High-Barrier, Biodegradable Films with Polyvinyl Alcohol/Polylactic Acid + Wax Double Coatings: Influence of Relative Humidity on Transport Properties and Suitability for Modified Atmosphere Packaging Applications.

Polyvinyl alcohol (PVOH) exhibits outstanding gas-barrier properties, which favor its use as a biodegradable, high-barrier coating on food-packaging films, possibly in combination with modified atmospheres. Nonetheless, its high sensitivity to water can result in a severe loss of barrier properties, significantly limiting its applications with fresh foods and in high-humidity conditions. In this work, the water vapor (PWV) and oxygen permeability (PO2) of high-barrier biodegradable films with PVOH/PLA + wax double coatings were extensively characterized in a wide range of relative humidity (from 30 to 90%), aimed at understanding the extent of the interaction of water with the wax and the polymer matrices and the impact of this on the permeation process. What is more, a mathematical model was applied to the PWV data set in order to assess its potential to predict the permeability of the multilayer films by varying storage/working relative humidity (RH) conditions. The carbon dioxide permeability (PCO2) of the films was further evaluated, and the corresponding permselectivity values were calculated. The study was finally augmented through modified atmosphere packaging (MAP) tests, which were carried out on double-coated films loaded with 0 and 5% wax, and UV-Vis analyses. The results pointed out the efficacy of the PLA + wax coating layer in hampering the permeation of water molecules, thus reducing PVOH swelling, as well as the UV-shielding ability of the multilayer structures. Moreover, the MAP tests underlined the suitability of the double-coated films for being used as a sustainable alternative for the preservation of foods under modified atmospheres.

Understanding the Impact of Biodegradable Microplastics on Living Organisms Entering the Food Chain: A Review.

Microplastics (MPs) pollution has emerged as one of the world's most serious environmental issues, with harmful consequences for ecosystems and human health. One proposed solution to their accumulation in the environment is the replacement of nondegradable plastics with biodegradable ones. However, due to the lack of true biodegradability in some ecosystems, they also give rise to biodegradable microplastics (BioMPs) that negatively impact different ecosystems and living organisms. This review summarizes the current literature on the impact of BioMPs on some organisms-higher plants and fish-relevant to the food chain. Concerning the higher plants, the adverse effects of BioMPs on seed germination, plant biomass growth, penetration of nutrients through roots, oxidative stress, and changes in soil properties, all leading to reduced agricultural yield, have been critically discussed. Concerning fish, it emerged that BioMPs are more likely to be ingested than nonbiodegradable ones and accumulate in the animal's body, leading to impaired skeletal development, oxidative stress, and behavioral changes. Therefore, based on the reviewed pioneering literature, biodegradable plastics seem to be a new threat to environmental health rather than an effective solution to counteract MP pollution, even if serious knowledge gaps in this field highlight the need for additional rigorous investigations to understand the potential risks associated to BioMPs.

Optimization of Hazelnut Spread Based on Total or Partial Substitution of Palm Oil.

Palm oil is widely used in the manufacturing of hazelnut-based spreads due to its unique fatty acid and triacylglycerol profile and, thus, its crystallization behaviour, which makes it suitable for use in fat-based spreadable products. An interesting solution that enables the replacement of palm oil is given by oleogels made with high nutritional quality oil. In this study, the influence of the replacement of palm oil with different glycerol monostearate/olive oil-based oleogels, as well as the influence of the different amounts of GMS employed in oleogel preparation, on the oil binding capacity, spreadability, and rheological and sensory parameters of hazelnut cocoa spreads was investigated. A design of experiment (DoE) approach, with the adoption of the D-optimal design, was used to plan the cocoa hazelnut spread formulations, with the aim being to identify the optimal formulation with desirable quality parameters in terms of Casson's viscosity, spreadability, and oil binding capacity. The resulting optimized formulation was identified in a spread characterized by a total replacement of palm oil with an oleogel made of 95% olive oil and 5% GMS.

Assessment of Melt Compounding with Zeolites as an Effective Deodorization Strategy for Mixed Plastic Wastes and Comparison with Degassing.

