Influence of Solution Thermal and Structural History on the Nucleation of m-Hydroxybenzoic Acid Polymorphs

The influence of solution pretreatment on primary nucleation of m-hydroxybenzoic acid has been investigated through 550 cooling crystallization experiments. The metastable zone width has been determined at constant cooling rate, and the time and temperature of the preceding superheating step have been varied. m-Hydroxybenzoic acid has two polymorphs, and the influence of the polymorph used to prepare the solutions has also been investigated. There is an overall tendency in the experiments for the solution to exhibit a larger metastable zone width if it is superheated for a longer time and at a higher temperature, but under the investigated conditions this tendency is not very strong. The results show that the metastable form II preferentially crystallizes in all experiments and in particular when the solution has been more strongly superheated for several hours. However, when the time and/or the temperature of superheating is reduced, there is an increasing tendency to obtain the stable form I. This is most clearly found for solutions prepared by dissolving form I. When the solutions are prepared by dissolution of form II, this tendency is weaker in what appears to be a systematic way. It is hypothesized that, unless the solution is strongly superheated for several hours, it will contain for a significant period of time clusters of solute molecules that can retain some degree of structure from the dissolved crystal. This leads to "memory" effects in the solution, which may influence subsequent nucleation. The work includes a comprehensive review of previous published work on the influence of thermal history on nucleation in solutions and melts.