扫描电子显微镜和原子力显微镜评估形态和域尺寸。研究了不同的溶剂加工条件。发现使用 SAXS 评估的晶粒尺寸仅取决于橡胶状大多数 BCP 的加工。结构弛豫时间作为 PS 体积分数、温度、形态和结构尺寸的函数进行检查。远高于 PS 的玻璃化转变温度 ( T _g )，所有样品都表现出拉伸自相关衰减和扩散动力学。在 PS 的T _g附近，所有样本的动力学都是异常的，具有压缩自相关衰减和超扩散动力学。这种转变发生在 153 °C 或PS 的1.13 T _g时。在扩散区域（高温），结构弛豫时间取决于加工方法。接近 PS T _g（低温）时，结构弛豫时间与 PS 体积分数成比例。结构弛豫时间与晶粒尺寸无关，表明 PS 的非平衡态主导了这些强相分离 BCP 的结构动力学。