Biobased Films Based on Chitosan and Microcrystalline Cellulose for Sustainable Packaging Applications.

The transition to a more sustainable lifestyle requires a move away from petroleum-based sources and the investigation and funding of renewable and waste feedstocks to provide biobased sustainable materials. The formulation of films based on chitosan and microcrystalline cellulose with potential applications in the packaging sector has been demonstrated. Glycerol is also used as a plasticizer in the formulation of flexible films, while mucic acid is used as a valid alternative to acetic acid in such films. The film based on chitosan, microcrystalline cellulose, glycerol, and mucic acid shows properties and a performance similar to those of the film formulated with acetic acid, and, in addition, it seems that the photo-oxidation resistance of the film based on mucic acid is better than that of the material containing acetic acid. The films were characterized using spectroscopy (FTIR and UV-vis), tensile testing, water contact angle measurements, surface observations, and photo-oxidation resistance measurements. The presence of microcrystalline cellulose enhances the mechanical behavior, UV barrier properties, and surface hydrophobicity of the film. The feasibility of formulating chitosan-based films, with or without microcrystalline cellulose, which exhibit good properties and performances is demonstrated. Mucic acid instead of acetic acid is used in the formulation of these film.

Photo- and Water-Degradation Phenomena of ZnO Bio-Blend Based on Poly(lactic acid) and Polyamide 11.

The goal of this work was to investigate the morphological and chemical-physical changes induced by adding ZnO nanoparticles to bio-based polymeric materials based on polylactic acid (PLA) and polyamide 11 (PA11). Precisely, the photo- and water-degradation phenomena of nanocomposite materials were monitored. For this purpose, the formulation and characterization of novel bio-nanocomposite blends based on PLA and PA11 at a ratio of 70/30 wt.% filled with zinc oxide (ZnO) nanostructures at different percentages were performed. The effect of ZnO nanoparticles (≤2 wt.%) within the blends was thoroughly explored by employing thermogravimetry (TGA), size exclusion chromatography (SEC), matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) and scanning and transmission electron microscopy (SEM and TEM). Adding up to 1% wt. of ZnO resulted in a higher thermal stability of the PA11/PLA blends, with a decrement lower than 8% in terms of molar masses (MMs) values being obtained during blend processing at 200 °C. ZnO promoted trans-ester-amide reactions between the two polymers, leading to the formation of PLA/PA11 copolymers. These species could work as compatibilisers at the polymer interface, improving thermal and mechanical properties. However, the addition of higher quantities of ZnO affected such properties, influencing the photo-oxidative behaviour and thus thwarting the material's application for packaging use. The PLA and blend formulations were subjected to natural aging in seawater for two weeks under natural light exposure. The 0.5% wt. ZnO sample induced polymer degradation with a decrease of 34% in the MMs compared to the neat samples.

Flexible Perfluoropolyethers-Functionalized CNTs-Based UHMWPE Composites: A Study on Hydrogen Evolution, Conductivity and Thermal Stability.

Flexible conductive composites based on ultra-high molecular weight polyethylene (UHMWPE) filled with multi-walled carbon nanotubes (CNTs) modified by perfluoropolyethers (PFPEs) were produced. The bonding of PFPE chains, added in 1:1 and 2:1 weight ratios, on CNTs influences the dispersion of nanotubes in the UHMWPE matrix due to the non-polar nature of the polymer, facilitating the formation of nanofillers-rich conductive pathways and improving composites' electrical conductivity (two to five orders of magnitude more) in comparison to UHMWPE-based nanocomposites obtained with pristine CNTs. Electrochemical atomic force microscopy (EC-AFM) was used to evaluate the morphological changes during cyclic voltammetry (CV). The decrease of the overpotential for hydrogen oxidation peaks in samples containing PFPE-functionalized CNTs and hydrogen production (approximately -1.0 V vs. SHE) suggests that these samples could find application in fuel cell technology as well as in hydrogen storage devices. Carbon black-containing composites were prepared for comparative study with CNTs containing nanocomposites.

Understanding the Effects of Crosslinking and Reinforcement Agents on the Performance and Durability of Biopolymer Films for Cultural Heritage Protection.

In the last two decades, the naturally occurring polysaccharides, such as chitosan and pectin, have gained great attention having potential applications in different sectors, from biomedical to new generation packaging. Currently, the chitosan and pectic have been proposed as suitable materials also for the formulation of films and coatings for cultural heritage protection, as well as packaging films. Therefore, the formulation of biopolymer films, considering only naturally occurring polymers and additives, is a current challenging trend. This work reports on the formulation of chitosan (CS), pectin (PC), and chitosan:pectin (CS:PC) films, also containing natural crosslinking and reinforcement agents, such as citric acid (CA) and halloysite nanotubes (HNT), through the solvent casting technique. The produced films are characterized through water contact angle measurements, infrared and UV-visible spectroscopy and tensile test, while the durability of the CS:PC films is evaluated subjecting the film to accelerated UVB exposure and monitoring the photo-oxidation degradation in time though infrared spectroscopy. All obtained results suggest that both crosslinking and reinforcement agents have beneficial effects on the wettability, rigidity, and photo-oxidation resistance of biopolymer films. Therefore, these biopolymer films, also containing naturally occurring additives, have good properties and performance and they are suitable as coverage films for cultural heritage protection.

