Sonofragmentation of Organic Molecular Crystals vs Strength of Materials

Abstract

Mechanochemistry, the interface between the chemical and the mechanical worlds, includes the relationship between the chemical and mechanical properties of solids. In this work, fragmentation of organic molecular crystals during ultrasonic irradiation of slurries has been quantitatively investigated. This has particular relevance to nucleation processes during sonocrystallization, which is increasingly used in the processing and formulation of numerous pharmaceutical agents (PAs). We have discovered that the rates of sonofragmentation are very strongly correlated with the strength of the materials (as measured by Vickers hardness and Young's modulus). This is a mechanochemical extension of the Bell-Evans-Polanyi Principle or Hammond's Postulate: the kinetics (i.e., rates) of solid fracture correlate with thermodynamic properties of solids (e.g., Young's modulus). The mechanism of the particle breakage is consistent with a direct interaction between the shockwaves or localized microjets created by the ultrasound (through acoustic cavitation) and the solid particles in the slurry. Comparisons of the sonofragmentation patterns of ionic and molecular crystals showed that ionic crystals are more sensitive to sonofragmentation than molecular crystals for a given Young's modulus. The rates of sonofragmentation are proposed to correlate with the types and densities of imperfections in the crystals. © 2021 American Chemical Society. All rights reserved.