Transition Zone Theory Compared to Standard Models: Reexamining the Theory of Crystal Growth from Melts
Transition Zone Theory Compared to Standard Models: Reexamining the Theory of Crystal Growth from Melts
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DOI：
10.1021/acs.jpcc.0c03003
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发表时间：
2020-08-27
影响因子：
3.7
通讯作者：
Hou, Feier
中科院分区：
文献类型：
--
作者：
Martin, James D.;Hillis, Berkley G.;Hou, Feier
世纪初提出的描述晶体生长速率与温度关系的思想已成为公认的“标准模型”。具体来说，有人提出，速率是由热力学驱动力控制的，液体/固体界面表面能需要晶体生长发生在台阶或扭结部位，颗粒扩散/粘性弛豫也控制着生长速率。然而，如本文所述，这些基本假设是不一致的事实，即从过冷熔体晶体生长是微观不可逆的，以及众所周知的事实，即熔体和晶体中的短程和中程秩序基本上是等同的，排除了尖锐的界面的存在和材料扩散的需要。相比之下，我们最近介绍了结晶的过渡区理论，TZT（c），一个凝聚态的艾林的过渡态理论，使用Kauzmann的构型熵的概念和亚当和吉布斯的协同性的想法来描述控制晶体生长速率的系综特性模拟。在这里，TZT（c）模型被应用到用于评估粘度与标准模型的表观解耦的相同的无机氧化物和有机分子组，以及其他几种材料。毫无例外，TZT（c）模型提供了一个上级适合温度依赖的晶体生长速率数据。通过精确描述不同结晶系统的单一模型，从TZT（c）中提取的三个参数首次提供了一个平台，用于比较和对比影响结晶反应的化学/物理因素。
Ideas proposed at the beginning of the 20th century to describe the temperature dependence of crystal growth rates have become accepted as the "standard model." Specifically, it was proposed that rates are controlled by a thermodynamic driving force, liquid/solid interfacial surface energy requires crystal growth to occur at step or kink sites, and particle diffusion/viscous relaxation also controls the rate of growth. However, as described in this article, these underlying assumptions are inconsistent with the fact that crystal growth from supercooled melts is microscopically irreversible, and the well-known fact that short- and intermediate-range order in melts and crystals is essentially equivalent, precluding the existence of sharp interfaces and the need for material diffusion. By contrast, we recently introduced the Transition Zone Theory of crystallization, TZT(c), a condensed matter analogue of Eyring's transition state theory that uses Kauzmann's conception of configurational entropy and Adam and Gibbs' ideas of cooperativity to describe the ensemble characteristics governing crystal growth rates. Here, the TZT(c) model is applied to the same sets of inorganic oxides and organic molecules that were used to evaluate the apparent decoupling of viscosity from the standard model, as well as to several other materials. Without exception, the TZT(c) model provides a superior fit to temperature-dependent crystal growth-rate data. With a single model accurately describing diverse crystallizing systems, the three parameters extracted from TZT(c), for the first time, provide a platform with which to compare and contrast chemical/physical factors that influence crystallization reactions.