论文标题

在独立聚合物膜的玻璃过渡中的桥梁假设上

On the bridge hypothesis in the glass transition of freestanding polymer films

论文作者

Bonneau, Haggai, Arutkin, Maxence, Chen, Rainni, Forrest, James A, Raphael, Elie, Salez, Thomas

论文摘要

具有高分子量的独立薄聚合物膜显示出玻璃过渡温度的异常降低。具体而言,在这样的材料中,测得的玻璃转换温度以膜厚度的仿射方式演变,其斜率弱取决于分子量。 de Gennes提出了一种滑动机制,作为这些系统中假设的主要弛豫过程,在这些系统中,压力扭结可以通过所谓的桥梁以一种繁殖的方式传播,即从一个自由界面到另一个沿另一个界面到另一个界面,沿着聚合物大分子的骨架。在这里,通过考虑有限尺寸的随机步行的确切统计数据,我们详细介绍了桥梁假设。我们表明,滑动机制无法重现实验中出现的基本特征,并且我们表现出了这一事实背后的基本原因。

Freestanding thin polymer films with high molecular weights exhibit an anomalous decrease in the glass-transition temperature with film thickness. Specifically, in such materials, the measured glass-transition temperature evolves in an affine way with the film thickness, with a slope that weakly depends on the molecular weight. De Gennes proposed a sliding mechanism as the hypothetical dominant relaxation process in these systems, where stress kinks could propagate in a reptation-like fashion through so called bridges, i.e. from one free interface to the other along the backbones of polymer macromolecules. Here, by considering the exact statistics of finite-sized random walks within a confined box, we investigate in details the bridge hypothesis. We show that the sliding mechanism cannot reproduce the basic features appearing in the experiments, and we exhibit the fundamental reasons behind such a fact.

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