In Situ Investigation of Vapor-Deposited Glasses of Toluene and Ethylbenzene via Alternating Current Chip-Nanocalorimetry

J Chem Phys. 2013 Jan 14;138(2):024501. doi: 10.1063/1.4773354.


Vapor-deposited glasses of toluene and ethylbenzene have been characterized by in situ ac chip-nanocalorimetry. The high sensitivity of this method allows the detection of small changes in the heat capacity of nanogram size samples. We observe that vapor-deposited glasses have up to 4% lower heat capacities than the ordinary glass. The largest heat capacity decrease and the most kinetically stable glasses of toluene and ethylbenzene are observed in a range of deposition temperatures between 0.75 T(g) and 0.96 T(g). Compared to larger molecules, deposition rate has a minor influence on the kinetic stability of these glasses. For both toluene and ethylbenzene, the kinetic stability is strongly correlated with the heat capacity decrease for deposition temperatures above 0.8 T(g). In addition, ac-nanocalorimetry was used to follow the isothermal transformation of the stable glasses into the supercooled liquid at temperatures slightly above T(g). Toluene and ethylbenzene stable glasses exhibit a constant transformation rate which is consistent with the growth front mechanism recently demonstrated for tris-naphthylbenzene and indomethacin. The kinetic stability of the most stable toluene and ethylbenzene glasses is comparable to that observed for other stable glasses formed by vapor deposition.