Polylactide films produced with bixin and acetyl tributyl citrate: Functional properties for active packaging

Packaging materials are decisive to preserve the quality and nutritional value of food. Polylactide (PLA) is a biodegradable polymer with adequate mechanical properties for packaging applications, but its moderate oxygen barrier properties and high UV light transmission hamper its performance as packaging for oxygen- and light-sensitive products. Bixin, a carotenoid with coloring and antioxidant character, was used to improve the light barrier of PLA films plasticized or not with acetyl tri-butyl citrate (ATBC). The films were subjected to thermal treatment mimicking polymer processing temperatures. Despite more than 74 wt% of bixin degraded during heat treatment, films were still blocking up to 95% of UVA and 90% of UVB transmission. Plasticizing PLA with ATBC accelerated up to six times the bixin release into a food simulant, which allowed to reach relevant concentrations for food preservation. In conclusion, bixin is a promising natural antioxidant and UV-shielding additive of biodegradable packaging.     

Influence of melt processing on biodegradable nisin‐PBAT films intended for active food packaging applications

Biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) films incorporated with different levels of the antimicrobial peptide nisin were developed by melt processing. Structural, morphological, thermal, mechanical, and antimicrobial properties of the films were determined. The X‐ray diffraction patterns exhibited decreasing levels of intensity at 2θ values as the concentration of nisin increased. Scanning electron microscopy showed a heterogeneous morphology when higher amounts of nisin were incorporated. The antimicrobial films tested presented no significant differences in the melting temperature (123–125°C), and the crystallization temperature ranged from 69 to 75°C. The addition of nisin caused no significant modification in tensile strength values. However, results of Young's modulus and deformation at break differed significantly among samples. Active films demonstrated inhibition against the Gram‐positive bacterium Listeria monocytogenes. These results demonstrated that PBAT/nisin films produced by melt processing present a great potential for use as active food packaging materials aiming enhanced food safety. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43212.     

A review of biodegradable polymers: uses,current developments in the synthesis and characterization of biodegradable polyesters,blends of biodegradable polymers and recent advances in biodegradation studies

This review considers the uses of biodegradable polymers in terms of their relevance within current plastic waste management of packaging materials, biomedical applications and other uses; research papers and patents are catalogued. The chemical synthesis of polyesters and the microbial production of poly(hydroxyalkanoate)s, including recent publications in these areas, are covered and methods of characterization and structural analysis are outlined. Current research into two- and three-component blends is reviewed as a method of reducing overall costs and modifying both properties and biodegradation rates of materials. Finally, there is a summary of degradation processes. Both abiotic and biotic reactions are discussed, together with the development of biodegradation test methods, particularly with respect to composting. © 1998 Society of Chemical Industry     

Understanding external plasticization of melt extruded PHBV–wheat straw fibers biodegradable composites for food packaging

The objective of this work is to get further knowledge on the external plasticization mechanisms of melt extruded polyhydroxyl‐3‐butyrate‐co?3‐valerate (PHBV) when combined with wheat straw fibers (WSF). Different types of biodegradable substances, all authorized for food contact according to the European regulation, i.e., acetyltributyl citrate (ATBC), glycerol triacetate (GTA) and (PEG) at different molecular weights, were tested at different percentages (5, 10 and 20 wt %). Thermal and mechanical characterization of PHBV/plasticizer blends showed that a significant plasticizing effect was obtained using hydrophobic substances such as ATBC and GTA, with an increase of the elongation at break from 1.8% up to about 6% for an additive content of 10 wt %. However, the incorporation of WSF in plasticized PHBV led to a dramatic decrease in the elongation at break of composites, neutralizing the increase of this parameter by the addition of the plasticizers. The stress at break of plasticized films was also significantly decreased by the introduction of fibers. Such a loss of ductility was mainly explained by the occurrence of microscopic defects in the materials induced by the presence of fibers and to a poor adhesion at the fiber/matrix interface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41611.     

