Innovative Biobased and Sustainable Polymer Packaging Solutions for Extending Bread Shelf Life: A Review.

Sustainable packaging has been steadily gaining prominence within the food industry, with biobased materials emerging as a promising substitute for conventional petroleum-derived plastics. This review is dedicated to the examination of innovative biobased materials in the context of bread packaging. It aims to furnish a comprehensive survey of recent discoveries, fundamental properties, and potential applications. Commencing with an examination of the challenges posed by various bread types and the imperative of extending shelf life, the review underscores the beneficial role of biopolymers as internal coatings or external layers in preserving product freshness while upholding structural integrity. Furthermore, the introduction of biocomposites, resulting from the amalgamation of biopolymers with active biomolecules, fortifies barrier properties, thus shielding bread from moisture, oxygen, and external influences. The review also addresses the associated challenges and opportunities in utilizing biobased materials for bread packaging, accentuating the ongoing requirement for research and innovation to create advanced materials that ensure product integrity while diminishing the environmental footprint.

New Functional Bionanocomposites by Combining Hybrid Host-Guest Systems with a Fully Biobased Poly(lactic acid)/Poly(butylene succinate-co-adipate) (PLA/PBSA) Binary Blend.

In this study, we have developed innovative polymer nanocomposites by integrating magnesium-aluminum layered double hydroxide (LDH)-based nanocarriers modified with functional molecules into a fully biobased poly(lactic acid)/poly(butylene succinate-co-adipate) (PLA/PBSA) matrix. These LDH-based hybrid host-guest systems contain bioactive compounds like rosmarinic acid, ferulic acid, and glycyrrhetinic acid, known for their antioxidant, antimicrobial, and anti-inflammatory properties. The bioactive molecules can be gradually released from the nanocarriers over time, allowing for sustained and controlled delivery in various applications, such as active packaging or cosmetics. The morphological analysis of the polymer composites, prepared using a discontinuous mechanical mixer, revealed the presence of macroaggregates and nano-lamellae at the polymer interface. This resulted in an enhanced water vapor permeability compared to the original blend. Furthermore, the migration kinetics of active molecules from the thin films confirmed a controlled release mechanism based on their immobilization within the lamellar system. Scaling-up experiments evaluated the materials' morphology and mechanical and thermal properties. Remarkably, stretching deformation and a higher shear rate during the mixing process enhanced the dispersion and distribution of the nanocarriers, as confirmed by the favorable mechanical properties of the materials.

Investigation of Novel Flax Fiber/Epoxy Composites with Increased Biobased Content.

Currently, biobased epoxy resins derived from plant oils and natural fibers are available on the market and are a promising substitute for fossil-based products. The purpose of this work is to investigate novel lightweight thermoset fiber-reinforced composites with extremely high biobased content. Paying attention to the biobased content, following a cascade pathway, many trials were carried out with different types of resins and hardeners to select the best ones. The most promising formulations were then used to produce flax fiber reinforced composites by vacuum bagging process. The main biocomposite properties such as tensile, bending, and impact properties as well as the individuation of their glass transition temperatures (by DSC) were assessed. Three biocomposite systems were investigated with biobased content ranging from 60 to 91%, obtaining an elastic modulus that varied from 2.7 to 6.3 GPa, a flexural strength from 23 to 108.5 MPa, and Charpy impact strength from 11.9 to 12.2 kJ/m2. The properties reached by the new biocomposites are very encouraging; in fact, their stiffness vs. lightweight (calculated by the E/ρ3 ratio) is comparable to some typical epoxy-glass composites.

Upcycling of Poly(Lactic Acid) by Reactive Extrusion with Recycled Polycarbonate: Morphological and Mechanical Properties of Blends.

Poly(lactic acid) (PLA) is one of the most promising renewable polymers to be employed to foster ecological and renewable materials in many fields of application. To develop high-performance products, however, the thermal resistance and the impact properties should be improved. At the same time, it is also necessary to consider the end of life through the exploration of property assessment, following reprocessing. In this context the aim of the paper is to develop PLA/PC blends, obtained from recycled materials, in particular scraps from secondary processing, to close the recycling loop. Indeed, the blending of PLA with polycarbonate (PC) was demonstrated to be a successful strategy to improve thermomechanical properties that happens after several work cycles. The correlation between the compositions and properties was then investigated by considering the morphology of the blends; in addition, the reactive extrusions resulting in the formation of a PLA-PC co-polymer were investigated. The materials obtained are then examined by means of a dynamic-mechanical analysis (DMTA) to study the relaxations and transitions.

