We employ a new force-level statistical mechanical theory to predict spatial gradients of the structural relaxation time and T_g of polymer liquids near microscopically rough and smooth hard surfaces and contrast the results with vapor interface systems. Repulsive rough (smooth) surfaces induce large slowing down (modest speeding up) of the relaxation time compared to the bulk. Nevertheless, a remarkable degree of universality of distinctive dynamical behaviors is predicted for different polymer chemistries and all interfaces, including a double exponential form of the alpha time gradient, power law decoupling of the relaxation time from its bulk value with exponential spatial variation of the exponent, exponential spatial gradient of T_g, weak dependence of normalized T_g gradients on vitrification criterion, and near linear growth with cooling of the slowed down layer thickness near a rough hard interface. The results appear consistent with simulations and experiments, and multiple testable predictions are made.

中文翻译：

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固体基质附近的玻璃形成聚合物液体的弛豫、玻璃化温度和脆性的空间梯度理论

我们采用一种新的力级统计力学理论来预测微观粗糙和光滑硬表面附近聚合物液体的结构弛豫时间和T _g的空间梯度，并将结果与​​蒸汽界面系统进行对比。与本体相比，排斥的粗糙（光滑）表面会导致弛豫时间大幅减慢（适度加快）。然而，对于不同的聚合物化学和所有界面，预测了不同的动力学行为具有显着程度的普遍性，包括 α 时间梯度的双指数形式，弛豫时间与其体积值的幂律解耦以及指数的指数空间变化, T _{g的指数空间梯度}，归一化T _g梯度对玻璃化标准的弱依赖性，以及在粗糙硬界面附近随着减慢层厚度的冷却而接近线性增长。结果似乎与模拟和实验一致，并且做出了多个可检验的预测。