A Review of Bioplastics and Their Adoption in the Circular Economy.

The European Union is working towards the 2050 net-zero emissions goal and tackling the ever-growing environmental and sustainability crisis by implementing the European Green Deal. The shift towards a more sustainable society is intertwined with the production, use, and disposal of plastic in the European economy. Emissions generated by plastic production, plastic waste, littering and leakage in nature, insufficient recycling, are some of the issues addressed by the European Commission. Adoption of bioplastics-plastics that are biodegradable, bio-based, or both-is under assessment as one way to decouple society from the use of fossil resources, and to mitigate specific environmental risks related to plastic waste. In this work, we aim at reviewing the field of bioplastics, including standards and life cycle assessment studies, and discuss some of the challenges that can be currently identified with the adoption of these materials.

Bionanocomposite Films Containing Halloysite Nanotubes and Natural Antioxidants with Enhanced Performance and Durability as Promising Materials for Cultural Heritage Protection.

In the last decade, the interest toward the formulation of polymer films for cultural heritage protection continuously grew, and these films must be imperatively transparent, removable, and should not react/interact with surface of the artworks. In this research, bionanocomposite films, based on chitosan (Ch) and pectin (P) and containing naturally occurring fillers and antioxidants, were formulated by solvent casting methods and were accurately characterized. The natural halloysite nanotubes (HNT) have a two-fold role, specifically, physical compatibilizer and antioxidant carrier. Therefore, the theoretical solubility between Ch and P was estimated considering Hoy's method for solubility of polymers, while the optimum ratio between biopolymer constituents was assessed by ζ-potential measurements. The transparency, wettability, and mechanical behavior of Ch:P films, also in presence of HNT without and with antioxidants, were investigated. The beneficial effects of natural antioxidants, such as vanillic acid (VA) and quercetin (Q), on Ch:P/HNT durability were found.

Role of Organo-Modifier and Metal Impurities of Commercial Nanoclays in the Photo- and Thermo-Oxidation of Polyamide 11 Nanocomposites.

The photo-oxidative degradation processes of bio-based PA11 nanocomposites containing montmorillonite (MMT) and the organo-modified Cloisite®30B were investigated to discriminate the influence of organo-modified components on the polymer durability. Indeed, despite the extensive studies reported, there are still ambiguous points to be clarified from the chemical point of view. To this aim, UV-aged materials were analyzed by Size Exclusion Chromatography (SEC), Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry (MALDI-TOF MS). This enabled determining changes in both chemical structure and Molar Masses (MMs) induced by light, heat and oxygen exposure. The addition of organo-modified nanoclays strongly affected the PA11 light durability, triggering the macromolecular chains scission due to the typical αH, Norrish I and II mechanisms. However, the main contribution in boosting the photo-oxidative degradation is induced by iron impurities contained into the clays. Conversely, thermo-oxidation process performed at 215 °C was unambiguously affected by the presence of the organo-modifiers, whose presence determined an enhancement of crosslinking reactions.

Natural Compounds as Sustainable Additives for Biopolymers.

In the last few decades, the interest towards natural compounds, coming from a natural source and biodegradable, for biopolymers is always increasing because of a public request for the formulation of safe, eco-friendly, and sustainable materials. The main classes of natural compounds for biopolymers are: (i) naturally occurring fillers (nFil), such as nano-/micro- sized layered alumino-silicate: halloysite, bentonite, montmorillonite, hydroxyapatite, calcium carbonate, etc.; (ii) naturally occurring fibers (nFib), such as wood and vegetable fibers; (iii) naturally occurring antioxidant molecules (nAO), such as phenols, polyphenols, vitamins, and carotenoids. However, in this short review, the advantages and drawbacks, considering naturally occurring compounds as safe, eco-friendly, and sustainable additives for biopolymers, have been focused and discussed briefly, even taking into account the requests and needs of different application fields.

Improvement of oxidation resistance of polymer-based nanocomposites through sonication of carbonaceous nanoparticles.

The work aim is focused on two different aspects: first, the investigation of the effect of extended ultra-sound-assisted treatment (us) of carbonaceous nanoparticles, such as carbon nanotubes (CNTs) and carbon black (CB), on their radical scavenging activity, and second, the investigation of the oxidative resistance of polymer-based nanocomposites, containing us-treated CNTs and CB. Particularly, the CNTs and CB have been subjected to us sonication for different time intervals and the performed analysis reveals that both kinds of nanoparticles show decreased average hydrodynamic diameters and large content of surface defects. Really, the increased content of CNTs and CB defects, achieved during the sonication time, leads to an increased reactivity toward 1,1-diphenyl-2-pycryl (DPPH) radicals and an enhanced anti-oxidant activity toward macro-radicals, coming from the photo-degradation of the host polymer matrix. The studies of photo-oxidative behavior of the nanocomposites, based on Ultra High Molecular Weight (UHMWPE), reveal that the us treatment of the nanoparticles has a benefic effect on the oxidative resistance of the nanocomposites, especially at long exposure times. Overall, the ultra-sound-assisted treatment can be considered twofold powerful tool: (i) for disruption of the nanoparticles aggregations, and (ii) for capitalization of surface defects, amplifying and tuning in a controlled way the radical scavenging activity of the carbonaceous nanoparticles.