The emission of off-odors from mechanically recycled plastics severely limits their re-introduction into the market for the production of new objects, for the same use or even for less demanding applications, thus hindering the implementation of an effective circular economy for plastics. The addition of adsorbing agents during the extrusion of polymers represents one of the most promising strategy to reduce the odorous emissions of plastics, due to its characteristics of cost-effectiveness, flexibility and low energy consumption. The novelty of this work lies in the assessment of zeolites as VOC adsorbents during the extrusion of recycled plastics. They appear more suitable than other types of adsorbents, due to their ability to capture and "hold" the adsorbed substances at the high temperatures of the extrusion process. Moreover, the effectiveness of this deodorization strategy was compared with the traditional degassing technique. Two types of mixed polyolefin wastes, coming from completely different collection and recycling processes, were tested: Fil-S (Film-Small), deriving from post-consumer flexible films of small size, and PW (pulper waste), which is the residual plastic waste obtained from the paper recycling process. The melt compounding of the recycled materials with two micrometric zeolites (zeolite 13X and Z310) resulted as more effective in the off-odors removal with respect to degassing. In particular, the highest reduction (-45%) of the Average Odor Intensity (AOI) was measured for both PW/Z310 and Fil-S/13X systems at 4 wt% of the zeolites' amount, compared with the corresponding untreated recyclates. Finally, by combining degassing and melt compounding with zeolites, the best result was obtained for the composite Fil-S/13X, whose Average Odor Intensity resulted as quite close (+22%) to the one of the virgin LDPE.

New Materials and Technologies for Durability and Conservation of Building Heritage.

The increase in concrete structures' durability is a milestone to improve the sustainability of buildings and infrastructures. In order to ensure a prolonged service life, it is necessary to detect the deterioration of materials by means of monitoring systems aimed at evaluating not only the penetration of aggressive substances into concrete but also the corrosion of carbon-steel reinforcement. Therefore, proper data collection makes it possible to plan suitable restoration works which can be carried out with traditional or innovative techniques and materials. This work focuses on building heritage and it highlights the most recent findings for the conservation and restoration of reinforced concrete structures and masonry buildings.

Use of Hazelnut Perisperm as an Antioxidant for Production of Sustainable Biodegradable Active Films.

Utilization of food-waste-derived bioactive compounds with biodegradable polymers is an attractive strategy leading innovation in the food packaging sector and contributing to reduce the environmental concerns of plastic packaging disposal. In this field, this work is aimed to use hazelnut perisperm as an antioxidant agent in the production of biodegradable polymeric films for active packaging applications. For this purpose, hazelnut perisperm of a selected particle size (<250 µm) at different percentages (0%, 5% and 10% by weight) was added to a bioderived and compostable polymer suitable for food contact, known as Ecovio®. The blends were produced by a twin-screw extrusion process, while active films were prepared with a pilot lab-scale film blowing plant. The films were characterized in terms of physical−mechanical properties (thermal, tensile, oxygen barrier, optical, sealing ability) and antioxidant activity (DPPH), to investigate their potential use as active packaging. The results showed that the presence of the hazelnut perisperm confers significant antioxidant activity to the films, which is useful in counteracting lipid oxidation and preserve the quality of lipophilic foods, e.g., nut-dried fruits. An extension of the sealability temperature range of the films without compromising their strength was also highlighted. Moreover, the hazelnut perisperm causes a gradual decrease in the stiffness and mechanical strength of the films and an increase in the ductility of the system.

Development of Novel Blown Shrink Films from Poly(Lactide)/Poly(Butylene-Adipate-co-Terephthalate) Blends for Sustainable Food Packaging Applications.

