ABSTRACT:The preparation of nanocomposites of poly (ethylene terephthalate) (PET) and lamellar zirconium phosphorous compounds by melt extrusion was investigated. Two types of zirconium phosphorous compounds were synthesized by the direct precipitation reaction method: a-zirconium bis(monohydrogen orthophosphate) monohydrate (ZrP) and organic-inorganic hybrid layered zirconium phenylphosphonate (ZrPP). Composites containing 2 and 5 wt % ZrP and ZrPP were prepared in a twin-screw extruder and specimens were obtained by injection molding. The extent of dispersion of the layered filler in the composite matrix was investigated by X-ray diffraction and transmission electron microscopy (TEM). The crystallization and thermal properties were analyzed by differential scanning calorimetry and thermogravimetry, and the mechanical properties were evaluated by tensile tests. Whereas ZrP-containing composites showe characteristic diffraction peaks at 2y 11.78 (d ¼ 7.54 Å ), indicative of no delamination, ZrPP showed practically no low-angle diffraction peak at 2y 5.58 (d ¼ 15.24 Å ), indicating loss of the layered order. TEM images of ZrPP particles indicated the formation of an intercalated/partially delaminated nanocomposite. The behavior was attributed to the higher affinity of the polyester with phenyl groups on the platelet surface of ZrPP. In both cases, the addition of the fillers increased the crystallization rate and the modulus.

A hybrid material of polyaniline doped with dodecylbenzenesulfonic acid and conductive carbon black (PaniDBSA/CB) was prepared by in situ polymerization. The presence of low amount of CB (up to 25 wt %) resulted in a decrease in resistivity as compared to pure PaniDBSA. Composite with 25 wt % of CB presented the lowest resistivity and a tubular morphology characterized by microtubules with high aspect ratio evidenced by SEM examination. Higher amount of CB give rise to materials with higher resistivity values and a granular morphology, similar to pure carbon black. Ultraviolet-visible and electron paramagnetic resonance analyses were employed to evaluate the polaron concentration. X-ray diffraction was used to characterize the molecular structure of these composites. It was observed a decrease in the crystallinity degree and a shift of the polaron band transition toward lower wavelength as the amount of CB in the composite increases. From the EPR measurements, one can suggest that the higher chain order and polaron mobility is observed in hybrid with 25% of CB. This behavior is in agreement to the electrical resistivity values and SEM microscopy. The effect of CB on thermal stability of the composites was also investigated. The effect of the PaniDBSA/CB hybrid material on the processability and resistivity of the composites based on styrene-butadiene-styrene (SBS) block copolymer as the insulating matrix have been also evaluated.

Poly(lactic-co-glycolic acid) (PLGA) has been used in the field of tissue engineering as a scaffold due to its good biocompatibility, biodegradability and mechanical strength. With the aim to explore the degradability of PLGA electrospun nonwoven structures for oral mucosa tissue engineering applications, non-irradiated and gamma irradiated nonwovens were immersed in three different solutions, in which simulated body fluid (SBF) and artificial saliva are important for future oral mucosa tissue engineering. The nonwovens were immersed for 7, 15 and 30 days in SBF, culture media (DMEM) and artificial saliva at 37 °C. Before immersion in the solutions, the dosage of 15 kGy was applied for sterilization in one assay and compared with non-irradiated samples at the same timepoints. Samples were characterized using different techniques such as scanning electron microscopy (SEM), differential scanning calorimetric (DSC) and gel permeation chromatography (GPC) to evaluate the nonwoven degradation and Fourier-transform infrared spectroscopy (FTIR) to evaluate the chain scissions. Our results showed that PLGA nonwovens were constituted by semicrystalline fibers with moderate degradation properties up to thirty days. The non-irradiated samples exhibited slower kinetics of degradation than irradiated nonwovens. For immersion times longer than 7 days in the three different solutions, the mean diameter of irradiated fibers stayed in the same range, but significantly different from the control sample. On non-irradiated samples, the degradation kinetics was slower and the plateau in the diameter value was only attained after 30 days of immersion in the fluids. Plasticization (fluid absorption into the fiber structure) occurred in the bulk material, as confirmed by a decrease in Tg observed by DSC analyses of non-irradiated and irradiated nonwovens, in comparison with the respective controls. In addition, artificial saliva showed a higher capacity of influencing PLGA crystallization than SBF and DMEM. FTIR analyses showed typical PLGA chemical functional groups changes. These results will be important for future application of those PLGA electrospun nonwovens for oral mucosa regeneration.

BACKGROUND: Every minute, 1 million bottled drinks were purchased worldwide in 2017. Poly(ethylene terephthalate) (PET) bottles are highly recalcitrant wastes, taking at least 450 years to decompose naturally, and their accumulation in the environment triggers a series of environmental impacts. Recycling is an environmentally friendly alternative to PET waste management. A two-step PET depolymerization approach was studied in this work, comprising chemical glycolysis followed by enzymatic hydrolysis.RESULTS: In the glycolysis reaction, 100% PET was depolymerized in the presence of a eutectic solvent-based catalyst and ethylene glycol, releasing bis(2-hydroxyethyl) terephthalate (BHET) as the main product (70% yield). The recovered BHET was then hydrolysed by the highly efficient Candida antarctica lipase B, releasing terephthalic acid (TPA), achieving 0.98 of mole fraction in the best result of the experimental design. The overall yield of chemo-enzymatic depolymerization of PET into TPA was 57%. CONCLUSION: Using this integrated approach, a high overall yield of TPA from PET could be achieved within a short process timeframe (24 h).

ObstractThe biodegradable aliphatic oligoester oligo(trimethylene separate) (OTS) was synthesized by polycondensation and used to plasticize poly(lactic acid) (PLA). Casting films of PLA and PLA/OTS with concentrations of 1, 5 and 10 wt.% were prepared, and these films were characterized by thermal analyses, crystallinity, rheology and mechanical tests. DSC revealed the decrease in the T g of PLA films with addition of the oligomer and a partial immiscibility. Addition of OTS to PLA slightly decrease the thermal stability as well as increase the degree of crystallinity of these films. Dynamic-mechanical analyses of casting films showed that the PLA/OTS system presented lower storage modulus than PLA and mechanical test revealed an increased in the elongation at break for PLA films containing the oligoester. The results make possible to conclude that the oligomer synthesized from bio-based monomers acts as a plasticizer of PLA increasing the PLA ductility. Keywords: plasticization poly(lactic acid), oligoesters, trimethylene sebacate, cast films.Aiming to investigate the efficiency of oligoester as PLA biodegradable plasticizers, a oligoester based on two