Statistical Approach to Crystal Nucleation in Glass-Forming Liquids

In this work, methods of description of crystal nucleation by using the statistical approach are analyzed. Findings from classical nucleation theory (CNT) for the average time of formation of the first supercritical nucleus are linked with experimental data on nucleation in glass-forming liquids stemming from repetitive cooling protocols both under isothermal and isochronal conditions. It is shown that statistical methods of lifetime analysis, frequently used in medicine, public health, and social and behavioral sciences, are applicable to crystal nucleation problems in glass-forming liquids and are very useful tools for their exploration. Identifying lifetime with the time to nucleate as a random variable in homogeneous and non-homogeneous Poisson processes, solutions for the nucleation rate under steady-state conditions are presented using the hazard rate and related parameters. This approach supplies us with a more detailed description of nucleation going beyond CNT. In particular, we show that cumulative hazard estimation enables one to derive the plotting positions for visually examining distributional model assumptions. As the crystallization of glass-forming melts can involve more than one type of nucleation processes, linear dependencies of the cumulative hazard function are used to facilitate assignment of lifetimes to each nucleation mechanism.

Automated summary

This work analyzes the methods of crystal nucleation description using statistical approaches, linking classical nucleation theory findings with experimental data on nucleation in glass-forming liquids. Statistical methods of lifetime analysis are shown to be applicable and useful for exploring crystal nucleation problems. Solutions for nucleation rate under steady-state conditions are presented, providing a more detailed description of nucleation beyond classical nucleation theory. Cumulative hazard estimation enables visually examining distributional model assumptions.