Heat-shrinkable films, largely made of polyolefins and widely employed in the packaging sector as collation or barrier films, due to their short service life, are held responsible for high environmental impact. One possible strategy for reduction in their carbon footprint can be the use of biodegradable polymers. Thus, this work aimed to develop novel, heat-shrinkable, fully biodegradable films for green packaging applications and to analyze their functional performance. Films were obtained from blends of amorphous polylactic acid (PLA) and poly(butylene-adipate-co-terephthalate) (PBAT) at different mass ratios and compatibilized with a chain extender. They were produced by means of a lab-scale film blowing extrusion apparatus and characterized in terms of physical-mechanical properties and shrinkability. The influence of the processing parameters during the extrusion blowing process on the films' behavior was investigated, highlighting the effects of blend composition and stretching drawing conditions. Shrinkage tests demonstrated that the produced films have shrinkability values in the typical range of mono-oriented films (ca. 60-80% in machine direction and ca. 10-20% in transverse direction). Moreover, the shrinkage in machine direction increases both with the mass flow rate, the take-up ratio to blow-up ratio and the bubble cooling of the film blowing process, and with the PLA content into the blend. In particular, films at higher PLA content also exhibit higher transparency and stiffness.

Antimicrobial, sealable and biodegradable packaging to maintain the quality of shredded carrots and pineapple juice during storage.

Increasing consumer demand for foods with high nutritional quality, prolonged shelf life and low environmental impact of the package, is driving innovation towards the development of new packaging. Multifunctional food packaging films, biodegradable, heat-sealable and antimicrobial, were developed. A PLA coating layer incorporating either sodium benzoate, potassium sorbate, or a combination of them was deposited onto a poly(lactic) acid/poly(butylene adipate-co-terephthalate) substrate film. The effectiveness of the developed systems to preserve the quality of foods was tested in shelf-life experiments performed on shredded carrots and pineapple juice, selected as model processed raw foods. The best performance was observed for the active film containing potassium sorbate: microbial populations increased less rapidly and were 0.7-1.8 log CFU/g lower at the end of storage period in this film than in control packs. Of the two model foods, the pineapple juice was better preserved: after 7 days in active packaging, color change and microbial counts of juice were below that of control, observed after one day and after 3 days of storage respectively. Moreover, the incorporation of the active phases did not significantly affect the mechanical, barrier and optical properties of the films, opening new ways to prolong shelf-life of minimally processed foods. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-022-05435-y.

Effect of PVOH/PLA + Wax Coatings on Physical and Functional Properties of Biodegradable Food Packaging Films.

Biodegradable polymers suffer from inherent performance limitations that severely limit their practical application. Their functionalization by coating technology is a promising strategy to significantly improve their physical properties for food packaging. In this study, we investigated the double coating technique to produce multifunctional, high barrier and heat-sealable biodegradable films. The systems consisted of a web layer, made of poly(lactide) (PLA) and poly(butylene-adipate-co-terephthalate) (PBAT), which was first coated with a poly(vinyl) alcohol based layer, providing high barrier, and then with a second layer of PLA + ethylene-bis-stereamide (EBS) wax (from 0 to 20%), to provide sealability and improve moisture resistance. The films were fully characterized in terms of chemical, thermal, morphological, surface and functional properties. The deposition of the PVOH coating alone, with a thickness of 5 µm, led to a decrease in the oxygen transmission rate from 2200 cm3/m2 d bar, for the neat substrate (thickness of 22 µm), to 8.14 cm3/m2 d bar (thickness of 27 µm). The deposition of the second PLA layer did not affect the barrier properties but provided heat sealability, with a maximum bonding strength equal to 6.53 N/25 mm. The EBS wax incorporation into the PLA slightly increased the surface hydrophobicity, since the water contact angle passed from 65.4°, for the neat polylactide layer, to 71° for the 20% wax concentration. With respect to the substrate, the double-coated films exhibited increased stiffness, with an elastic modulus ca. three times higher, and a reduced elongation at break, which, however still remained above 75%. Overall, the developed double-coated films exhibited performances comparable to those of the most common synthetic polymer films used in the packaging industry, underlining their suitability for the packaging of sensitive foods with high O2-barrier requirements.

Nanosilicates in Compatibilized Mixed Recycled Polyolefins: Rheological Behavior and Film Production in a Circular Approach.