Development of extrusion blown films of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blends for flexible packaging

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a biodegradable polymer with significant potential for use in food packaging. However, its limited melt strength poses a challenge when employing film-blowing techniques to produce flexible packaging. To overcome this obstacle, we developed blends consisting of 70 wt% PHBV and 30 wt% poly(butylene-co-succinate-co-adipate) (PBSA). Organic peroxides such as dicumyl peroxide and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, were utilized as reactive compatibilizers to enhance the interfacial adhesion between the polymers. Additionally, acetyl tributyl citrate (ATBC) was employed as a plasticizer to improve processability and ductility. The inclusion of organic peroxides resulted in the formation of long-branched structures, as confirmed by the van-Gurp-Palmen plot. The melt flow index decreased from 30 to 9.8 g/10 min without ATBC and 15.5 g/10 min with ATBC. Successful production of blown PHBV/PBSA films was achieved on a pilot scale (bubble height 180 cm). These films exhibited heat-sealing capability and increased impact strength (7.7 kJ/m²). Moreover, the films maintained a maximum elongation at break of 4% during a 3-month storage experiment with frozen food. Food safety was assessed through overall migration experiments, and the non-plasticized films received approval. In conclusion, the compatibilized PHBV/PBSA blends demonstrate great potential as materials for manufacturing film-blown flexible packaging.     

Preparation and characterization of antistatic packaging for electronic components based on poly(lactic acid)/carbon black composites

Poly(lactic acid) (PLA) is a biodegradable aliphatic polymer obtained from renewable sources; its main application is in the packaging sector. Electronic components require the use of antistatic packaging that prevents damage and electric shock. As PLA has no conductive characteristics, it requires the addition of allotropic carbon forms such as conductive carbon black to make the polymer less resistive as the dissipative material and making it suitable for the manufacture of antistatic packaging. In this study, PLA was melt blended with 5, 10, and 15 wt % of carbon black. The composites were prepared using a high-speed mixer. Samples were characterized by Izod impact resistance tests, scanning electron microscopy, thermal properties, electrical characterization, and biodegradation tests in garden soil. The addition of carbon black in the PLA matrix increases the temperature of degradation and decreases the crystallinity degree and the impact resistance of the composites. However, carbon black is a great option to increase the electrical conductivity of PLA. The addition of carbon black in PLA makes the composite less resistive and suitable for use as antistatic packaging for the transportation and storage of electronic components. Furthermore, this composite does not cause damage to the environment as the carbon black does not interfere in the degradation mechanism of PLA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47273.     

Preparation and characterization of green-based anti-ultraviolet and antidripping biodegradable film

The biodegradable materials cannot meet the requirements as the agricultural film due to the poor UV resistance and antidripping performance. The work herein thus presented the development of the green-based anti-ultraviolet and antidripping multifunctional composite films using poly(butyleneadipate-co-terephthalate), microfibrillated cellulose (MFC), and soybean protein isolate (SPI) as the raw materials in the presence of other agents. The resulting composite films were systematically characterized using scanning electron microscope, thermogravimetry analysis (TG), UV, and rheometer measurements. The morphology changed obviously after introducing the MFC and SPI into the substrate film. In addition, the results indicated that the addition of MFC and SPI had a positive effect on the thermal stability and heat preservation of the film, respectively. The contact angle results indicated that SPI was an ideal antidripping agent and the MFC could be used as the release agent. The time of the first water drop of the film containing 2.5 g MFC and 2.0 g SPI was 6 min and 46 s, and the time of each 10 drops was less than 60 s, showing the advantages of using MFC as the release agent and SPI as the antidripping agent. The resulting multifunctional biodegradable films can be widely used in the agricultural and packaging fields.     