Antimicrobial and Gas Barrier Crustaceans and Fungal Chitin-Based Coatings on Biodegradable Bioplastic Films.

Chitin nanofibrils (CN) can be obtained from crustaceans and fungal sources and can be used for preparing coatings for bioplastic films, that are fundamental for developing a safe and sustainable biodegradable food packaging. Coatings with different concentrations of CN from shrimps were applied on different bioplastic substrates, like Poly (butylene succinate-co-adipate)/Poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PBSA/PHBV) blend, Polybutylene succinate (PBS), and Polybutylene adipate terephthalate/Poly(lactic acid) (PBAT/PLA) blend, but the adhesion to the substrates was scarce. On the contrary, the fungal-based CN showed a better adhesion. Additionally, it was found that the use of an additive based on oligomeric lactic acid was useful to prepare a coating with an improved adhesion to bioplastics. The gas barrier properties to oxygen and water vapour of coated and un-coated films were measured, revealing an improvement of these properties thanks to applied coatings, especially towards the oxygen. Antimicrobial properties and biodegradation capacity were also evaluated revealing an antibacterial effect of the coatings that did not significantly interfere with their biodegradability. The results are discussed and interpreted considering the correlation between composition and macromolecular structures with the observed functional properties.

Micromechanical Deformation Processes and Failure of PBS Based Composites Containing Ultra-Short Cellulosic Fibers for Injection Molding Applications.

The use of biobased thermoplastic polymers has gained great attention in the last years as a potential alternative to fossil-based thermoplastic polymers. Biobased polymers in fact offer advantages not only in terms of reduced dependence on fossil resources but they also lower the CO2 footprint in accordance with sustainability and climate protection goals. To improve the properties of these materials, reinforcement with biobased fibers is a promising solution; however, it must be kept in mind that the fibers aspect ratio and the interfacial adhesion between the reinforcement and the matrix plays an important role influencing both physical and mechanical properties of the biocomposites. In this paper, the possibility of producing composites by injection molding, based on polybutylene succinate and ultra-short cellulosic fibers has been explored as a potential biobased solution. Thermo-mechanical properties of the composites were investigated, paying particular attention to the local micromechanical deformation processes, investigated by dilatometric tests, and failure mechanisms. Analytical models were also applied to predict the elastic and flexural modulus and the interfacial properties of the biocomposites. Good results were achieved, demonstrating the that this class of biocomposite can be exploited. Compared to pure PBS, the composites with 30 wt.% of cellulose fibers increased the Young's modulus by 154%, the flexural modulus by 130% and the heat deflection temperature by 9%.

Improvement of Interfacial Adhesion and Thermomechanical Properties of PLA Based Composites with Wheat/Rice Bran.

The present work aims to enhance the use of agricultural byproducts for the production of bio-composites by melt extrusion. It is well known that in the production of such bio-composites, the weak point is the filler-matrix interface, for this reason the adhesion between a polylactic acid (PLA)/poly(butylene succinate)(PBSA) blend and rice and wheat bran platelets was enhanced by a treatment method applied on the fillers using a suitable beeswax. Moreover, the coupling action of beeswax and inorganic fillers (such as talc and calcium carbonate) were investigated to improve the thermo-mechanical properties of the final composites. Through rheological (MFI), morphological (SEM), thermal (TGA, DSC), mechanical (Tensile, Impact), thermomechanical (HDT) characterizations and the application of analytical models, the optimum among the tested formulations was then selected.

Analytical Modeling of Stress Relaxation and Evaluation of the Activation Volume Variation: Effect of Temperature and Plasticizer Content for Poly(3-hydroxybutyrate-3-hydroxyvalerate).

In this study, stress-relaxation tests that have been carried out at different temperatures (quite below the heat deflection temperature) on a poly(3-hydroxybutyrate-3hydroxyvalerate) (PHB-HV) matrix containing different amounts of the acetyl tributyl citrate plasticizer (added at 5 and 10 wt %) are investigated. The analytical modeling of the stress relaxation behavior by the coupling of Eyring's approach and the Guiu and Pratt model is successful. The activation volume results achieved are very interesting; in fact, not only the dependence of the activation volume from temperature is confirmed (and it resulted in dependence from the α' relaxation temperature) but also, for the first time, the dependence of the activation volume from the plasticizer content is shown. In particular, the presence of a linear relationship between the activation volume and the plasticizer volume content is observed.