Currently, plastic packaging represents a global challenge and has become a key point of attention for governments, media and consumers due to the visibility of the waste it generates. Despite their high resource efficiency, the perceived non-recyclability of polymeric films risks precluding them from being a relevant packaging solution in a circular economy approach. In this regard, the aim of this study was to implement a strategy to try closing the loop, via the mechanical recycling of post-consumer flexible packaging of small size (denoted as Fil-s) to obtain new films. In particular, two lots of Fil-s were used, which are PE/PP blends differing for the PP content and the presence of polar contaminants. The suitability for film blowing extrusion of these recycled materials, as such and after the addition of a compatibilizer and/or a lamellar nanosilicate, was evaluated. It was first evidenced that the difficulty of producing blown films with the pristine recycled materials, due to the frequent bubble breakages, occurring even at low draw ratios. Moreover, the shear and extensional rheological behavior of all Fil-s based systems was usefully correlated with their processability features, evidencing the key roles of the nanofiller to stabilize the bubble and of the compatibilizer to ensure a uniform film deformation, avoiding its premature breakage. Even if the adopted upgrading strategies allowed the production of blown films with both types of Fil-s, the different components of the recycled matrices were proven to significantly affect their processability and final film performances.

Study on Improving the Processability and Properties of Mixed Polyolefin Post-Consumer Plastics for Piping Applications.

This study focuses on the upgrading strategies to make Fil-s (acronym for film-small), a polyolefin-based material coming from the mechanical recycling of post-consumer flexible packaging, fit for re-use in the piping sector. The effects of washing treatments (at cold and hot conditions) and the addition of an experimental compatibilizer on the chemical-physical properties of Fil-s were first assessed. The measurements of some key properties (density, melt flow index, flexural modulus, yield strength), for both Fil-s as such and the different developed Fil-s based systems, was also conducted in order to evaluate the suitability of this complex and challenging waste stream to replace virgin PE-based pipe and fitting products, in compliance to ASTM D3350 standard. The outcomes of the present work contributed to define a code, for each Fil-s system investigated, useful for identifying the level of their performance in piping applications. All the recyclates were extruded as pipes by using a pilot scale plant, but the process resulted more stable and continuous with the compatibilized Fil-s, as it was deducible from its flow properties. Moreover, the best mechanical performances were exhibited by the hot-washed Fil-s pipes, with an increase in pipe stiffness equal to 65% respect to the unwashed sample.

Development of Eco-Sustainable PBAT-Based Blown Films and Performance Analysis for Food Packaging Applications.

In this work, eco-sustainable blown films with improved performance, suitable for flexible packaging applications requiring high ductility, were developed and characterized. Films were made by blending two bioplastics with complementary properties-the ductile and flexible poly(butylene-adipate-co-terephthalate) (PBAT) and the rigid and brittle poly(lactic acid) (PLA)-at a 60/40 mass ratio. With the aim of improving the blends' performance, the effects of two types of PLA, differing for viscosity and stereoregularity, and the addition of a commercial polymer chain extender (Joncryl®), were analyzed. The use of the PLA with a viscosity ratio closer to PBAT and lower stereoregularity led to a finer morphology and better interfacial adhesion between the phases, and the addition of the chain extender further reduced the size of the dispersed phase domains, with beneficial effects on the mechanical response of the produced films. The best system composition, made by the blend of PBAT, amorphous PLA, and the compatibilizer, proved to have improved mechanical properties, with a good balance between stiffness and ductility and also good transparency and sealability, which are desirable features for flexible packaging applications.

Preparation and Characterization of Polypropylene/Carbon Nanotubes (PP/CNTs) Nanocomposites as Potential Strain Gauges for Structural Health Monitoring.

Polypropylene/carbon nanotubes (PP/CNTs) nanocomposites with different CNTs concentrations (i.e., 1, 2, 3, 5 and 7 wt%) were prepared and tested as strain gauges for structures monitoring. Such sensors were embedded in cementitious mortar prisms and tested in 3-point bending mode recording impedance variation at increasing load. First, thermal (differential scanning calorimetry (DSC), thermo-gravimetric analysis (TGA)), mechanical (tensile tests) and morphological (FE-SEM) properties of nanocomposites blends were assessed. Then, strain-sensing tests were carried out on PP/CNTs strips embedded in cementitious mortars. PP/CNTs nanocomposites blends with CNTs content of 1, 2 and 3 wt% did not show significant results because these concentrations are below the electrical percolation threshold (EPT). On the contrary, PP/CNTs nanocomposites with 5 and 7 wt% of CNTs showed interesting sensing properties. In particular, the best result was highlighted for the PP/CNT nanocomposite with 5 wt% CNTs for which an average gauge factor (GF) of approx. 1400 was measured. Moreover, load-unload cycles reported a good recovery of the initial impedance. Finally, a comparison with some literature results, in terms of GF, was done demonstrating the benefits deriving from the use of PP/CNTs strips as strain-gauges instead of using conductive fillers in the bulk matrix.

