Kinetics of crystallization preceded by metastable-phase formation

A theoretical description is proposed of the kinetics of overall crystallization when the appearance of the stable crystalline (SC) phase is preceded by the formation of a metastable phase. A general formula is derived for the fraction αs of volume of the SC phase crystallized at time t. This formula is used for obtaining the αs(t) function in the case of Kolmogorov–Johnson–Mehl–Avrami kinetics of overall crystallization. The time t1/2 at which half of the transformation of the parent phase into the SC one is accomplished is determined and it is found that this time is the sum of the times for half completion of the two successive phase transformations of the parent phase into the metastable one and of the latter into the SC phase. A general condition for formation of a long living metastable phase is formulated in terms of the nucleation and growth rates of the metastable and the SC phases. The general results are applied to melt crystallization and an expression for the temperature dependence of t1/2 is...

[1]  Toru Takahashi On the role of cubic structure in ice nucleation , 1982 .

[2]  D. Turnbull Metastable structures in metallurgy , 1981 .

[3]  P. Barham,et al.  An approach to the formation and growth of new phases with application to polymer crystallization: effect of finite size, metastability, and Ostwald's rule of stages , 1994, Journal of Materials Science.

[4]  H. Reiss,et al.  Homogeneous nucleation rates for water , 1993 .

[5]  M. Avrami Kinetics of Phase Change. II Transformation‐Time Relations for Random Distribution of Nuclei , 1940 .

[6]  D. Rasmussen Thermodynamics and nucleation phenomena — A set of experimental observations , 1982 .

[7]  D. Verdoes,et al.  Induction time and metastability limit in new phase formation , 1991 .

[8]  K. Sato,et al.  Polymorphic transformations in crystal growth , 1993 .

[9]  S. Toschev,et al.  Non‐steady State nucleation in the formation of isotropic and anisotropic phases , 1968 .

[10]  J. C. Brice,et al.  The Growth of Crystals from Liquids , 1974 .

[11]  Max Volmer,et al.  Kinetik der Phasenbildung , 1939 .

[12]  S. Matsumoto,et al.  Diamond synthesis from gas phase in microwave plasma , 1983 .

[13]  T. Nakada,et al.  A novel approach to the solubility measurement of protein crystals by two-beam interferometry , 1996 .

[14]  A. Keller,et al.  Dependence of the lamellar thickness of an extended-chain single crystal of polyethylene on the degree of supercooling and the pressure , 1995 .

[15]  L. Dufour,et al.  Thermodynamics of clouds , 1963 .

[16]  O. Söhnel,et al.  Precipitation: Basic Principles and Industrial Applications , 1992 .

[17]  N. Garti,et al.  Crystallization and polymorphism of fats and fatty acids , 1988 .

[18]  Kiyotaka Sato,et al.  Kinetics of melt crystallization and transformation of tripalmitin polymorphs , 1987 .

[19]  J. Christian,et al.  The theory of transformations in metals and alloys , 2003 .

[20]  J. W. RODGER,et al.  Lehrbuch der Allgemeinen Chemie , 1893, Nature.

[21]  D. Kashchiev,et al.  Transition from island to layer growth of thin films: A Monte Carlo simulation , 1977 .

[22]  A. E. Nielsen Kinetics of precipitation , 1964 .

[23]  J. Schmelzer,et al.  Ostwald's Rule of Stages: The Effect of Elastic Strains and External Pressure , 1998 .

[24]  D. Kashchiev Growth kinetics of dislocation-free interfaces and growth mode of thin films , 1977 .

[25]  M. Hikosaka,et al.  Role of Transient Metastable Hexagonal Phase in the Formation of Extended Chain Single Crystals of Vinylidene Fluoride and Trifluoroethylene Copolymers , 1994 .