Unusual Transformation of Mixed Isomer Decahydroisoquinoline Stable Glasses

J Phys Chem B. 2023 Jul 6;127(26):5948-5958. doi: 10.1021/acs.jpcb.3c00459. Epub 2023 Jun 23.

Abstract

Dielectric relaxation was used to characterize the ability of vapor-deposited mixtures of cis- and trans-decahydroisoquinoline (DHIQ) to form glasses with a high kinetic stability. Vapor-deposited mixtures are technologically relevant, and the effect of mixing on glass stability is a relatively unexplored area. Mixed isomers and pure trans-DHIQ form highly stable glasses that isothermally transform in approximately 104 τα (where τα is the structural relaxation time of the supercooled liquid). Isomeric composition of the glasses does not play a significant role in the maximum kinetic stability of the resulting films. Secondary relaxations in DHIQ are associated with an intramolecular conformational change and are suppressed to a significant extent in highly stable glasses. During isothermal annealing experiments, stable glasses were found to transform initially via a growth front mechanism that transitions to a homogeneous bulk mechanism. Surprisingly, the time dependence of the bulk transformation is different from that reported for other stable glasses and cannot be interpreted in terms of a simple nucleation and growth model.