Pro-Degradant Activity of Naturally Occurring Compounds on Polyethylene in Accelerate Weathering Conditions.

In this work, naturally occurring compounds, such as Vitamin E (VE) and Ferulic Acid (FA), at high concentrations, have been considered as pro-degradant agents for Low Density Polyethylene (PE). However, all obtained results using the naturally occurring molecules as pro-oxidant agents for PE have been compared with the results achieved using a classical pro-oxidant agent, such as calcium stearate (Ca stearate) and with neat PE. The preliminary characterization, through rheological, mechanical and thermal analysis, of the PE-based systems highlights that the used naturally occurring molecules are able to exert a slight plasticizing action on PE and subsequently the PE rigidity and crystallinity slightly decrease, while the ductility increases. To assess the pro-degradant activity of the considered naturally occurring compounds, thin films of neat PE and PE-based systems containing 2 and 3 wt.% Ca stearate, VE and FA have been produced and subjected to accelerated weathering upon UVB light exposure. All obtained results point out that the VE and FA, at these high concentrations, exert a clear pro-oxidant activity in PE and this pro-oxidant activity is very similar to that exerted by Ca stearate. Moreover, the VE and FA at high concentrations can be considered as suitable eco-friendly pro-degradant additives for PE, also in order to control the polyolefin degradation times.

Sonication-Induced Modification of Carbon Nanotubes: Effect on the Rheological and Thermo-Oxidative Behaviour of Polymer-Based Nanocomposites.

The aim of this work is the investigation of the effect of ultrasound treatment on the structural characteristics of carbon nanotubes (CNTs) and the consequent influence that the shortening induced by sonication exerts on the morphology, rheological behaviour and thermo-oxidative resistance of ultra-high molecular weight polyethylene (UHMWPE)-based nanocomposites. First, CNTs have been subjected to sonication for different time intervals and the performed spectroscopic and morphological analyses reveal that a dramatic decrease of the CNT's original length occurs with increased sonication time. The reduction of the initial length of CNTs strongly affects the nanocomposite rheological behaviour, which progressively changes from solid-like to liquid-like as the CNT sonication time increases. The study of the thermo-oxidative behaviour of the investigated nanocomposites reveals that the CNT sonication has a detrimental effect on the thermo-oxidative stability of nanocomposites, especially for long exposure times. The worsening of the thermo-oxidative resistance of sonicated CNT-containing nanocomposites could be attributed to the lower thermal conductivity of low-aspect-ratio CNTs, which causes the increase of the local temperature at the polymer/nanofillers interphase, with the consequent acceleration of the degradative phenomena.

Nitrogen-Doped Carbon Nanodots-Ionogels: Preparation, Characterization, and Radical Scavenging Activity.

Hybrid diimidazolium-based ionogels were obtained by dispersing nitrogen-doped carbon nanodots (NCNDs) in ionic liquid (IL) solutions and by using dicationic organic salts as gelators. The properties of the NCND-ionogels were studied in terms of thermal stability, mechanical strength, morphology, rheological, and microscopic analyses. Insights into the formation of the hybrid soft material were attained from kinetics of sol-gel phase transition and from estimating the size of the aggregates, obtained from opacity and resonance light-scattering measurements. We demonstrate that, on one hand, NCNDs were able to favor the gel formation both in the presence of gelating and nongelating ILs. On the other hand, the gelatinous matrix retains and, in some cases, improves the properties of NCNDs. The NCND-ionogels showed the typical fluorescence emission of the carbon dots and a notable antiradical activity, with higher efficiency as compared to the single components. The presented hybrid materials hold great promise for topical applications in antioxidant fields.

Biopolyester-based systems containing naturally occurring compounds with enhanced thermo-oxidative stability.

BACKGROUND: This work presents a sustainable approach for the stabilization of polylactic acid (PLA) against thermo-oxidative aging. METHODS: Naturally occurring phenolic and polyphenolic compounds, such as ferulic acid (FerAc), vanillic acid (VanAc), quercetin (Querc) and vitamin E (VitE), were introduced into PLA. RESULTS: The preliminary characterization of the systems formulated containing different amounts of natural stabilizers showed that all compounds used acted as plasticizers, leading to a decrease in rheological functions with respect to neat PLA, without significantly modifying the crystallinity of the raw material. The study of the thermo-oxidative behavior of neat PLA and PLA/natural compound systems, performed by spectrometric and thermal analyses, indicated that all stabilizers considered were able to exert a remarkable antioxidant action against thermo-oxidative phenomena. CONCLUSIONS: All natural compounds considered are thus proposed as ecofriendly stabilizers, to get fully bio-based polymer systems with enhanced thermo-oxidative stability, suitable for biomedical applications.