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Biodegradable blends based on plasticized poly(lactic acid) PLA and thermoplastic starch (TPS) have been obtained. The influence of the PLA plasticizer as a compatibility agent has been studied by using two different plasticizers such as neat oligomeric lactic acid (OLA) and functionalized with maleic acid (mOLA). In particular, the morphological, thermal, and mechanical properties have been studied as well as the shape memory ability of the melt-processed materials. Therefore, the influence of the interaction between different plasticizers and the PLA matrix as well as the compatibility between the two polymeric phases on the thermally-activated shape memory properties have been studied. It is very interesting to use the same additive able to act as both plasticizer and compatibilizer, decreasing the glass transition temperature of PLA to a temperature close to the physiological one, obtaining a material suitable for potential biomedical applications. In particular, we obtain that OLA-plasticized blend (oPLA/TPS) show very good thermally-activated capability at 45 °C and 50% deformation, while the blend obtained by using maleic OLA (moPLA/TPS) did not show shape memory behavior at 45 °C and 50% deformation. This fact is due to their morphological changes and the loss of two well-distinguished phases, one acting as fixed phase and the other one acting as switching phase to typically obtain shape memory response. Therefore, the thermally-activated shape memory results show that it is very important to make a balance between plasticizer and compatibilizer, considering the need of two well-established phases to obtain shape memory response.

In this work, the in vitro degradation behavior of nanofibers was investigated in phosphate buffer solution (PBS) and simulated body fluid (SBF) to study their degradation behavior, as well as their bioactivity. The degradation was studied at different immersion times in order to evaluate how the presence of Mg-based nanoparticles can affect the degradation in terms of morphology, crystallinity, degradation rate and pH changes, and finally to evaluate the bioactivity of PCL-based electrospun nanofibers. We found that the degradation of the materials takes more than 3 months; however, the presence of nanoparticles seems to have an accelerating effect on the degradation of the electrospun nanofibers based on PCL. In fact, a reduction in diameter of almost 50% was observed with the highest content of both types of nanoparticles and an increase in crystallinity after 296 days of immersion in PBS. Moreover, the carbonyl index was calculated from an FTIR analysis, and a reduction of 20–30% was observed due to the degradation effect. Additionally, the bioactivity of PCL-based electrospun nanofibers was studied and the formation of crystals on the nanofibers surface was detected, except for neat electrospun PCL related to the formation of NaCl and apatites, depending on the amount and type of nanoparticles. The presence of apatites was confirmed by an XRD analysis and FT-IR analysis observing the characteristic peaks; furthermore, the EDX analysis demonstrated the formation of apatites than can be reconducted to the presence of HA when 20 wt% of nanoparticles is added to the PCL electrospun fibers.

In this work, a comparative study between the morphology, the thermal and the mechanical properties of poly(ɛ-caprolactone) (PCL)-based electrospun fiber mats reinforced with both MgO and Mg(OH) nanoparticles, is carried out. Both MgO and Mg(OH) nanoparticles have been added in a range of concentrations such as 0.5, 1, 5, 10, 20 wt% with respect to the PCL matrix, with the aim of improving their mechanical properties in comparison with neat PCL electrospun fibers. From the morphological point of view, electrospun fibers are randomly collected and an increase in the average fiber diameter with the addition of nanoparticles is observed. The addition of both types of nanoparticles lower the onset degradation temperature as well as the maximum degradation temperature of neat ePCL of about 50 °C with the higher content of nanoparticles. Furthermore, PCL electrospun nanofiber mats show a degree of crystallinity of 53%, which is quite high. However, the addition of 20 wt% of both MgO and Mg(OH) lowers the crystallinity of the reinforced electrospun fibers to 50% and 43% for PCL + MgO 20 wt% and Mg(OH) 20 wt%, respectively.

This review aims to point out the importance of the synergic effects of two relevant and appealing polymeric issues: electrospun fibers and shape-memory properties. The attention is focused specifically on the design and processing of electrospun polymeric fibers with shape-memory capabilities and their potential application fields. It is shown that this field needs to be explored more from both scientific and industrial points of view; however, very promising results have been obtained up to now in the biomedical field and also as sensors and actuators and in electronics.

In this work, different poly (lactic acid) (PLA)-based nanocomposite electrospun fibers, reinforced with both organic and inorganic nanoparticles, were obtained. As organic fibers, cellulose nanocrystals, CNC, both neat and functionalized by “grafting from” reaction, chitosan and graphene were used; meanwhile, hydroxyapatite and silver nanoparticles were used as inorganic fibers. All of the nanoparticles were added at 1 wt% with respect to the PLA matrix in order to be able to compare their effect. The main aim of this work was to study the morphological, thermal and mechanical properties of the different systems, looking for differences between the effects of the addition of organic or inorganic nanoparticles. No differences were found in either the glass transition temperature or the melting temperature between the different electrospun systems. However, systems reinforced with both neat and functionalized CNC exhibited an enhanced degree of crystallinity of the electrospun fibers, by up to 12.3%. From a mechanical point of view, both organic and inorganic nanoparticles exhibited a decreased elastic modulus and tensile strength in comparison to neat electrospun PLA fibers, improving their elongation at break. Furthermore, all of the organic and inorganic reinforced systems disintegrated under composting conditions after 35 days.