A Brief Review of Poly (Butylene Succinate) (PBS) and Its Main Copolymers: Synthesis, Blends, Composites, Biodegradability, and Applications.

PBS, an acronym for poly (butylene succinate), is an aliphatic polyester that is attracting increasing attention due to the possibility of bio-based production, as well as its balanced properties, enhanced processability, and excellent biodegradability. This brief review has the aim to provide the status concerning the synthesis, production, thermal, morphological and mechanical properties underlying biodegradation ability, and major applications of PBS and its principal copolymers.

Liquid and Solid Functional Bio-Based Coatings.

The development of new bio-based coating materials to be applied on cellulosic and plastic based substrates, with improved performances compared to currently available products and at the same time with improved sustainable end of life options, is a challenge of our times. Enabling cellulose or bioplastics with proper functional coatings, based on biopolymer and functional materials deriving from agro-food waste streams, will improve their performance, allowing them to effectively replace fossil products in the personal care, tableware and food packaging sectors. To achieve these challenging objectives some molecules can be used in wet or solid coating formulations, e.g., cutin as a hydrophobic water- and grease-repellent coating, polysaccharides such as chitosan-chitin as an antimicrobial coating, and proteins as a gas barrier. This review collects the available knowledge on functional coatings with a focus on the raw materials used and methods of dispersion/application. It considers, in addition, the correlation with the desired final properties of the applied coatings, thus discussing their potential.

Analysis of the Damage Mechanism around the Crack Tip for Two Rubber-Toughened PLA-Based Blends.

The toughening mechanisms of poly(lactic acid; PLA) blended with two different elastomers, namely poly (butylene adipate-co-terephtalate; PBAT) and polyolefin elastomers with grafted glycidyl methacrylate (POE-g-GMA), at 10 and 20 wt.%, were investigated. Tensile and Charpy impact tests showed a general improvement in the performance of the PLA. The morphology of the dispersed phases showed that PBAT is in the form of spheres while POE-g-GMA has a dual sphere/fibre morphology. To correlate the micromechanical deformation mechanism with the macroscopical mechanical behaviour, the analysis of the subcritical crack tip damaged zone of double-notched specimens subjected to a four-point bending test (according to the single-edge double-notch four-point bend (SEDN-4PB) technique) was carried out using several microscopic techniques (SEM, polarized TOM and TEM). The damage was mainly generated by shear yielding deformation although voids associated with dilatational bands were observed.

Chain Extension of Poly(Lactic Acid) (PLA)-Based Blends and Composites Containing Bran with Biobased Compounds for Controlling Their Processability and Recyclability.

The present work focused on the research, design, and study of innovative chain extender systems of renewable origin for PLA-based biocomposites, reinforced with wheat bran as filler. The majority of employed chain extender compounds belongs to fossil world, affecting the biodegradability property which characterizes biopolymers. The aim of this work was thus to find promising biobased and sustainable alternatives to provide the same enhancements. According to this objective, epoxidized soybean oil (ESO) was chosen as principal component of the chain extender systems, together with a dicarboxylic acid, malic acid (MA), or succinic acid (SA). The reactivity of the modifier systems was previously studied through thermogravimetric analysis (TGA) and IR spectroscopy, to hypothesize the reaction mechanism in bran-filled blends. Hence, small-scale extrusion was carried out to investigate the effects of ESO/MA and ESO/SA on formulations of different composition (both pure PLA blends and composites). The variation of melt fluidity parameters was analyzed to define the optimized concentration of modifier systems. A comparison between the effects on blends of designed biobased systems and the action of fossil-based Joncryl was performed, to understand if the developed green solutions could represent competitive and efficient substitutes. The modified composites were characterized in terms of mechanical tests, degradation and thermal studies (TGA and DSC), and morphological analysis (SEM), to figure out their main features and to understand their potential in possible industrial applications.

Volume Change during Creep and Micromechanical Deformation Processes in PLA-PBSA Binary Blends.