Antioxidant packaging development and optimization using agroindustrial wastes

The increasing use of non-biodegradable materials and the difficulty in recycling most of the available packaging have been pushing the development of biodegradable packaging. In this study, the potential uses of agroindustrial wastes to produce biodegradable films with antioxidant capacity were investigated. Starch films were produced by casting method using bran from jaboticaba peel, mango peel, and broccoli stalk. The influence of the concentration or type of bran in the properties of the films was evaluated through a central composite design. The results were analyzed by response surface and desirability function. Except for elongation and water solubility, the fitted equations were predictive in all studied properties. The films prepared from a higher concentration of mango peel exhibited better antioxidant capacity, while the broccoli stalk had no significant effect on antioxidant properties. The optimal formulation of the film (2.8% of jaboticaba peel and 20.0% of mango peel) and their predicted response variables (0.8 MPa for tensile strength, 40.0 MPa for Young's modulus, 4.5 mg/ml for IC₅₀, and 41.6% for inhibition percentage) were defined according to the results. The optimization was satisfactory and the film presented high antioxidant capacity and moderate mechanical properties, proving to be an alternative to replace plastic packaging.     

Tributyl citrate as an effective plasticizer for biodegradable polymers: effect of plasticizer on free volume and transport and mechanical properties

The effectiveness of tributyl citrate (TbC) as a plasticizer for polylactide and polyhydroxybutyrate was analysed in order to improve the ductility of these polymers and make them good candidates for food packaging applications. Although the thermal and mechanical properties have been widely studied in the literature, the effect of the plasticizer on free volume and transport properties has not been deeply analysed. The free volume was characterized using positron annihilation lifetime spectroscopy observing its linear increase with TbC content. The permeability to water vapour, oxygen and carbon dioxide was determined and the obtained results were related to the changes in glass transition temperature, level of crystallinity of the samples and free volume. This work would allow a better understanding of the effect of the plasticizer on the barrier and mechanical properties of polymers allowing the development of competitive materials for packaging applications. © 2018 Society of Chemical Industry     

Pullulan‐based films and coatings for food packaging: Present applications,emerging opportunities,and future challenges

Societal and industrial demands for lower environmental impact, cost effectiveness, and high‐performance goods and services are increasingly impacting the choice of technologies which are developed and deployed in consumer products. Like many other sectors, food packaging is moving to new technologies; the use of biopolymers is one of the most promising strategies toward an optimized use of traditional packaging materials (e.g., oil‐based plastics) without impairing the goal of extending shelf life. Among other food packaging materials, pullulan is attracting much attention due to its unique features. The goal of this review is to provide an overview of current and emerging applications of pullulan within the food packaging sector. In particular, the functional properties of interest for the food packaging industry will be discussed in light of the physicochemical attributes of this exopolysaccharide. Future challenges that may dictate the successful penetration of pullulan in the food packaging market are also outlined. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40539.     

Grafting of vinyl acetate onto low density polyethylene—starch biodegradable films for printing and packaging applications

Starch‐based biodegradable low‐density polyethylene (LDPE) films were used for graft copolymerization of vinyl acetate with ceric ammonium nitrate (CAN) in aqueous acidic medium as redox initiator with nitric acid. The extent of grafting was examined by Fourier‐transform infrared (FTIR) spectroscopy, attenuated total reflectance (ATR) spectroscopy, X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The objective behind the grafting of vinyl acetate onto the LDPE–starch biodegradable films is to make these suitable for printing and packaging applications without affecting the biodegradability of the original films. Copyright © 2004 Society of Chemical Industry     

A computer‐aided methodology to design safe food packaging and related systems

A specific “Failure Mode, Effects, and Criticality Analysis” (FMECA) methodology has been developed to detect substances, materials, and steps that are critical for the safety of packaging systems used in food contact and related applications. Contamination levels in the finished product beyond acceptable thresholds are screened via a systematic analysis of crossed mass transfer between components and a serialization of mass‐transfer instances during product lifetime. The whole framework, including physical modeling and expert systems, has been integrated within the open‐source simulation software FMECAengine. The whole approach is illustrated on three case studies representative of applications along the food packaging supply chain: (1) identification of critical routes of the contamination by printing ink constituents, (2) concurrent engineering of multipurpose packaging, and (3) application to surveys or control plans. The implementation of this framework within industrial commitments such as compliance with EU regulations and ISO 22000 type food safety management systems is discussed. © 2013 American Institute of Chemical Engineers AIChE J, 59: 1183–1212, 2013     

Kinetics of diffusion of a pollutant from a recycled polymer through a functional barrier: Recycling plastics for food packaging

