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 n-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 (D_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 (E_A) were calculated based on the temperature dependence of the D_P using the Arrhenius approach. In total, 290 D_P values for 55 individual substances were determined, and 38 E_A values were derived from these data. The E_A correlated well with the molecular volume of the investigated substances. Moreover, the pre-exponential factor D₀ showed a correlation with E_A. These correlations enabled the establishment of diffusion modeling parameters for PLA, allowing the prediction of D_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.