In this paper, creep measurements were carried out on poly(lactic acid) (PLA) and its blends with poly(butylene succinate-adipate) (PBSA) to investigate the specific micromechanical behavior of these materials, which are promising for replacing fossil-based plastics in several applications. Two different PBSA contents at 15 and 20 wt.% were investigated, and the binary blends were named 85-15 and 80-20, respectively. Measurements of the volume strain, using an optical extensometer, were carried out with a universal testing machine in creep configuration to determine, accompanied by SEM images, the deformation processes occurring in a biopolymeric blend. With the aim of correlating the creep and the dilatation variation, analytical models were applied for the first time in biopolymeric binary blends. By using an Eyring plot, a significant change in the curves was found, and it coincided with the onset of the cavitation/debonding mechanism. Furthermore, starting from the data of the pure PLA matrix, using the Eyring relationship, an apparent stress concentration factor was calculated for PLA-PBSA systems. From this study, it emerged that the introduction of PBSA particles causes an increment in the apparent stress intensity factor, and this can be ascribed to the lower adhesion between the two biopolymers. Furthermore, as also confirmed by SEM analysis, it was found that debonding was the main micromechanical mechanism responsible for the volume variation under creep configuration; it was found that debonding starts earlier (at a lower stress level) for the 85-15 blend.

On the Use of Paper Sludge as Filler in Biocomposites for Injection Moulding.

The potential use of paper sludge (PS) as filler in the production of bio-composites based on poly lactic acid (PLA) and polybutylene adipate terephthalate (PBAT) was investigated. PS/PLA/PBAT composites, with addition of acetyl tributyl citrate (ATBC) as biobased plasticizer, were produced with PS loadings up to 30 wt.% by twin-screw extrusion followed by injection moulding. The composites were characterized by rheological measurements, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and mechanical tests (tensile and impact resistance) to study the effect of PS on the processability, thermal stability, crystallinity and mechanical performance of polymeric matrix. The optimized composites at higher PS content were successfully processed to produce pots for horticulture and, in view of this application, preliminary phytotoxicity tests were conducted using the germination test on Lepidium sativum L. seeds. Results revealed that developed composites up to 30 wt.% PS had good processability by extrusion and injection moulding showing that PS is a potential substitute of calcium carbonate as filler in the production of bio-composites, and the absence of phytotoxic effects showed the possibility of their use in the production of pots/items for applications in floriculture and/or horticulture.

Effect of a Bio-Based Dispersing Aid (Einar® 101) on PLA-Arbocel® Biocomposites: Evaluation of the Interfacial Shear Stress on the Final Mechanical Properties.

In this paper, the production and the characterization of poly (lactic) acid (PLA)-based composites containing different amounts (from 10 wt.% to 25 wt.%) of ultra-short cellulose fibers (Arbocel 600 BE/PU) have been investigated. On the basis of a previous study, it was observed that the addition of the cellulose fibers led to an embrittlement of the composite. Consequently, in order to obtain a composite with enhanced impact resistance and elongation at break, the effect of the Einar 101 addition (a bio-based dispersing aid additive) was analyzed. The role of the adhesion between the fiber and the matrix, coupled with a better fiber dispersion, was thus evaluated. Also, the consequences on the final mechanical properties (tensile and impact test) caused by the Einar addition were investigated. Analytical models were also applied in order to obtain an evaluation of the variation of the interfacial shear stress (IFSS) (strictly correlated to the fiber-matrix adhesion) caused by the Einar introduction. Furthermore, due to the very low aspect ratio of the Arbocel fibers, a suitable Bader and Boyer model variation was adopted in order to have a better quantitative estimation of the IFSS value.

On the Use of Biobased Waxes to Tune Thermal and Mechanical Properties of Polyhydroxyalkanoates-Bran Biocomposites.

In this work, processability and mechanical performances of bio-composites based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) containing 5, 10, and 15 wt % of bran fibers, untreated and treated with natural carnauba and bee waxes were evaluated. Wheat bran, the main byproduct of flour milling, was used as filler to reduce the final cost of the PHBV-based composites and, in the same time, to find a potential valorization to this agro-food by-product, widely available at low cost. The results showed that the wheat bran powder did not act as reinforcement, but as filler for PHBV, due to an unfavorable aspect ratio of the particles and poor adhesion with the polymeric matrix, with consequent moderate loss in mechanical properties (tensile strength and elongation at break). The surface treatment of the wheat bran particles with waxes, and in particular with beeswax, was found to improve the mechanical performance in terms of tensile properties and impact resistance of the composites, enhancing the adhesion between the PHBV-based polymeric matrix and the bran fibers, as confirmed by predictive analytic models and dynamic mechanical analysis results.

Evaluation of Mussel Shells Powder as Reinforcement for PLA-Based Biocomposites.

