The performance characteristics of polylactic acid (PLA) as an active food packaging film can be highly influenced by the incorporation of active agents (AAs) into PLA, and the type of processing technique. In this review, the effect of processing techniques and the addition of natural AAs on the properties related to PLA performance as a packaging material are summarized and described through a systematic analysis, giving new insights about the relation between processing techniques, types of AA, physical–mechanical properties, barriers, optical properties, compostability, controlled release, and functionalities in order to contribute to the progress made in designing antioxidant and antimicrobial PLA packaging films. The addition of AAs into PLA films affected their optical properties and influenced polymer chain reordering, modifying their thermal properties, functionality, and compostability in terms of the chemical nature of AAs. The mechanical and barrier performance of PLA was affected by the AA’s dispersion degree and crystallinity changes resulting from specific processing techniques. In addition, hydrophobicity and AA concentration also modified the barrier properties of PLA. The release kinetics of AAs from PLA were tuned, modifying diffusion coefficient of the AAs in terms of the different physical properties of the films that resulted from specific processing techniques. Several developments based on the incorporation of antimicrobial and antioxidant substances into PLA have displayed outstanding activities for food protection against microbial growth and oxidation.
A new active coating was developed by using Cucumis metuliferus fruit extract as antioxidant additive with the aim of obtaining an easy way to functionalize low-density polyethylene (LDPE) films for food packaging applications. Thus, an extraction protocol was first optimized to determine the total phenolic compounds and the antioxidant activity of CM. The aqueous CM antioxidant extract was then incorporated into cellulose acetate (CA) film-forming solution in different concentrations (1, 3 and 5 wt.%) to be further coated in corona-treated LDPE to obtain LDPE/CA-CM bilayer systems. CA and CA-CM film-forming solutions were successfully coated onto the surface of LDPE, showing good adhesion in the final bilayer structure. The optical, microstructural, thermal, mechanical and oxygen barrier performance, as well as the antioxidant activity, were evaluated. The active coating casted onto the LDPE film did not affect the high transparency of LDPE and improved the oxygen barrier performance. The antioxidant effectiveness of bilayer packaging was confirmed by release studies of Cucumis metuliferus from the cellulose acetate layer to a fatty food simulant. Finally, the LDPE/CA-CM active materials were also tested for their application in minimally processed fruits, and they demonstrated their ability to reduce the oxidation process of fresh cut apples. Thus, the obtained results suggest that CA-CM-based coating can be used to easily introduce active functionality to typically used LDPE at industrial level and enhance its oxygen barrier, without affecting the high transparency, revealing their potential application in the active food packaging sector to extend the shelf-life of packaged food by prevention of lipid oxidation of fatty food or by prevention fruit browning.
Antioxidant biocomposites have been successfully developed from cellulose acetate, eco-friendly triethyl citrate plasticizer and onion extract as a source of natural antioxidants. First, an onion extraction process was optimized to obtain the extract with highest antioxidant power. Extracts under absolute ethanol and ethanol 85% were the extracts with the highest antioxidant activity, which were the characterized through different methods, DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS (2,2ʹ-azinobis(3-ethylbenzothiazoline-6-sulphonate)), that measure radical scavenger activity, and polyphenolic and flavonoid content. Afterwards, the extract was incorporated in cellulose acetate as polymer matrix owing to develop an active material intended to oxidative sensitive food products packaging. Different concentrations of onion extract and plasticizer were statistically studied by using response surface methodology in order to analyze the influence of both factors on the release of active compounds and therefore the antioxidant activity of these materials.
Microcellular nanocomposite foams functionalized with cinnamaldehyde (Ci) were obtained through two-step supercritical foaming and impregnation processing. PLA nanocomposite foams with different C30B concentrations (1, 2, and 3 wt.%) were obtained by foaming with scCO2 at 25 MPa and 135 °C and impregnated with Ci at 12 MPa and 40 °C. The effect of the C30B content and Ci incorporation on the morphological, structural, thermal, and release properties of the developed foams were investigated. The incorporation of Ci was not influenced by C30B’s addition. The presence of C30B and Ci incorporation reduced the average pore diameter slightly and the crystallinity degree of the foams extensively. Simultaneously, the experimental and theoretical characterization of the Ci release from the PLA nanocomposite foams in EtOH 50% was analyzed. The mechanism of Ci release from the foams was defined as a quasi-Fickian diffusion process that could be successfully described using the Korsmeyer–Peppas model. The active PLA foams presented a higher potential of migration and faster release when compared with that reported in commonly used PLA films, showing that biopolymeric foams could be potentially used as active food packaging to improve the migration of active compounds with low migration potentials in order to improve their biological activity in foods.
The deterioration of the physical–mechanical properties and loss of the chemical safety of plastics after consumption are topics of concern for food packaging applications. Incorporating nanoclays is an alternative to improve the performance of recycled plastics. However, properties and overall migration from polymer/clay nanocomposites to food require to be evaluated case-by-case. This work aimed to investigate the effect of organic modifier types of clays on the structural, thermal and mechanical properties and the overall migration of nanocomposites based on 50/50 virgin and recycled post-consumer polypropylene blend (VPP/RPP) and organoclays for food packaging applications. The clay with the most hydrophobic organic modifier caused higher thermal stability of the nanocomposites and greater intercalation of polypropylene between clay mineral layers but increased the overall migration to a fatty food simulant. This migration value was higher from the 50/50 VPP/RPP film than from VPP. Nonetheless, clays reduced the migration and even more when the clay had greater hydrophilicity because of lower interactions between the nanocomposite and the fatty simulant. Conversely, nanocomposites and VPP/RPP control films exhibited low migration values in the acid and non-acid food simulants. Regarding tensile parameters, elongation at break values of PP film significantly increased with RPP addition, but the incorporation of organoclays reduced its ductility to values closer to the VPP.
Bionanocomposites based on Polylactide (PLA) and Polyhydroxybutyrate (PHB) blends were successfully obtained through a combined extrusion and impregnation process using supercritical CO2 (scCO2). Graphene oxide (GO) and cinnamaldehyde (Ci) were incorporated into the blends as nano-reinforcement and an active compound, respectively, separately, and simultaneously. From the results, cinnamaldehyde quantification values varied between 5.7% and 6.1% (w/w). When GO and Ci were incorporated, elongation percentage increased up to 16%, and, therefore, the mechanical properties were improved, with respect to neat PLA. The results indicated that the Ci diffusion through the blends and bionanocomposites was influenced by the nano-reinforcing incorporation. The disintegration capacity of the developed materials decreased with the incorporation of GO and PHB, up to 14 and 23 days of testing, respectively, without compromising the biodegradability characteristics of the final material.