While prior efforts have demonstrated that the morphologies of block copolymer (BC) bulk films can be controlled through judicious chemical design and thermal annealing, recent interest has focused on regulating the orientation of BC nanostructures and minimizing defects. Thermal processes developed to achieve this purpose for nonpolar BCs are not, however, suitable for orienting microphase‐ordered BCs composed of at least one block with charged moieties that can form thermally stable ionic clusters. To overcome this challenge, we have previously applied solvent‐vapor (SV) annealing to block ionomer (BI) bulk films composed of midblock‐sulfonated pentablock copolymers and established that this approach yields highly ordered morphologies that display evidence of improved in‐plane orientation. Here, we employ small‐angle X‐ray scattering to compare the effectiveness of three solvent‐related processes–SV annealing, SV permeation, and SV sorption–on BI ordering and grain growth, and offer explanations for observed differences on the basis of thermodynamic‐ and transport‐related considerations. Differences in the experimental design of these solvent‐related processes are found to affect nanostructural development, as evidenced by the extent of in‐plane grain growth.

中文翻译：

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带电荷的嵌段共聚物本体薄膜的有序化和晶粒长大：与溶剂有关的过程的比较

尽管先前的努力表明，可以通过明智的化学设计和热退火来控制嵌段共聚物（BC）块状薄膜的形貌，但最近的关注点已集中在调节BC纳米结构的取向和最大程度地减少缺陷上。但是，为实现非极性BC的目的而开发的热工艺不适用于定向由至少一个带电部分的嵌段组成的微相有序BC定向，该带电部分可以形成热稳定的离子簇。为了克服这一挑战，我们先前已将溶剂-蒸汽（SV）退火应用于由中嵌段磺化五嵌段共聚物组成的嵌段离聚物（BI）块状薄膜，并确定该方法可产生高度有序的形态，显示出改善的面内取向的证据。这里，我们使用小角度X射线散射来比较SV退火，SV渗透和SV吸附这三种与溶剂有关的过程对BI有序化和晶粒长大的有效性，并根据热力学和热力学为观察到的差异提供解释。与运输有关的注意事项。这些溶剂相关工艺的实验设计差异被发现会影响纳米结构的发展，这可以通过平面内晶粒的生长程度来证明。