Recycled polymers containing a pollutant can be used for food packaging if the food is protected by a functional barrier made of virgin polymer. The mathematical treatment of the diffusion of pollutant through the packaging is established when the diffusivity is constant and when there is no transfer through the packaging-food interface. A functional barrier not only reduces but also delays migration during a lag phase. An increase in the relative thickness of the functional barrier dramatically increases its efficiency. Practical examples are presented. The difficulties of control of migration through functional barriers are pointed out. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 597–607, 1997     

Antimicrobial nanocomposites and electrospun coatings based on poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) and copper oxide nanoparticles for active packaging and coating applications

Active biodegradable poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) melt mixed nanocomposites and bilayer structures containing copper oxide (CuO) nanoparticles were developed and characterized. The bilayer structures consisted of a bottom layer of compression molded PHBV3 (3% mol valerate) coated with an active electrospun fibers mat made with CuO nanoparticles and PHBV18 (18% valerate) derived from microbial mixed cultures and cheese whey. The results showed that the water vapor permeability increased with the CuO addition while the oxygen barrier properties were slightly enhanced by the addition of 0.05 wt % CuO nanoparticles to nanocomposite films but a negligible effect was registered for the bilayer structures. However, the mechanical properties were modified by the addition of CuO nanoparticles. Interestingly, by incorporating highly dispersed and distributed CuO nanoparticles in a coating by electrospinning, a lower metal oxide loading was required to exhibit significant bactericidal and virucidal performance against the food‐borne pathogens Salmonella enterica, Listeria monocytogenes, and murine norovirus. The biodisintegration tests of the samples under composting conditions showed that even the 0.05% CuO‐coated structures biodegraded within 35 days. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45673.     

Influence of high power ultrasound on physical–chemical properties of polypropylene films aimed for food packaging: barrier and contact angle features

Investigation was focused on the impact of high power ultrasound (HPUS), also called thermosonication, on the oxygen permeation properties (permeability, solubility and diffusion coefficients) of barrier films aimed for food packaging. For this purpose, biaxially oriented polypropylene (BOPP) coated with acrylic/polyvinylidene chloride (BOPPAcPVDC) and biaxially oriented coextruded polypropylene (BOPPcoex) were used. The physical–chemical profile of the samples was determined using goniometry. There is a significant impact only of extreme HPUS conditions (the longest time and the highest amplitude) on the permeability, solubility and diffusion coefficients of oxygen through the BOPP films. The highest influence on the oxygen permeability in both investigated BOPP samples involved an HPUS with an amplitude of 100% during a 6 min treatment. However, BOPP samples showed different sensitivities at lower HPUS treatments. © 2017 Society of Chemical Industry     

Composite sheets with biodegradable polymers and paper,the effect of paper strengthening agents on strength enhancement,and an evaluation of biodegradability

Composite sheets composed of biodegradable polymers (BP) and paper were prepared, and their physical and biodegradable properties were investigated. The paper sheets were soaked in BP emulsions and cured at 100°C for 20 min. The wet strength of composite sheets with the same basis weight increased significantly with increasing BP content, although dry strength increased only moderately. A 0.5% addition of a common wet paper‐strengthening agent, poly(amidoamine‐epichlorohydrin) (PAE) resin, enhanced the wet strength, which reached 9.3 MPa, of composite sheets consisting of a BP : paper ratio of 20 : 80. Further enhancement was achieved by the addition of polyvinylamines (PVAm). The wet tensile strength of composite sheets consisting of BP and paper (20 : 80) increased by 27% with the addition of 0.2% PVAm and 0.5% PAE, whereas it was enhanced by only 3–4% with the addition of 0.7% PAE. The biodegradability of the composite sheets was somewhat retarded by the addition of PAE and PVAm. However, a 90% weight loss was observed 60 days after placing composite sheet samples in soil. A similar weight loss was observed after 45 days for composites without additives and after 30 days for base paper alone. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 861–866, 2005     

Overmolded polylactide/jute-mat eco-composites: A new method to enhance the properties of natural fiber biodegradable composites

