Diffusion Coefficients and Activation Energies of Diffusion of Organic Molecules in Poly(lactic acid) Films

Poly(lactic acid) (PLA) is one of the most important bio-based and industrial compostable materials in food packaging. Its barrier properties towards oxygen and moisture are well documented. However, data on barrier properties of PLA towards organic molecules are scarce in the literature. This study investigated the diffusion of various organic molecules, including <i>n</i>-alkanes, 1-alcohols, 2-ketones, ethers, esters, amines, and aromatics, in two commercial PLA films with thicknesses of 20 µm and 30 µm. The diffusion coefficient (<i>D</i>_P) values were determined from lag time in permeation tests conducted at temperatures ranging from 20 °C to 90 °C. The films were also characterized in terms of crystallinity, rigid and mobile amorphous fractions, and molecular weight. Activation energies (<i>E</i>_A) were calculated based on the temperature dependence of the <i>D</i>_P using the Arrhenius approach. In total, 290 <i>D</i>_P values for 55 individual substances were determined, and 38 <i>E</i>_A values were derived from these data. The <i>E</i>_A correlated well with the molecular volume of the investigated substances. Moreover, the pre-exponential factor <i>D</i>₀ showed a correlation with <i>E</i>_A. These correlations enabled the establishment of diffusion modeling parameters for PLA, allowing the prediction of <i>D</i>_P for untested substances. The diffusion behavior of PLA was further compared with the literature data for polyethylene terephthalate and polyethylene naphthalate, providing insights into the relative performance of these materials.