The use of biodegradable polymers is of great importance nowadays in many applications. Some of the most commonly used biopolymers are polylactic acid (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) due to their superior properties and availability. In this manuscript, we use a facile and green modification method of organoclay (OC) by antimicrobial natural rosin which is considered as a toxicity-free reinforcing material, thus keeping the green character of the material. It increases the interlayer spacing between the clay platelets. This was proven by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) and found to impart antimicrobial properties to PLA/PBAT blends. The morphology of the resulting blends was conducted using scanning and transmission electron microscopies (SEM and TEM), and evidence of exfoliation and intercalation was observed. The thermal properties of the blends were studied using differential scanning calorimetry (DSC), and a detailed study of the crystallization of both PLA and PBAT was reported showing cold crystallization behavior of PLA. The final effect on mechanical and antimicrobial properties was also investigated. The obtained results reveal excellent possibility of using expanded OC modified PLA/PBAT polymer blends by adding a green material, antimicrobial natural rosin, for food packaging and biomembranes applications.
Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.
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