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Measuring diffusivity in supercooled liquid nanoscale films using inert gas permeation. II. Diffusion of Ar, Kr, Xe, and CH4 through methanol
Authors:Matthiesen Jesper  Smith R Scott  Kay Bruce D
Affiliation:Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, P.O. Box 999, Mail Stop K8-88, Richland, Washington 99352, USA.
Abstract:We present an experimental technique to measure the diffusivity of supercooled liquids at temperatures near their T(g). The approach uses the permeation of inert gases through supercooled liquid overlayers as a measure of the diffusivity of the supercooled liquid itself. The desorption spectra of the probe gas are used to extract the low temperature supercooled liquid diffusivities. In the preceding companion paper, we derived equations using ideal model simulations from which the diffusivity could be extracted using the desorption peak times for isothermal or peak temperatures for temperature programmed desorption experiments. Here, we discuss the experimental conditions for which these equations are valid and demonstrate their utility using amorphous methanol with Ar, Kr, Xe, and CH(4) as probe gases. The approach offers a new method by which the diffusivities of supercooled liquids can be measured in the experimentally challenging temperature regime near the glass transition temperature.
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