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.
The emerging field of printed electronics uses large amounts of printing and coating solvents during fabrication, which commonly are deposited and evaporated within spaces available to workers. It is in this context unfortunate that many of the currently employed solvents are non-desirable from health, safety, or environmental perspectives. Here, we address this issue through the development of a tool for the straightforward identification of functional and “green” replacement solvents. In short, the tool organizes a large set of solvents according to their Hansen solubility parameters, ink properties, and sustainability descriptors, and through systematic iteration delivers suggestions for green alternative solvents with similar dissolution capacity as the current non-sustainable solvent. We exemplify the merit of the tool in a case study on a multi-solute ink for high-performance light-emitting electrochemical cells, where a non-desired solvent was successfully replaced by two benign alternatives. The green-solvent selection tool is freely available at: www.opeg-umu.se/green-solvent-tool.
While ordinary glasses transform into supercooled liquid via a homogeneous bulk mechanism, thin film glasses of higher stability transform heterogeneously by a front propagating from the surface and/or the interfaces. In this work, we use quasi-adiabatic fast scanning nanocalorimetry to determine the heat capacity of thin glassy layers of indomethacin vapor-deposited in a broad temperature range of 110 K below the glass transition temperature. Their variation in fictive temperature amounts to 40 K. We show that a propagating front is the initial transformation mechanism in all cases. Using an ad hoc surface normalization procedure we determine the corresponding growth front velocity for the whole range of deposition temperatures. Although the transformation rate changes by a factor of 10 between the most and less stable samples, the relation between the mobility of the front and the thermodynamic stability of the glass is not uniquely defined. Glasses grown above 280 K, which are at equilibrium with the supercooled liquid, present a different dependence of the growth front velocity on fictive temperature compared to glasses grown out of equilibrium at Tdep < 250 K. These glasses transform faster with increasing Tf. Our data clarify previous reports and support the evidence that the fictive temperature alone is not an absolute indicator of the properties of the glass, at least when its structure is not completely isotropic. To interpret the data, we propose that the growth front velocity depends on three terms: the mobility of the liquid at a given temperature, the mobility of the glass and the arrangement of the molecules in the glass.
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