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Abstract In this work, the thermal degradation and the disintegrability under composting conditions of melt-processed blends based on ethylene-vinyl acetate and thermoplastic starch, EVA/TPS, as well as their nanocomposites, reinforced with natural bentonite, were studied. A special emphasis was first put on the influence of starch on the morphology, thermomechanical properties and hydrophilicity of these blends before composting analysis. In fact, the materials were characterized in terms of morphological, mechanical, thermal and structural properties as well as wettability performance, obtaining information about the immiscibility of the blends and their compatibilization when natural bentonite is used. The thermal stability of starch was increased according with the EVA content in the blend, while the compatibility between both polymeric phases was increased by adding the nanoclays. Consequently, the disintegration under composting condition at laboratory scale level of the obtained materials was conducted and the thermal and chemical-structural properties as well as the surface microstructural changes of recovered samples at different stages of disintegration were studied. Disintegration tests showed that EVA/TPS blends and their nanocomposites presented positive interactions, which delay the disintegration of TPS matrix in compost, thus improving TPS stability. Moreover, blending biodegradable polymers such as TPS with non-biodegradable polymers like EVA leads to the increase of compostable polymer percentage in partially-degradable materials giving a possible solution for the end-life of these materials after their use. Highlights • The thermal, chemical-structural as well as surface microstructural changes of disintegrated sample were studied. • Natural bentonite increase the EVA/TPS compatibility delaying the disintegration of TPS matrix in compost. • Melt-blending TPS with EVA increase the stability of starch-based materials. [ABSTRACT FROM AUTHOR]

In this work the thermally-activated shape memory response of biodegradable nanocomposites based on PLA/PCL blend reinforced with different type of cellulose nanocrystals has been reported, and compared with those of the neat matrix, at the same transition temperature of 55 °C and at the same different deformations, 50%, 100% and 150%. In particular, cellulose nanocrystals have been synthesized and then functionalized by “grafting from” reaction by ring opening polymerization of both PLLA and PCL using the OH groups onto the cellulose nanocrystals surface as initiators for the reaction. The morphology, thermal and mechanical analysis have been performed in order to obtain the parameters for the thermo-mechanical shape memory cycles. Moreover, the addition of the CNC-based nanofillers on the compatibility of PLA-PCL blends in 70:30 proportion has been evaluated. All the biodegradable nanocomposite formulations showed excellent shape memory response, similar to those of the neat matrix, with strain recovery ratio and strain fixity ratio higher than 80% and 90%, respectively. This fact indicates that in this case, the shape memory response of the nanocomposites is mainly controlled by the response of the neat blend and they are slightly influenced by the increase of compatibility between the components of the blend. In addition, all nanocomposite films were fully disintegrated under composting conditions confirming their biodegradable nature, obtaining that the presence of CNC-based nanofillers speeds up the disintegration rate of the nanocomposites in comparison with the pure matrix. [ABSTRACT FROM AUTHOR]

In this work, the effect of the addition of different amount of nanosized hydroxyapatite (nHA) on the shape memory behavior of blends based on poly (lactic acid) (PLA) and poly (ε-caprolactone) (PCL) has been studied. In particular PLA/PCL blend with 70 wt % PLA has been reinforced with 0.5, 1 and 3 wt % nHA. Moreover, the relationship between the morphology and the final properties of the nanocomposites has been investigated by field emission scanning electron microscopy, confocal Raman spectroscopy and atomic force microscopy. In particular, PeakForce has been used to study quantitative nanomechanical properties of the multifunctional materials leading to conclusion that nHA increase the phase separation between PLA and PCL as well as act as reinforcements for the PCL-rich phase of the nanocomposites. Furthermore, excellent thermally-activated shape memory response has been obtained for all the nanocomposites at 55 °C. Finally, the disintegration under composting conditions at laboratory scale level was studied in order to confirm the biodegradable character of these nanocomposites. Indeed, these materials are able to be used for biomedical issues as well as for packaging applications where both thermally-activated shape memory effect and biodegradability are requested. [ABSTRACT FROM AUTHOR]

Fully biobased edible films were prepared using native potato starch plasticized with glycerol and further reinforced with catechin (Cat) and starch nanocrystals (SNC) obtained by acidic hydrolysis from waxy maize starch granules. The thermal stability of starch nanocrystals obtained at different pH was studied, resulting on a decreasing in thermal stability at higher pH values. The X-ray diffraction patterns of the plasticized reinforced materials display complete destructuration of starch by solvent casting process. Plasticized films showed lower onset degradation temperatures than non-plasticized starch film. The reduction of the inter- and intra-molecular bonds interaction within the polymer matrix due to glycerol presence leads to a decrease of the thermal stability of the whole system. On the other hand, Cat and SNC produced an increase on the thermal stability of the bionanocomposites delaying the beginning of the thermal decomposition of starch/glycerol systems of about 20 °C. The mechanical performance was also improved in the ternary bionanocomposite edible films. All the edible films were fully disintegrated in compost conditions suggesting their possible applications as biodegradable edible films for packaging. [ABSTRACT FROM AUTHOR]

Blending commercial homopolymers represents a low cost and an easy scalable process to extend the use of the pristine homopolymers to an industrial level. Actually, the processing of blends by extrusion is the usual solution followed in the industry. However, commonly polymer blends are immiscible, provoking phase separation, which can be in the macro, micro or nano scale, depending on the polymers as well as on the processing conditions, affecting the final properties of the blends. Therefore, this paper aims to study the shape memory behavior in biodegradable blends based on poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) in different concentrations. A completely thermal and mechanical characterization of the blends was performed, correlating the results with the observed morphology. In addition, two different biodegradation studies were performed in order to correlate the effect of each homopolymer with the degradation behavior of the biodegradable blends. [ABSTRACT FROM AUTHOR]

Smart and functional properties of coumarin and PCL-based polyurethane (PU) nanocomposites reinforced with both pristine silica nanoparticles and silica nanoparticles modified with coumarin, have been studied. Coumarin is a photo-responsive derivative, which induces photo-crosslinking when it is incorporated in the PU moieties. Swelling measurements were performed to study the photo-crosslinking fraction and the results are in concordance with the degree of crosslinking (DC) calculated by UV measurements. Shape memory behavior was studied by thermo-mechanical cycles, by measuring the strain recovery and shape fixity ratios of the photo-crosslinked films. The modification of silica nanoparticles allows an improvement in the dispersion of the reinforcements into the PU matrix, which leads to an enhancement of the shape memory properties. Finally, the materials were disintegrated under composting conditions at laboratory scale level to confirm their biodisintegrable behavior. Image 1 • Functional polyurethanes based on poly-e-caprolactone and coumarin have been evaluated as coatings. • Photo-crosslinking degree was measured by swelling and the results are in concordance with UV measurements. • The incorporation of coumarin-functionalized silica nanoparticles leads to a enhancement of the shape memory performance. • The nanocomposites were completely disintegrated after 14 days under composting conditions. [ABSTRACT FROM AUTHOR]