Evaluation of the Suitability of Poly(Lactide)/Poly(Butylene-Adipate-co-Terephthalate) Blown Films for Chilled and Frozen Food Packaging Applications.

The use of biopolymers can reduce the environmental impact generated by plastic materials. Among biopolymers, blends made of poly(lactide) (PLA) and poly(butylene-adipate-co-terephthalate) (PBAT) prove to have adequate performances for food packaging applications. Therefore, the present work deals with the production and the characterization of blown films based on PLA and PBAT blends in a wide range of compositions, in order to evaluate their suitability as chilled and frozen food packaging materials, thus extending their range of applications. The blends were fully characterized: they showed the typical two-phase structure, with a morphology varying from fibrillar to globular in accordance with their viscosity ratio. The increase of PBAT content in the blends led to a decrease of the barrier properties to oxygen and water vapor, and to an increase of the toughness of the films. The mechanical properties of the most ductile blends were also evaluated at 4 °C and -25 °C. The decrease in temperature caused an increase of the stiffness and a decrease of the ductility of the films to a different extent, depending upon the blend composition. The blend with 40% of PLA revealed to be a good candidate for chilled food packaging applications, while the blend with a PLA content of 20% revealed to be the best composition as frozen food packaging material.

Erratum: Effect of Porosity and Crystallinity on 3D Printed PLA Properties. Polymers 2019, 11, 1487.

The authors wish to make a change to the published paper [...].

Effect of Porosity and Crystallinity on 3D Printed PLA Properties.

Additive manufacturing (AM) is a promising technology for the rapid tooling and fabrication of complex geometry components. Among all AM techniques, fused filament fabrication (FFF) is the most widely used technique for polymers. However, the consistency and properties control of the FFF product remains a challenging issue. This study aims to investigate physical changes during the 3D printing of polylactic acid (PLA). The correlations between the porosity, crystallinity and mechanical properties of the printed parts were studied. Moreover, the effects of the build-platform temperature were investigated. The experimental results confirmed the anisotropy of printed objects due to the occurrence of orientation phenomena during the filament deposition and the formation both of ordered and disordered crystalline forms (α and δ, respectively). A heat treatment post-3D printing was proposed as an effective method to improve mechanical properties by optimizing the crystallinity (transforming the δ form into the α one) and overcoming the anisotropy of the 3D printed object.

Nanotechnology-Based Strategy to Upgrade the Performances of Plastic Flexible Film Waste.

The aim of this work was to improve the performances of Fil-s (film-small), a recycled material obtained from plastic flexible film waste that is made of polyethylene and a minor amount of polypropylene, with traces of polar contaminants (polyamides, maleic anhydride, etc.). The idea was to upgrade the material's mechanical properties by applying a nanotechnology-based strategy that takes advantage of the composition of Fil-s. In particular, different amounts of copolyamide (CoPA) and its masterbatch with an organic-modified nanosilicate were melt compounded with Fil-s in a twin-screw extruder. The good affinity between Fil-s and CoPA, proved by means of spectroscopic and rheological analysis, allowed for the obtaining of a well-refined morphology for the neat and hybrid blends. This resulted in very interesting increments of the strain at break, which was particularly impressive (10 times higher) in the case of the blend with the lower amount of copolyamide masterbatch, but without sacrificing the stiffness and strength of Fil-s.

An Easy Route to Wettability Changes of Polyethylene Terephthalate⁻Silicon Oxide Substrate Films for High Barrier Applications, Surface-Modified with a Self-Assembled Monolayer of Fluoroalkylsilanes.

