Powell C Travis, Xi Hanmi, Sun Ye, Gunn Erica, Chen Yinshan, Ediger M D, Yu Lian
School of Pharmacy and Department of Chemistry, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53706, United States.
J Phys Chem B. 2015 Aug 6;119(31):10124-30. doi: 10.1021/acs.jpcb.5b05389. Epub 2015 Jul 23.
Molecular liquids can develop a fast mode of crystal growth ("GC growth") near the glass transition temperature. This phenomenon remains imperfectly understood with several explanations proposed. We report that GC growth in o-terphenyl conserves the overall volume, despite a 5% higher density of the crystal, and produces fine crystal grains with the same unit cell as normally grown crystals. These results indicate that GC growth continuously creates voids and free surfaces, possibly by fracture. This aspect of the phenomenon has not been considered by previous treatments and is a difficulty for those models that hypothesize a 5% strain without voids. Given the existence of even faster crystal growth on the free surface of molecular glasses, we consider the possibility that GC growth is facilitated by fracture and surface mobility. This notion has support from the fact that GC growth and surface growth are both highly correlated with surface diffusivity and with fast crystal growth along preformed cracks in the glass.
分子液体在玻璃化转变温度附近能够形成一种快速的晶体生长模式(“GC生长”)。对于这一现象,尽管已经提出了几种解释,但仍未得到充分理解。我们报告称,邻三联苯中的GC生长能保持总体积不变,尽管晶体密度高出5%,并且能产生与正常生长晶体具有相同晶胞的细晶粒。这些结果表明,GC生长可能通过断裂持续产生空隙和自由表面。该现象的这一方面在以往的研究中未被考虑,对于那些假设无空隙的5%应变的模型来说是一个难题。鉴于分子玻璃自由表面上存在甚至更快的晶体生长,我们考虑GC生长是由断裂和表面迁移率促进的可能性。这一观点得到了以下事实的支持:GC生长和表面生长都与表面扩散率以及沿着玻璃中预先形成的裂纹的快速晶体生长高度相关。