School of Engineering, University of California , Merced, California 95343, United States.
Department of Chemical Engineering and Materials Research Institute, Pennsylvania State University , University Park, Pennsylvania 16802, United States.
ACS Appl Mater Interfaces. 2017 Jan 25;9(3):3142-3148. doi: 10.1021/acsami.6b14159. Epub 2017 Jan 11.
Polymerization of allyl alcohol adsorbed and sheared at a silicon oxide interface is studied using tribo-tests in vapor phase lubrication conditions and reactive molecular dynamics simulations. The load dependences of product formation obtained from experiments and simulations were consistent, indicating that the atomic-scale processes observable in the simulations were relevant to the experiments. Analysis of the experimental results in the context of mechanically assisted thermal reaction theory, combined with the atomistic details available from the simulations, suggested that the association reaction pathway of allyl alcohol molecules induced by mechanical shear is quite different from chemically induced polymerization reactions. Findings suggested that some degree of distortion of the molecule from its equilibrium state is necessary for mechanically induced chemical reactions to occur and such a distortion occurs during mechanical shear when molecules are covalently anchored to one of the sliding surfaces.
采用摩擦试验和反应分子动力学模拟研究了在氧化硅界面吸附和剪切的烯丙醇的聚合。从实验和模拟中获得的产物形成的负载依赖性是一致的，这表明在模拟中观察到的原子尺度过程与实验相关。根据机械辅助热反应理论对实验结果进行分析，并结合模拟中提供的原子细节，表明机械剪切诱导的烯丙醇分子的缔合反应途径与化学诱导的聚合反应有很大的不同。研究结果表明，机械诱导化学反应的发生需要分子从其平衡态发生一定程度的变形，并且当分子共价锚定在滑动表面之一时，这种变形会在机械剪切过程中发生。
