RESUMO
The product of ozonolysis, glycero-(9,10-trioxolane)-trioleate (ozonide of oleic acid triglyceride, [OTOA]), was incorporated into polylactic acid/polycaprolactone (PLA/PCL) blend films in the amount of 1, 5, 10, 20, 30 and 40% w/w. The morphological, mechanical, thermal and antibacterial properties of the biodegradable PLA/PCL films after the OTOA addition were studied. According to DSC and XRD data, the degree of crystallinity of the PLA/PCL + OTOA films showed a general decreasing trend with an increase in OTOA content. Thus, a significant decrease from 34.0% for the reference PLA/PCL film to 15.7% for the PLA/PCL + 40% OTOA film was established using DSC. Observed results could be explained by the plasticizing effect of OTOA. On the other hand, the PLA/PCL film with 20% OTOA does not follow this trend, showing an increase in crystallinity both via DSC (20.3%) and XRD (34.6%). OTOA molecules, acting as a plasticizer, reduce the entropic barrier for nuclei formation, leading to large number of PLA spherulites in the plasticized PLA/PCL matrix. In addition, OTOA molecules could decrease the local melt viscosity at the vicinity of the growing lamellae, leading to faster crystal growth. Morphological analysis showed that the structure of the films with an OTOA concentration above 20% drastically changed. Specifically, an interface between the PLA/PCL matrix and OTOA was formed, thereby forming a capsule with the embedded antibacterial agent. The moisture permeability of the resulting PLA/PCL + OTOA films decreased due to the formation of uniformly distributed hydrophobic amorphous zones that prevented water penetration. This architecture affects the tensile characteristics of the films: strength decreases to 5.6 MPa, elastic modulus E by 40%. The behavior of film elasticity is associated with the redistribution of amorphous regions in the matrix. Additionally, PLA/PCL + OTOA films with 20, 30 and 40% of OTOA showed good antibacterial properties on Pseudomonas aeruginosa, Raoultella terrigena (Klebsiella terrigena) and Agrobacterium tumefaciens, making the developed films potentially promising materials for wound-dressing applications.
RESUMO
Electrical conduction and oxygen diffusion mobility in the bixbyite ( Ia3Ì ) and rhombohedral ( R3Ì ) polymorphs of the Ln6MoO12-Δ (Ln = Er, Tm, Yb; Δ = δ, δ1, δ2; δ1 > δ2) heavy lanthanide molybdates, belonging to new, previously unexplored classes of potential mixed (ionic-electronic) conductors, have been studied in the range of 200-900 °C. The oxygen self-diffusion coefficient in bixbyite ( Ia3Ì ) Yb6MoO12-δ phase estimated by the temperature-programmed heteroexchange with C18O2 was shown to be much higher than that for rhombohedral ( R3Ì ) RI (with large oxygen deficiency) and ( R3Ì ) RII (with small oxygen deficiency) Ln6MoO12-Δ (Ln = Tm, Yb; Δ = δ1; δ1 > δ2) oxides. According to the activation energy for total conduction in ambient air, 0.99, 0.93, and 1.01 eV in Er6MoO12-δ, Tm6MoO12-δ, and Yb6MoO12-δ bixbyites, respectively, oxygen ion conductivity prevails in the range â¼200-500 °C. Oxygen mobility data for the rhombohedral Ln6MoO12-Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) phases RI and RII indicate that the oxygen in these phases exhibits mobility at much higher temperatures, such as those above 600-700 °C. Accordingly, below 600-700 °C they have predominantly electronic conductivity. As shown by total conductivity study of Ln6MoO12-δ (Ln = Er, Tm, Yb) bixbyites ( Ia3Ì ) and rhombohedral phases Ln6MoO12-Δ (Ln = Er, Tm, Yb; Δ = δ1, δ2) ( R3Ì ) in dry and wet air, the proton conductivity contribution exists only in Ln6MoO12-δ (Ln = Er, Tm, Yb) bixbyites up to 450-600 °C and decreases with a decreasing of the lanthanide ionic radius. The obtained data on the mobility of oxygen and the presence of proton contribution in bixbyites in the 300-600 °C temperature range make it possible to confirm unequivocally that Ln6MoO12-δ (Ln = Er, Tm, Yb) bixbyites are mixed electron-proton conductors at these temperatures.
