Dense Glass Packing Can Slow Reactions with an Atmospheric Gas

Previous work utilizing crystal polymorphs has established the importance of the molecular packing environment for modulating solid-gas reactivity. Here, we show, for the first time, that the chemical stability of an amorphous material in contact with a reactive gas can be significantly improved by controlling glass packing. We utilize the reaction of indomethacin with ammonia as this system has been well-characterized for crystalline polymorphs. For these experiments, physical vapor deposition (PVD) is used to prepare glasses of indomethacin with a range of densities and thermal stabilities. The indomethacin-ammonia reactivity is assessed through the increase in mass of glassy thin films exposed to ammonia gas, as characterized by a quartz crystal microbalance. Indomethacin glasses vapor-deposited at substrate temperatures below the glass transition temperature (T_g) show unprecedented decrease in reaction rates relative to the liquid-cooled glass, by as much as 1 order of magnitude, with the densest glasses having the slowest reactions. The diminished solubility of ammonia in dense PVD glasses is found to be a major factor in their remarkable chemical stability. As chemically stable amorphous solids are in demand for applications including pharmaceuticals and organic electronics, this work provides a strategy to improve performance of these materials.