Environmentally friendly, biodegradable composites were prepared via overmolding of poly(lactic acid) (PLA) onto PLA/jute-mat, named as “ecosheets,” reinforced continuous fiber composite sheets. Film stacking procedure was used to prepare ecosheets via using a hot-press. The fiber orientation was changed as −45°/+45° and 0°/0°. −45°/+45° orientation exhibited higher properties as compared to 0°/0° for ecosheets; therefore, this construction was used to produce overmolded composites (OMCs). The mechanical tests showed that flexural modulus and strength of OMCs were improved in comparison to neat PLA. The dynamic mechanical analysis exhibited that the thermomechanical resistance of PLA was enhanced for OMCs. Scanning electron microscopy investigation showed that the jute/PLA interphase needs to be improved to further increase the properties. It was concluded that one of the biggest advantages of this novel technique was the increase of mechanical properties of PLA without altering the density. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48692.     

Utilization of ramon seeds (Brosimum alicastrum swarts) as a new source material for thermoplastic starch production

The development and characterization of biodegradable polymers deriving from renewable natural sources has attracted much attention. The aim of this work was to partially characterize a thermoplastic starch obtained from the starch of seeds from the ramon tree (TPS‐RS) as an option to substitute thermoplastic starch from corn (TPS‐CS), in some of its applications. At 55% of relative humidity (RH), TPS‐RS had higher tensile strength and deformation than TPS‐CS. X‐ray diffraction analysis showed similar values in residual crystallinity (percentage of crystallinity that remains after plasticization process) in both TPS. The SEM micrographs showed a few remnant granular structures in the TPS‐RS. The FTIR showed a greater intensity in band at 1016 cm^?1 in the TPS‐CS and TPS‐RS in comparison with their corresponding native starch, indicating an increase in the amorphous region after plasticization. The TGA analysis showed greater thermal stability in TPS‐CS (340 °C) compared with TPS‐RS (327 °C). In addition, the glass transition temperature in both TPS was 24 °C. The results obtained represent a starting point to potentialize the use of TPS‐RS instead of TPS‐CS for the development of new biodegradable materials for practical applications in different areas. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44235.     

食品软包装用透明高阻隔涂料：PVA涂料研究进展

聚乙烯醇（PVA）因其良好的透明性和成膜性以及优异的氧气和有机溶剂阻隔性，可用于透明、易回收、环境友好型的食品高阻隔软包装材料。但因其涂层对湿度敏感性差且不具备水蒸气阻隔性能而制约其发展。针对这一问题，目前主要有两种解决方法：一种是PVA化学交联，PVA能进行多元醇的酯化、醚化、缩醛化等化学反应；另一种是制备PVA-纳米复合涂料，PVA与纳米层状材料如蒙脱土（MMT）以及氧化石墨烯（GO）复合涂料的研究已取得较大进展。为此，分别从PVA的阻隔性及其影响因素、化学交联PVA涂料以及PVA-纳米复合涂料的最新研究进展进行了综述，分析了改性PVA涂料面临的问题，展望其未来研究方向。     

Synthesis and properties of hydrophilic polymers,part 11: Synthesis,biodegradability, and metal complexation of copolymers of ethylenediaminetetraacetic acid dianhydride and lactose

The synthesis and characterization of poly(ethylenediaminetetraacetic acid‐co‐lactose) of high molar mass (132 kg mol^?1) is described. The polycondensate with pendant carboxylic groups was shown to be hydrolytically and microbiologically degradable by using conventional microbiological methods. The metal complexing properties of the polyester were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II), Pb(II), and Al(III) ions in aqueous solution using the liquid‐phase polymer‐based retention (LPR) method. In addition, the complexing capacity of the Cu(II)‐saturated copolymer was determined by TGA to be 182 mg g^?1 polymer. According to the retention profiles determined as a function of filtration factor by using LPR in conjunction with inductively coupled plasma spectrometry, Cr(III) and Fe(III) showed a strong interaction with this polymer under these conditions, indicated by retention values of 100% at pH 5. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2932–2939, 2007