November 7, 2010
Journal Article

Measuring Diffusivity in Supercooled Liquid Nanoscale Films using Inert Gas Permeation: II. Diffusion of AR, KR, Xe, and CH4 through Methanol

Abstract

We present an experimental technique to measure the diffusivity of supercooled liquids at temperatures near their Tg. 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 is 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 TPD 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 CH4 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.

Revised: May 4, 2011 | Published: November 7, 2010

Citation

Matthiesen J., R.S. Smith, and B.D. Kay. 2010. Measuring Diffusivity in Supercooled Liquid Nanoscale Films using Inert Gas Permeation: II. Diffusion of AR, KR, Xe, and CH4 through Methanol. Journal of Chemical Physics 133, no. 17:174505-11. PNNL-SA-74281. doi:10.1063/1.3497648