Nano-biocomposite films based on poly (lactic acid) (PLA) were prepared by adding thymol (8 wt.%) and a commercial montmorillonite (D43B) at different concentrations (2.5 and 5 wt.%). The antioxidant, antimicrobial, and disintegration properties of all films were determined. A kinetic study was carried out to evaluate the thymol release from the polymer matrix into ethanol 10% (v/v) as food simulant. The nanostructured networks formed in binary and ternary systems were of interest in controlling the release of thymol into the food simulant. The results indicated that the diffusion of thymol through the PLA matrix was influenced by the presence of the nanoclay. Disintegration tests demonstrated that the incorporation of both additives promoted the breakdown of the polymer matrix due to the presence of the reactive hydroxyl group in the thymol structure and ammonium groups in D43B. Active films containing thymol and D43B efficiently enhanced the antioxidant activity (inhibition values higher than 77%) of the nano-biocomposites. Finally, the addition of 8 wt.% thymol and 2.5 wt.% D43B significantly increased the antibacterial activity against Escherichia coli and Staphylococcus aureus 8325-4, resulting in a clear advantage to improve the shelf-life of perishable packaged food.

Thymol and silver nanoparticles (Ag-NPs) were used to develop poly(lactic acid) (PLA)-based films with antioxidant and antibacterial performance. Different amounts of thymol (6 and 8 wt%) and 1 wt% Ag-NPs were added to PLA to produce the active films. Ag-NPs and thymol were successfully identified in the nanocomposite structures using spectroscopic techniques. A kinetic study was performed to evaluate the release of thymol and Ag-NPs from the nanocomposites to an aqueous food simulant (ethanol 10%, v/v) at 40 °C. The diffusion of thymol from the polymer matrix was affected by the presence of non-migrating Ag-NPs, which showed non-Fickian release behavior. The ternary system including 1 wt% Ag-NPs and 8 wt% thymol showed clear antibacterial performance by reducing the cell viability of Escherichia coli and Staphylococcus aureus by around 40% after 3 and 24 h of storage at 4, 25, and 37 °C compared to neat PLA. Significant antioxidant behavior of all active films was also confirmed using the 2,2-diphenyl-1-picrylhydrazyl (DPPH) method. The obtained nanocomposite films based on PLA and the addition of Ag-NPs and thymol were proven to have combined antioxidant and antibacterial performance, with controlled release of thymol. These formulations have potential applications in the development of innovative and customized active packaging systems to increase the shelf-life of food products.

In this work poly("-caprolactone) (PCL) based electrospun mats were prepared by blending PCL with microcrystalline cellulose (MCC) and poly(3-hydroxybutyrate) (PHB). The electrospinning processing parameters were firstly optimized with the aim to obtain scalable PCL-based electrospun mats to be used in the industrial sector. Neat PCL as well as PCL-MCC and PCL-PHB based mats in different proportions (99:1; 95:5; 90:10) were prepared. A complete morphological, thermal and mechanical characterization of the developed materials was carried out. Scanning electron microscopy (SEM) observations showed that the addition of PHB to the PCL matrix considerably reduced the formation of beads. Both the addition of MCC and PHB reduced the thermal stability of PCL, but obtained materials with enough thermal stability for the intended use. The electrospun PCL fibers show greatly reduced flexibility with respect to the PCL bulk material, however when PCL is blended with PHB their stretchability is increased, changing their elongation at break from 35% to 70% when 10 wt% of PHB is blended with PCL. However, the mechanical response of the different blends increases with respect to the neat electrospun PCL, offering the possibility to modulate their properties according to the required industrial applications.

In this paper flexible electrospun mats based on poly(lactic acid) (PLA) blended with 25 wt% of poly(hydroxibutyrate) (PHB) and further plasticized with three different concentration of oligomeric lactic acid (OLA) were developed. The morphological, structural, thermal and mechanical performance of electrospun mats was evaluated. OLA improves the crystallization rate of PLA presenting better interaction with PLA than with PHB. The incorporation of OLA to PLA-PHB blends produced a decrease on the viscosity of the polymeric solutions, leading to a reduction of the fibers diameters by increasing the amount of OLA plasticizer in the final blends. The highest amount of OLA of 20 wt% respect to PLA-PHB blend produced some bead defects in the fibers, which leads to a reduction of the mechanical performance of woven no-woven electrospun mats. Furthermore, all the electrospun mats were disintegrated in composting conditions showing their interest as compostable materials. The ternary system PLA-PHB-OLA15, showed the best results in term of structural and mechanical properties as well as appropriate disintegration in compost suggesting their potential applications as agricultural mulch films.

