We present an experimental method for measuring diffusion of lubricants (or any highly viscous fluid) in polymers using Fourier transform infrared (FT-IR) attenuated total reflection (ATR) spectroscopy. Unlike the conventional FT-IR ATR diffusion measurement, in which a polymer sample is sandwiched between the penetrant and an internal reflection element (IRE), in this method, a thin layer of penetrant (for example, a lubricant) is sandwiched between the IRE and the polymer sample. This allows accurate control and measurement of the thickness of the lubricant layer, which, in turn, facilitates subsequent data analysis. The diffusion is studied by monitoring the time-resolved change in absorbance of either a unique polymer or penetrant band. A feature of this new method is that it can provide an estimate of solubility, as well as an estimate of the diffusivity of the penetrant in the polymer. Using this method, we studied the diffusion of mineral oil and a commercial fluorocarbon ether lubricant (Krytox® 143AC‡) in poly(propylene) (PP) film at room temperature. The experimental data was modeled using a Fickian model with impermeable and saturated boundary conditions applied at the IRE/lubricant and lubricant/polymer interfaces, respectively. The diffusivity and solubility of mineral oil in PP were found to be 1.34 ± 0.35 (×10−10) cm2/s and 0.77 ± 0.13 (×10−2) g/g of PP, respectively. The current model was unable to quantitatively describe the diffusion of the Krytox® 143AC in the PP, possibly due to excessive swelling.
Changes in Thermodynamic Interactions at Highly Immiscible Polymer/Polymer Interfaces due to Deuterium Labeling