Nanoconfined Solid–Solid Transitions: Attempt To Separate the Size and Surface Effects

Abstract

The solid–solid phase transitions in ammonium nitrate, ammonium perchlorate, and sodium nitrite confined to native and organically modified silica nanopores are analyzed by differential scanning calorimetry. The study reveals the effect of nanoconfinement on the transition temperature and links it to the kinetic parameters of the process. It is suggested that the effect of nanoconfinement is primarily the surface interaction effect in the native pores and the size effect in organically modified pores. It has been found that in organically modified pores the transition temperature is always depressed relative to the bulk, whereas in the native pores its behavior is generally unpredictable. Kinetic analysis of the transitions in terms of a nucleation model indicates that the experimentally observed shifts in temperature can be explained by a combination of changes in the free energy of nucleation and preexponential factor of the respective processes.