In this work, different nanocomposite electrospun fiber mats were obtained based on poly(e-caprolactone) (PCL) and reinforced with both organic and inorganic nanoparticles. In particular, on one side, cellulose nanocrystals (CNC) were synthesized and functionalized by “grafting from” reaction, using their superficial OH– group to graft PCL chains. On the other side, commercial chitosan, graphene as organic, while silver, hydroxyapatite, and fumed silica nanoparticles were used as inorganic reinforcements. All the nanoparticles were added at 1 wt% with respect to the PCL polymeric matrix in order to compare the different behavior of the woven no-woven nanocomposite electrospun fibers with a fixed amount of both organic and inorganic nanoparticles. From the thermal point of view, no difference was found between the effect of the addition of organic or inorganic nanoparticles, with no significant variation in the Tg (glass transition temperature), Tm (melting temperature), and the degree of crystallinity, leading in all cases to high crystallinity electrospun mats. From the mechanical point of view, the highest values of Young modulus were obtained when graphene, CNC, and silver nanoparticles were added to the PCL electrospun fibers. Moreover, all the nanoparticles used, both organic and inorganic, increased the flexibility of the electrospun mats, increasing their elongation at break.

Biodegradable multicomponent films based on poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) plasticized with oligomeric lactic acid (OLA), reinforced with synthetized cellulose nanocrystals (CNC) and modified by a natural additive with antimicrobial activity (carvacrol) were formulated and processed by extrusion. Morphological, mechanical, thermal, migration and barrier properties were tested to determine the effect of different components in comparison with neat poly(lactic acid). Results showed the positive effect of CNC in the five components based films, with the increase of the Young’s modulus of the PLA_PHB_10Carv_15OLA, associated with an increase in the elongation at break (from 150% to 410%), by showing an OTR reduction of 67%. Disintegrability in compost conditions and enzymatic degradation were tested to evaluate the post-use of these films. All formulations disintegrated in less than 17 days, while proteinase K preferentially degraded the amorphous regions, and crystallinity degree of the nanocomposite films increased as a consequence of enzyme action.

Starch nanocrystals (SNCs) were successfully synthesized by acid hydrolysis of waxy barley starch and were characterized by X-ray diffraction, scanning and transmission electron microscopy. Nanocomposites based on ethylene-co-vinyl acetate (EVA) and SNCs were produced by melt-processing using a microextruder. Interesting is to note that SNCs do not lose their crystalline nature during melt-processing. Moreover, the mechanical and thermal properties of the neat matrix were improved by the addition of SNCs thanks to the strong hydrogen bonding between the nanofillers surface and the acetate groups of the matrix. The introduction of 2 wt.% and 5 wt.% of SNCs into the matrix, lead to an increase of its elastic modulus of about 50% and 100%, respectively. Moreover, the addition of SNCs provoked an increase of the thermal stability of about 10 °C respect to the neat matrix. These results clearly revealed the possibility to introduce SNCs in a polymeric matrix by extrusion enabling to reach materials with enhanced mechanical and thermal properties due to beneficial hydrogen bonding between SNCs and EVA.

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.

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.

Fully bio-based and biodegradable active films based on poly(lactic acid) (PLA) blended with poly(3-hydroxybutyrate) (PHB) and incorporating lactic acid oligomers (OLA) as plasticizers and carvacrol as active agent were extruded and fully characterized in their functional properties for antimicrobial active packaging. PLA_PHB films showed good barrier to water vapor, while the resistance to oxygen diffusion decreased with the addition of OLA and carvacrol. Their overall migration in aqueous food simulant was determined and no significant changes were observed by the addition of carvacrol and OLA to the PLA_PHB formulations. However, the effect of both additives in fatty food simulant can be considered a positive feature for the potential protection of foodstuff with high fat content. Moreover, the antioxidant and antimicrobial activities of the proposed formulations increased by the presence of carvacrol, with enhanced activity against Staphylococcus aureus if compared to Escherichia coli at short and long incubation times. These results underlined the specific antimicrobial properties of these bio-films suggesting their applicability in active food packaging.

