Evaluation of Growth Front Velocity in Ultrastable Glasses of Indomethacin over a Wide Temperature Interval

TitleEvaluation of Growth Front Velocity in Ultrastable Glasses of Indomethacin over a Wide Temperature Interval
Publication TypeJournal Article
Year of Publication2014
AuthorsRodríguez-Tinoco, C, Gonzalez-Silveira, M, Ràfols-Ribé, J, Lopeandía, AF, Mora, MTC-, Rodríguez-Viejo, J
JournalThe Journal of Physical Chemistry B
Keywordsgrowth front, indomethacin, nanocalorimetry, supercooled liquid, ultrastable glasses

Ultrastable thin film glasses transform into supercooled liquid via propagating fronts starting from the surface and/or interfaces. In this paper, we analyze the consequences of this mechanism in the interpretation of specific heat curves of ultrastable glasses of indomethacin for samples with varying thickness from 20 nm up to several microns. We demonstrate that ultrastable films above 20 nm have identical fictive temperatures and that the apparent change of onset temperature in the specific heat curves originates from the mechanism of transformation and the normalization procedure. An ad hoc surface normalization of the heat capacity yields curves which collapse into a single one irrespective of their thickness. Furthermore, we fit the surface-normalized specific heat curves with a heterogeneous transformation model to evaluate the velocity of the growth front over a much wider temperature interval than previously reported. Our data expands previous values up to Tg + 75 K, covering 12 orders of magnitude in relaxation times. The results are consistent with preceding experimental and theoretical studies. Interestingly, the mobility of the supercooled liquid in the region behind the transformation front remains constant throughout the thickness of the layers.

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