Institut für Physik der Universität Rostock, Universitätsplatz, 18051 Rostock, Germany.
J Chem Phys. 2011 Feb 7;134(5):054511. doi: 10.1063/1.3548870.
A general thermodynamic analysis of nucleation-growth processes in confined space in initially metastable states of the ambient phase is performed based on the generalized Gibbs approach to the description of heterogeneous systems. In particular, it is shown analytically how the parameters of critical clusters and clusters in stable equilibrium with the ambient phase depend on the volume of the system for initially fixed intensive state parameters of the ambient phase. Qualitatively, the results are shown to be similar independent on the boundary conditions employed. It is demonstrated further that the behavior of systems in confined space is directly related to the kinetics of phase transformation processes in spatially extended systems, when ensembles of clusters are formed. The results of the thermodynamic analysis of cluster formation and growth in a confined space are employed then, in particular, to the derivation of kinetic equations for the description of the process of coarsening or Ostwald ripening. In the analysis of both the nucleation in confined space and the description of Ostwald ripening, no specific assumptions concerning the equations of state of the system under consideration and the number of components both in the ambient and newly evolving phases are made. Consequently, the results are of very general nature and hold always as far as the necessary condition for the possibility of a phase transformation is fulfilled.
基于广义 Gibbs 方法对非均匀系统的描述，对初始亚稳相环境相中受限空间内成核-生长过程进行了一般热力学分析。特别是，分析了对于初始固定的环境相强度状态参数，临界团簇和与环境相处于稳定平衡的团簇的参数如何随系统体积而变化。定性地说，无论采用何种边界条件，结果都表现出相似性。进一步证明，当形成团簇系时，受限空间中系统的行为与空间扩展系统中相转变过程的动力学直接相关。然后，特别是将受限空间中团簇形成和生长的热力学分析结果用于推导描述粗化或奥斯特瓦尔德熟化过程的动力学方程。在受限空间中成核的分析和对奥斯特瓦尔德熟化的描述中，没有对所考虑系统的状态方程和环境相以及新演化相中的成分数做出具体的假设。因此，只要满足相变的必要条件，结果就是非常普遍的。