In this work, a systematic study on the humidity-activated shape memory properties of dual-responsive shape memory bionanocomposites with both humidity- and thermally-activated shape memory effects is reported. The study is performed through humidity-mechanical cycles in an Instron machine with a temperature chamber equipped with an ultrasonic humidity generator. In particular, the bionanocomposites studied are based on blends of ethylene–vinyl acetate (EVA) and thermoplastic starch reinforced with natural bentonite. In our previous work, thermomechanical cycles are performed by using EVA-induced crystallization and a preliminary humidity-activated shape memory test is designed. Herein, the shape memory results of both blends and their nanocomposites reflect the very good ability to humidity-activated recover of the initial shape with values higher than 80%. Moreover, the ability to fix the temporary shape of this systems is very good, especially when nanofillers are added. The compatibilizer effect of natural bentonite is demonstrated by means of different techniques such as scanning emission microscopy and mapping by confocal Raman spectroscopy.

Carbon fiber composite laminates have good electrical properties due to the performance of the fibers, but the composite anisotropy induces a quite lower conductivity through the thickness. In fact, in this direction the fiber bundles are separated by insulating epoxy matrix. In this work, CNTs (carbon nanotubes) with different geometries and functionalization have been added to an epoxy resin to improve the electrical performance. The nanofilled matrix has been used to produce carbon fiber (CF) composites for aerospace applications. Multiscale modeling was used to predict some important parameters such as percolation threshold and the model has been successfully verified with experimental results. The results reported show a good improvement of the electrical and mechanical properties both in the matrix and in the composites. In particular, in composites with the nanocomposite matrix, an improvement of one order of magnitude in the electrical conductivity through the laminate thickness has been achieved.

Active nanocomposite films based on poly(lactic acid) (PLA), thymol and silver nanoparticles (Ag-NPs) were prepared and characterized. PLA films containing 6 and 8 wt% thymol and 1 wt% Ag-NPs were processed by extrusion to obtain binary and ternary formulations. The addition of thymol and Ag-NPs modified the PLA thermal, optical and barrier properties; in particular water vapour permeability (WVP), maintaining oxygen transmission rate (OTR) values unchanged. Homogeneous surfaces in all films were obtained as proved by FESEM micrographs. The presence of the active additives enhanced the disintegration rate of PLA under composting conditions, which was completed in 14 days. Results suggest that these nanocomposite films could be considered promising degradable active packaging materials with low environmental impact.

Electrospun biobased and biodegradable nanocomposites for sustainable flexible films were developed. Poly(lactic acid) (PLA) was blended with 25Â wt% of poly(hydroxybutyrate) (PHB) to produce bead-less fibers and plasticized with 15Â wt% of acetyl(tributyl citrate) (ATBC) to obtain flexible materials. The system was further loaded with cellulose nanocrystals (CNC) in 1Â wt% and 5Â wt% to obtain bionanocomposites with improved thermal and mechanical resistance. The morphological, structural, thermal and mechanical performance of electrospun bionanocomposites was investigated. The effect of ATBC was characterized by a decrease of the glass transition temperature and an increase in the elongation at break. Meanwhile, CNC improved the thermal and mechanical resistance of mats. Thus, good performance for the intended use was achieved for the bionanocomposite loaded with 1Â wt% of CNC (PLA¿PHB¿ATBC¿CNC1), which also showed appropriate surface water resistance. All electrospun bionanocomposites were fully disintegrated under composting conditions showing their possible applications as compostable flexible film materials.

Blends of poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) plasticized with a lactic acid oligomer (OLA) added at three different concentrations (15, 20 and 30 wt% by weight), were prepared by an optimized extrusion process to improve the processability and mechanical properties of these biopolymers for flexible film manufacturing. Morphological, chemical, thermal, mechanical, barrier and migration properties were investigated and formulations with desired performance in eco-friendly films were selected. The efficiency of OLA as plasticizer for PLA_PHB blends was demonstrated by the significant decrease of their glass transition temperatures and a considerable improvement of their ductile properties. The measured improvements in the barrier properties are related to the higher crystallinity of the plasticized PLA_PHB blends, while the overall migration test underlined that all the proposed formulations maintained migration levels below admitted levels. The PLA_PHB blend with 30 wt% OLA was selected as the optimum formulation for food packaging, since it offered the best compromise between ductility and oxygen and water vapor barrier properties with practically no migration.

Bio-based films formed by poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) plasticized with an oligomer of the lactic acid (OLA) were used as supporting matrices for an antibacterial agent (carvacrol). This paper reports the main features of the processing and physico-chemical characterization of these innovative biodegradable material based films, which were extruded and further submitted to filmature process. The effect of the addition of carvacrol and OLA on their microstructure, chemical, thermal and mechanical properties was assessed. The presence of these additives did not affect the thermal stability of PLA_PHB films, but resulted in a decrease in their crystallinity and in the elastic modulus for the active formulations. The obtained results showed the effective presence of additives in the PLA or the PLA_PHB matrix after processing at high temperatures, making them able to be used in active and bio-based formulations with antioxidant/antimicrobial performance.