This work reports on the first attempt to prepare bioderived polymer films by blending polylactic acid (PLA) and poly(dodecylene furanoate) (PDoF). This blend, containing 10 wt% PDoF, was filled with reduced graphene oxide (rGO) in variable weight fractions (from 0.25 to 2 phr), and the resulting nanocomposites were characterized to assess their microstructural, thermal, mechanical, optical, electrical, and gas barrier properties. The PLA/PDoF blend resulted as immiscible, and the addition of rGO, which preferentially segregated in the PDoF phase, resulted in smaller (from 2.6 to 1.6 µm) and more irregularly shaped PDoF domains and in a higher PLA/PDoF interfacial interaction, which suggests the role of rGO as a blend compatibilizer. rGO also increased PLA crystallinity, and this phenomenon was more pronounced when PDoF was also present, thus evidencing a synergism between PDoF and rGO in accelerating the crystallization kinetics of PLA. Dynamic mechanical thermal analysis (DMTA) showed that the glass transition of PDoF, observed at approx. 5 °C, shifted to a higher temperature upon rGO addition. The addition of 10 wt% PDoF in PLA increased the strain at break from 5.3% to 13.0% (+145%), and the addition of 0.25 phr of rGO increased the tensile strength from 35.6 MPa to 40.2 MPa (+13%), without significantly modifying the strain at break. Moreover, rGO decreased the electrical resistivity of the films, and the relatively high percolation threshold (between 1 and 2 phr) was probably linked to the low aspect ratio of rGO nanosheets and their preferential distribution inside PDoF domains. PDoF and rGO also modified the optical transparency of PLA, resulting in a continuous decrease in transmittance in the visible/NIR range. Finally, rGO strongly modified the gas barrier properties, with a remarkable decrease in diffusivity and permeability to gases such as O₂, N_2, and CO₂. Overall, the presented results highlighted the positive and sometimes synergistic role of PDoF and rGO in tuning the thermomechanical and functional properties of PLA, with simultaneous enhancement of ductility, crystallization kinetics, and gas barrier performance, and these novel polymer nanocomposites could thus be promising for packaging applications.

The CO₂ transport process was studied in a series of amine-modified epoxy resins having different cross-linking densities but the same chemical environment for the penetrant molecules. Positron Annihilation Lifetime Spectroscopy (PALS) was used to monitor the free volume structure of the samples and experimentally evaluate their fractional free volume f_h(T) and its temperature evolution. The analysis of the free volume hole size distribution showed that all the holes have a size large enough to accommodate the penetrant molecules at temperatures T above the glass transition temperature T_g. The measured gas diffusion constants at T > T_g have been reproduced in the framework of the free volume theory of diffusion using a novel procedure based on the use of f_h(T) as an input experimental parameter.

The efficient separation and removal of carbon dioxide (${CO}_2$) from its mixtures is an important technological challenge to limit effects resulting from the increase of the carbon dioxide concentration in the atmosphere. Membrane technology is an environmentally friendly approach, highly scalable and less energy-consuming than conventional methods such as adsorption, absorption and cryogenic separation. Hybrid membrane materials incorporating inorganic filler nanostructures in polymer matrices having polyethylene glycol (PEG) as a plasticized additive are promising membrane materials given the presence of ${CO}_2$-philic polar functional groups of PEGs and the structural refinements on the blend matrix consequent to the filler distribution. In this review, literature information on hybrid polymer/PEG membranes are critically reviewed to discuss how filler dispersion in the blend matrix gives rise to enhanced ${CO}_2$ separation performances with respect to those obtained with traditional mixed matrix membranes where filler nanostructures are dispersed in the neat polymer. The discussion will be focused on the correlation between the ${CO}_2$ transport properties, membrane structural properties and defect resulting from the polymer-filler incompatibility. It is shown that hybrid polymer/PEG membranes with dispersed filler nanostructures simultaneously offer improved ${CO}_2$ separation performances and enhanced mechanical properties compared with nanocomposite ones where filler particles are dispersed in the neat polymer matrix. PEG addition enhances the filler-matrix compatibility, delays filler aggregation and limits the formation of filler-matrix interface defects.