TY - JOUR
T1 - Evaluation of growth front velocity in ultrastable glasses of indomethacin over a wide temperature interval
AU - Rodríguez-Tinoco, Cristian
AU - Gonzalez-Silveira, Marta
AU - Ràfols-Ribé, Joan
AU - Lopeandía, Aitor F.
AU - Clavaguera-Mora, Maria Teresa
AU - Rodríguez-Viejo, Javier
PY - 2014/9/11
Y1 - 2014/9/11
N2 - © 2014 American Chemical Society. 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. (Figure Presented).
AB - © 2014 American Chemical Society. 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. (Figure Presented).
U2 - 10.1021/jp506782d
DO - 10.1021/jp506782d
M3 - Article
SN - 1520-6106
VL - 118
SP - 10795
EP - 10801
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
ER -