The use of biopolyesters, as polymeric matrices, and natural fillers derived from wastes or by-products of food production to achieve biocomposites is nowadays a reality. The present paper aims to valorize mussel shells, 95% made of calcium carbonate (CaCO3), converting them into high-value added products. The objective of this work was to verify if CaCO3, obtained from Mediterranean Sea mussel shells, can be used as filler for a compostable matrix made of Polylactic acid (PLA) and Poly(butylene adipate-co-terephthalate) (PBAT). Thermal, mechanical, morphological and physical properties of these biocomposites were evaluated, and the micromechanical mechanism controlling stiffness and strength was investigated by analytical predictive models. The performances of these biocomposites were comparable with those of biocomposites produced with standard calcium carbonate. Thus, the present study has proved that the utilization of a waste, such as mussel shell, can become a resource for biocomposites production, and can be an effective option for further industrial scale-up.

Preparation and Compatibilization of PBS/Whey Protein Isolate Based Blends.

In this paper the production of biopolymeric blends of poly(butylene succinate) PBS and plasticized whey protein (PWP), obtained from a natural by-product from cheese manufacturing, has been investigated for the production of films and/or sheets. In order to add the highest possible whey protein content, different formulations (from 30 to 50 wt.%) were studied. It was found that by increasing the amount of PWP added to PBS, the mechanical properties were worsened accordingly. This trend was attributed to the low compatibility between PWP and PBS. Consequently, the effect of the addition of soy lecithin and glycerol monostearate (GMS) as compatibilizers was investigated and compared to the use of whey protein modified with oleate and laurate groups obtained by Schotten-Baumann reaction. Soy lecithin and the Schotten-Baumann modified whey were effective in compatibilizing the PWP/PBS blend. In fact, a significant increase in elastic modulus, tensile strength and elongation at break with respect to the not compatibilized blend was observed and the length of aliphatic chains as well as the degree of modification of the Schotten-Baumann proteins affected the results. Moreover, thanks to DSC investigations, these compatibilizers were also found effective in increasing the PBS crystallinity.

Sustainable Micro and Nano Additives for Controlling the Migration of a Biobased Plasticizer from PLA-Based Flexible Films.

Plasticized poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blend-based films containing chitin nanofibrils (CN) and calcium carbonate were prepared by extrusion and compression molding. On the basis of previous studies, processability was controlled by the use of a few percent of a commercial acrylic copolymer acting as melt strength enhancer and calcium carbonate. Furthermore, acetyl n-tributyl citrate (ATBC), a renewable and biodegradable plasticizer (notoriously adopted in PLA based products) was added to facilitate not only the processability but also to increase the mechanical flexibility and toughness. However, during the storage of these films, a partial loss of plasticizer was observed. The consequence of this is not only correlated to the change of the mechanical properties making the films more rigid but also to the crystallization and development of surficial oiliness. The effect of the addition of calcium carbonate (nanometric and micrometric) and natural nanofibers (chitin nanofibrils) to reduce/control the plasticizer migration was investigated. The prediction of plasticizer migration from the films' core to the external surface was carried out and the diffusion coefficients, obtained by regression of the experimental migration data plotted as the square root of time, were evaluated for different blends compositions. The results of the diffusion coefficients, obtained thanks to migration tests, showed that the CN can slow the plasticizer migration. However, the best result was achieved with micrometric calcium carbonate while nanometric calcium carbonate results were less effective due to favoring of some bio polyesters' chain scission. The use of both micrometric calcium carbonate and CN was counterproductive due to the agglomeration phenomena that were observed.

Flat Die Extruded Biocompatible Poly(Lactic Acid) (PLA)/Poly(Butylene Succinate) (PBS) Based Films.

Biodegradable polymers are promising materials for films and sheets used in many widely diffused applications like packaging, personal care products and sanitary products, where the synergy of high biocompatibility and reduced environmental impact can be particularly significant. Plasticized poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) blend-based films, showing high cytocompatibility and improved flexibility than pure PLA, were prepared by laboratory extrusion and their processability was controlled by the use of a few percent of a commercial melt strength enhancer, based on acrylic copolymers and micro-calcium carbonate. The melt strength enhancer was also found effective in reducing the crystallinity of the films. The process was upscaled by producing flat die extruded films in which elongation at break and tear resistance were improved than pure PLA. The in vitro biocompatibility, investigated through the contact of flat die extruded films with cells, namely, keratinocytes and mesenchymal stromal cells, resulted improved with respect to low density polyethylene (LDPE). Moreover, the PLA-based materials were able to affect immunomodulatory behavior of cells and showed a slight indirect anti-microbial effect. These properties could be exploited in several applications, where the contact with skin and body is relevant.