School of Pharmacy and Department of Chemistry, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.
J Phys Chem A. 2013 Dec 19;117(50):13303-9. doi: 10.1021/jp404944s. Epub 2013 Aug 1.
Surface self-diffusion coefficients have been determined for the organic glass Nifedipine using the method of surface grating decay. The flattening of 1000 nm surface gratings occurs by viscous flow at 12 K or more above the glass transition temperature and by surface diffusion at lower temperatures. Surface diffusion is at least 10(7) times faster than bulk diffusion, indicating a highly mobile surface. Nifedipine glasses have faster surface diffusion than the previously studied Indomethacin glasses, despite their similar bulk relaxation times. Both glasses exhibit fast surface crystal growth, and its rate scales with surface diffusivity. The observed rate of surface diffusion implies substantial surface rearrangement during the preparation of low-energy glasses by vapor deposition. The Random First Order Transition Theory and the Coupling Model successfully predict the large surface-enhancement of mobility and its increase on cooling, but disagree with the experimental observation of the faster surface diffusion of Nifedipine.
使用表面光栅衰减法测定了有机玻璃硝苯地平的表面自扩散系数。在玻璃化转变温度以上 12 K 或更高温度下,通过粘性流动使 1000nm 表面光栅变平,而在较低温度下则通过表面扩散。表面扩散速度至少比体扩散快 10(7)倍,表明表面具有很高的迁移率。尽管硝苯地平玻璃的体松弛时间与之前研究的吲哚美辛玻璃相似,但它们的表面扩散速度更快。两种玻璃都表现出快速的表面晶体生长,其速率与表面扩散系数成正比。观察到的表面扩散速率表明,在通过气相沉积制备低能量玻璃时,表面会发生大量的重新排列。随机一级相变理论和偶合模型成功地预测了迁移率的大幅增强及其随冷却而增加,但与硝苯地平的表面扩散速度更快的实验观察结果不一致。