Inorganic⁻organic multilayer films consisting of polymers coated with thin inorganic oxidic layers (e.g., SiOx) ensure very high barrier performances against gas and vapor permeation, what makes them packaging materials suitable for sophisticated technical applications, including the encapsulation of photovoltaic devices or quantum dots, barrier films for optical displays, and transparent greenhouse screens. In these fields, surface coating or texturing of the multilayer protective films are effective technologies to improve their self-clean ability, thus reducing the required maintenance and ensuring longer durability and better performances. In this work, we used the self-assembled monolayer (SAM) technique to modify the surface and wetting properties of commercial polyethylene terephthalate-silicon oxide substrate (PET-SiOx) films developed for technical applications requiring a combined high barrier and transparency. The selected surface modifier was the 1H,1H,2H,2H-per-fluorodecyltrichlorosilane (FDTS). The reagent mixture composition was optimized for the lowest water and oil wettability, as well as the highest self-cleaning capacity and performance stability. In particular, for the used PET-SiOx film the best FDTS/film surface for both the lowest water and oil wettability was found to be equal to 26.5 mM/dm², which changes the surface behavior from very hydrophilic (static water contact angle (CAw) = 21.5°) to hydrophobic (CAw = 101°), and gives a significant increment of the static oil contact angle (CAo) from 27° to 60°. Interestingly, the results demonstrated that the SAM reaction occurred also on the uncoated the PET side. After the SAM treatment, a small increase of the water vapor permeability is observed, probably due to a crack or defect onset of the SiOx coating of the SAM modified films. On this point, atomic force measurements demonstrated an increment of the SiOx coating layer roughness after the SAM treatment execution. Finally, the transparency changes of the SAM treated films, measured in the wavelength range 400⁻800 nm, were always small, so that the results were acceptable for the films' use in applications where high transparency is required.

3D Printing of PLA/clay Nanocomposites: Influence of Printing Temperature on Printed Samples Properties.

In this study, the possibility of using a layered silicate-reinforced polylactic acid (PLA) in additive manufacturing applications was investigated. In particular, the aim of this work was to study the influence of printing temperature in the 3D printing process of PLA/clay nanocomposites. For this reason, two PLA grades (4032D and 2003D, D-isomer content 1.5 and 4, respectively) were melt-compounded by a twin screw extruder with a layered silicate (Cloisite 30B) at 4 wt %. Then, PLA and PLA/clay feedstock filaments (diameter 1.75 mm) were produced using a single screw extruder. Dog-bone and prismatic specimens were 3D printed using the FDM technique at three different temperatures, which were progressively increased from melting temperature (185⁻200⁻215 °C for PLA 4032D and 165⁻180⁻195 °C for PLA 2003D). PLA and PLA/clay specimens were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and tensile tests. Moreover, the morphology of the 3D printed specimens was investigated using optical microscopy and contact angle measurements. The different polymer matrix and the resulting nanocomposite morphology strongly influenced 3D printed specimen properties. DMA on PLA/clay filaments reported an increase in storage modulus both at ambient temperature and above the glass transition temperature in comparison to neat PLA filaments. Furthermore, the presence of nanoclay increased thermal stability, as demonstrated by TGA, and acted as a nucleating agent, as observed from the DSC measurements. Finally, for 3D printed samples, when increasing printing temperature, a different behavior was observed for the two PLA grades and their nanocomposites. In particular, 3D printed nanocomposite samples exhibited higher elastic modulus than neat PLA specimens, but for PLA 4032D+C30B, elastic modulus increased at increasing printing temperature while for PLA 2003D+C30B slightly decreased. Such different behavior can be explained considering the different polymer macromolecular structure and the different nanocomposite morphology (exfoliated in PLA 4032D matrix and intercalated in PLA 2003D matrix).

Binders alternative to Portland cement and waste management for sustainable construction-part 1.

This review presents "a state of the art" report on sustainability in construction materials. The authors propose different solutions to make the concrete industry more environmentally friendly in order to reduce greenhouse gases emissions and consumption of non-renewable resources. Part 1-the present paper-focuses on the use of binders alternative to Portland cement, including sulfoaluminate cements, alkali-activated materials, and geopolymers. Part 2 will be dedicated to traditional Portland-free binders and waste management and recycling in mortar and concrete production.