The properties of macromolecules in presence of an interface could be considerably modified due to confinement effects. When phase separations are performed in nanoconfined domains, the concurrent presence of high-energy interfaces and conformational entropy constraints of the macromolecules causes profound differences in polymer aggregation behavior. Here, thermodynamics of a polymer chain in solution, confined by a three-dimensional cubic interface, is studied by means of Monte Carlo method, focusing on the chain conformational entropy penalty arising from the excluded volume effects. The presented method might become a general tool for a preliminary evaluation of the thermodynamic effects due to the confinement of a polymer system. Further, the interface effects on Thermally Induced Phase Separation (TIPS) of polymer solutions, confined by High-Pressure Homogenization, are experimentally studied, regarding final morphologies. It is confirmed how peculiar polymer morphologies are obtained only when the TIPS develops under nanoconfinement degrees above a threshold one. © 2017 American Institute of Chemical Engineers AIChE J, 2017

中文翻译：

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聚合物链的约束：蒙特卡罗方法的熵研究

由于限制作用，在存在界面的情况下大分子的性质可能会大大改变。当在纳米约束域中进行相分离时，高能界面的同时存在和大分子的构象熵约束导致聚合物聚集行为的深刻差异。在这里，通过蒙特卡罗方法研究了在三维立体界面范围内的聚合物链在溶液中的热力学，重点研究了由于排除体积效应而产生的链构象熵损失。由于聚合物体系的局限性，提出的方法可能成为初步评估热力学效应的通用工具。此外，界面对聚合物溶液的热诱导相分离（TIPS）产生影响，关于最终形态，进行了高压均质化限制的实验研究。可以确定的是，只有当TIPS在高于阈值1的纳米约束度下发展时，才能获得独特的聚合物形态。©2017美国化学工程师学会AIChE的Ĵ，2017年