Kearns Kenneth L, Swallen Stephen F, Ediger M D, Wu Tian, Sun Ye, Yu Lian
Department of Chemistry, University of Wisconsin--Madison, Madison, Wisconsin, 53706, USA.
J Phys Chem B. 2008 Apr 24;112(16):4934-42. doi: 10.1021/jp7113384. Epub 2008 Apr 3.
Physical vapor deposition was employed to prepare amorphous samples of indomethacin and 1,3,5-(tris)naphthylbenzene. By depositing onto substrates held somewhat below the glass transition temperature and varying the deposition rate from 15 to 0.2 nm/s, glasses with low enthalpies and exceptional kinetic stability were prepared. Glasses with fictive temperatures that are as much as 40 K lower than those prepared by cooling the liquid can be made by vapor deposition. As compared to an ordinary glass, the most stable vapor-deposited samples moved about 40% toward the bottom of the potential energy landscape for amorphous materials. These results support the hypothesis that enhanced surface mobility allows stable glass formation by vapor deposition. A comparison of the enthalpy content of vapor-deposited glasses with aged glasses was used to evaluate the difference between bulk and surface dynamics for indomethacin; the dynamics in the top few nanometers of the glass are about 7 orders of magnitude faster than those in the bulk at Tg - 20 K.
采用物理气相沉积法制备了吲哚美辛和1,3,5-(三)萘基苯的非晶态样品。通过沉积在略低于玻璃化转变温度的基底上,并将沉积速率从15 nm/s变化到0.2 nm/s,制备出了具有低焓值和优异动力学稳定性的玻璃态物质。通过气相沉积可以制备出虚构温度比通过冷却液体制备的玻璃态物质低多达40 K的玻璃。与普通玻璃相比,最稳定的气相沉积样品在非晶态材料的势能景观中向底部移动了约40%。这些结果支持了这样的假设,即增强的表面迁移率允许通过气相沉积形成稳定的玻璃态。通过比较气相沉积玻璃与老化玻璃的焓含量,来评估吲哚美辛在体相和表面动力学之间的差异;在玻璃态物质顶部几纳米处的动力学比在Tg - 20 K时体相中的动力学快约7个数量级。