Controlling polymer/substrate interfaces without modifying chemistry is nowadays possible by finely tuning the formation of adsorbed layers. The complex processes leading to irreversible attachment of chains onto solid substrates are governed by two mechanisms: molecular rearrangement and potential-driven adsorption. Here we introduce an analytical method to differentiate these two mechanisms. By analyzing experiments and simulations, we investigate how changes in thermal energy and interaction potential affect equilibrium and nonequilibrium components of the adsorption kinetics. We find that the adsorption process is thermally activated, with activation energy comparable to that of local noncooperative processes. On the other hand, the final adsorbed amount depends on the interface interaction only (i.e., it is temperature independent in experiments). We identify a universal linear relation between the growth rates at short and long adsorption times, suggesting that the monomer pinning mechanism is independent of surface coverage, while the progressive limitation of free sites significantly limits the adsorption rate.

中文翻译：

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聚合物在固体基质上的吸附机理

如今，通过微调吸附层的形成，可以在不改变化学成分的情况下控制聚合物/基材界面。导致链不可逆地附着在固体基质上的复杂过程受两种机制控制：分子重排和电位驱动吸附。在这里，我们介绍一种分析方法来区分这两种机制。通过分析实验和模拟，我们研究了热能和相互作用势的变化如何影响吸附动力学的平衡和非平衡分量。我们发现吸附过程是热活化的，其活化能与局部非合作过程的活化能相当。另一方面，最终吸附量仅取决于界面相互作用（即，它在实验中与温度无关）。我们确定了短吸附时间和长吸附时间的生长速率之间存在普遍的线性关系，这表明单体钉扎机制与表面覆盖无关，而自由位点的逐渐限制显着限制了吸附速率。