The research of starch as a matrix material for manufacturing biodegradable films has been gaining popularity in recent years, indicating its potential and possible limitations. To compete with conventional petroleum-based plastics, an enhancement of their low resistance to water and limited mechanical properties is essential. This review aims to discuss the various types of nanofillers and additives that have been used in plasticized starch films including nanoclays (montmorillonite, halloysite, kaolinite, etc.), poly-saccharide nanofillers (cellulose, starch, chitin, and chitosan nanomaterials), metal oxides (titanium dioxide, zinc oxide, zirconium oxide, etc.), and essential oils (carvacrol, eugenol, cinnamic acid). These reinforcements are frequently used to enhance several physical characteristics including mechanical properties, thermal stability, moisture resistance, oxygen barrier capabilities, and biodegradation rate, providing antimicrobial and antioxidant properties. This paper will provide an overview of the development of starch-based nanocomposite films and coatings applied in food packaging systems through the application of reinforcements and additives.

Nowadays, plastic contamination worldwide is a concerning reality that can be addressed with appropriate society education as well as looking for innovative polymeric alternatives based on the reuse of waste and recycling with a circular economy point of view, thus taking into consideration that a future world without plastic is quite impossible to conceive. In this regard, in this review, we focus on sustainable polymeric materials, biodegradable and bio-based polymers, additives, and micro/nanoparticles to be used to obtain new environmentally friendly polymeric-based materials. Although biodegradable polymers possess poorer overall properties than traditional ones, they have gained a huge interest in many industrial sectors due to their inherent biodegradability in natural environments. Therefore, several strategies have been proposed to improve their properties and extend their industrial applications. Blending strategies, as well as the development of composites and nanocomposites, have shown promising perspectives for improving their performances, emphasizing biopolymeric blend formulations and bio-based micro and nanoparticles to produce fully sustainable polymeric-based materials. The Review also summarizes recent developments in polymeric blends, composites, and nanocomposite plasticization, with a particular focus on naturally derived plasticizers and their chemical modifications to increase their compatibility with the polymeric matrices. The current state of the art of the most important bio-based and biodegradable polymers is also reviewed, mainly focusing on their synthesis and processing methods scalable to the industrial sector, such as melt and solution blending approaches like melt-extrusion, injection molding, film forming as well as solution electrospinning, among others, without neglecting their degradation processes.

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.

Boosting the transport and selectivity properties of membranes based on polymers of intrinsic microporosity (PIMs) toward one specific working analyte of interest is challenging. In this work, a novel family of PIM membranes, prepared by casting and exhibiting optima mechanical properties and high thermal stability, was synthesized from 4,4'-(2,2,2-trifluoro-1-phenylethane-1,1-diyl) bis(benzene-1,2-diol) and two tetrafluoro-nitrile derivatives. Gas permeability measurements evidenced a CO₂/CH₄ selectivity up to 170% relative to the reference polymer, PIM-1, in agreement with their calculated fractional free volume and the analysis of the textural properties by N₂ and CO₂ gas adsorption. Besides, the chemical modification by acid hydrolysis of the PIM membranes favored the permeability for lithium ions (LiCl 2M, 6 × 10^-9 cm²·s^-1) compared to other alkali metal analogs such as sodium (NaCl 2M, 7.38 × 10^-10 cm²·s^-1) and potassium (KCl 2M, 1.05 × 10^-9 cm²·s^-1). Moreover, the complete mitigation of the crossover of redox species with higher molecular sizes than the ions from alkali metal salts was confirmed by using in-line benchtop NMR methods. Additionally, the modified PIM membranes were measured in a symmetric electrochemical flow cell using an aqueous electrolyte by combining lithium ferro/ferricyanide redox compounds and lithium chloride. The electrochemical tests showed low polarization, high-rate capability, and capacity retention values of 99% when cycled at 10 mA·cm^-2 for over 50 cycles. Based on these results, these polymers could be used as highly selective and conducting membranes in electrodialysis for lithium separation and lithium-based redox flow batteries and as a protective layer in high-energy density lithium metal batteries.

Biodegradable and bio-based polymers, such as starch and gelatin, are emerging as an important alternative to the use of conventional polymers. In this work, different proportions (1/1, 1/1.5, 1/2, and 1/2.5) of these bio-based polymers will be investigated, with the primary objective of considering their strong moisture dependence as an advantage instead of a problem, as commonly considered. For this interesting challenge, the humidity-activated shape memory effect has been studied in both neat and plasticized starch. Additionally, for the first time, to the best of our knowledge, the shape-memory behavior activated by humidity in gelatin, as well as in starch/gelatin blends, is reported. In all cases, starch, gelatin, and their plasticized blends show excellent values in terms of strain fixity ratio, obtaining values of about 100% in all cases, and strain recovery ratio, with values higher than 90% for the samples studied. Moreover, considering their potential application as food packaging, mechanical response, wettability, water permeability, water uptake rate, and roughness is also studied in this work, taking into account the effect of the different amounts of gelatin on the final behavior of the materials.