Bionanocomposites materials for food packaging applications: Concepts and future outlook

Carbohydrate Polymers 193 (2018) 19–27

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Carbohydrate Polymers journal homepage: www.elsevier.com/locate/carbpol

Bionanocomposites materials for food packaging applications: Concepts and future outlook

T

⁎

Ahmed M. Youssefa, , Samah. M. El-Sayedb a b

Packing and Packaging Materials Department, National Research Centre, 33 El Bohouth St. (Former El Tahrir St.), Dokki, Giza, Egypt, P.O. 12622 Dairy Science Department, Food Industries and Nutrition Division, National Research Centre, 33 El Bohouth St. (Former El Tahrir St.), Dokki, Giza, 12622, Egypt

A R T I C LE I N FO

A B S T R A C T

Keywords: Bionanocomposites Nanoparticles Packaging application Barrier properties Antibacterial activity

Bionanocomposites materials open a chance for the usage of novel, high performance, lightweight, and ecofriendly composite materials making them take place the traditional non-biodegradable plastic packaging materials. Biopolymers like polysaccharides such as chitosan (CS), carboxymethyl cellulose (CMC), starch and cellophane could be used to resolve environmental hazards owing to their biodegradability and non-toxicity. In addition these advantages, polysaccharides have some disadvantages for example poor mechanical properties and low resistance to water. Therefore, nanomaterials are used to improve the thermal, mechanical and gas barrier properties without hindering their biodegradable and non-toxic characters. Furthermore, the most favorable nanomaterials are layered silicate nanoclays for example montmorillonite (MMT) and kaolinite, zinc oxide (ZnO-NPs), titanium dioxide (TiO2-NPs), and silver nanoparticles (Ag-NPs). In packaging application, the improvement of barrier properties of prepared films against oxygen, carbon dioxide, flavor compounds diffusion through the packaging films. Wide varieties of nanomaterials are suitable to offer smart and/or intelligent properties for food packaging materials, as demonstrated by oxygen scavenging capability, antimicrobial activity, and sign of the level of exposure to various harmful features for instance oxygen levels or insufficient temperatures. The compatibility between nanomaterials and polymers matrix consider the most challenge for the preparation of bionanocomposites as well as getting whole distribution of nanoparticles into the polymer matrix. We keen in this review the development of packaging materials performance and their mechanical, degradability and thermal stability as well as antibacterial activity for utilization of bionanocomposites in different packaging application is considered.

1. Introduction Nanotechnology is considering an important tool for the improvement of advanced materials. By 2020 it has been expected that nanotechnology will influence at least $3 trillion through the worldwide economy, generating a request for 6 million employers in different production field (Duncan, 2011). The universal nanotechnology associated to food packaging was US$4.13 billion in 2008, which has been predictable to at about 12% compound annually enlargement rate. Through this global tendency, it is predictable that nanotechnology will offer the main drive in the progress of novel packaging applications systems for satisfying consumer’s requirements.

Nanotechnology covers the characterization, preparation and/or influence of structures, devices or materials that have at least one dimension that is about 1–100 nm in length. When the particle size is reduced lower this threshold, the fabricated material shows chemical and physical properties which are meaningfully diverse from the properties of macro-scale materials contain the identical materials. Classic nanomaterials could be classified into main three classes, particulates, platelets and fibers (Youssef, Bujdos et al., 2013; Youssef, Kamel, & El-Samahy, 2013). As a result of their nano-sized, polymer nanocomposites materials own extremely large surface-to-volume ratio and surface activity, by adding it to compatible polymers matrix with different loadings, the adding of this nanomaterials will dramatically

Abbreviations: APS, ammonium peroxidisulfate; Ag-NPs, silver nanoparticles; Au-NPs, gold nanoparticles; CH, chitosan; CMC, carboxymethyl cellulose; EVOH, ethylene vinyl alcohol; PCL, poly(caprolactone); PEO, poly (ethylene oxide); PGA, poly (glycolic acid); PHB, poly (hydroxybutyrates); PLA, poly (lactic acid); PVA, polyvinyl alcohol; PC, polycarbonate; PS, polystyrene; PANI, polyaniline; TGA, thermal graphmetric analysis; DSC, differential scanning calorimety; CNW, cellulose nanowhiskers; K, kaolinite; LNP, lignin nanoparticles; LDPE, low density poly (ethylene); MIC, lowest inhibition concentration; MMT, montmorillonite; NFC, nanofibrillated cellulose; NCC, nanocrystalline cellulose; MFC, microfibrillated cellulose; NPs, nanoparticles; RIT, comparative inhibition time; XRD, X-ray diffraction pattern; Tg, glass transition temperature; TiO2-NPs, titanium dioxide nanoparticles; WVP, water vapor permeability; OTR, oxygen transmission rate; ZnO-NPs, zinc oxide; SEM, scanning electron microscopy; TEM, transmission electron microscopy; MAP, modified atmosphere packaging ⁎ Corresponding author. E-mail address: [email protected] (A.M. Youssef). https://doi.org/10.1016/j.carbpol.2018.03.088 Received 22 January 2018; Received in revised form 16 February 2018; Accepted 24 March 2018 Available online 27 March 2018 0144-8617/ © 2018 Elsevier Ltd. All rights reserved.

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4. Packaging

develop the material properties of the resultant polymer nanocomposites, for example, enhanced mechanical, thermal stability and improved electrical conductivity (Thostenson, Li, & Chou, 2005; Uskokovic, 2007). Therefore, nanomaterials are favorable for improving the barrier and mechanical properties of food packaging materials, in addition to the improvement of innovative structures for smart and active packaging applications. Food packaging carries on growing in respond to the improvement of nanotechnology and material, accompanied by the changing consumers’ request. Nowadays international market, packaging not only is important to facilitate real supply in addition to conservation of food products, but also to simplify their end-use suitability and communication at the consumer levels. Packaging offers control and protects food products over distribution and storage from outside and inner disapproving conditions, for instance, microorganism, gasses, odors, water vapor, dust, and mechanical shock.

Packaging typically covers a number of types. The first type, identified as the primary packaging, that contains the materials or package which directly contact with the food. Or is the package in which a unit of the product is accessible in the market for example a bag of peanuts, a can of tuna, a jar of jam or the cover surround a chocolate candy all considered as models of primary packages. Also, Primary packaging is frequently limited in an outer or secondary package for transport and storage. For example, a carton box of tuna containing, approximately, 20 or 40 separate cans of tuna. Secondary packages can be gathered into a ‘lot’ controlled in a tertiary package, etc. Food packaging is, by itself, a huge multidisciplinary area of studies, research, and development. To achieve good food products (quality & safety) through storage and transportation, and to extend food products shelf-life through avoiding disapproving issues or conditions for instance chemical contaminants, damage microorganisms, oxygen, moisture and light barrier, etc., packaging materials produce suitable physical and chemical conditions for food products which are vital to gain a suitable shelf life and preservative food products (Yam, Takhistov, & Miltz, 2005). Current packaging has made more progress as results of international styles and consumer favorites. These improvements are focused on to achieve better food quality and safety (Yam et al., 2005). Additionally, by the move on the way to globalization, packaging requirements too extended shelf life, besides monitoring the safety and the quality of the packages products based upon international standards. Nanotechnology could statement all these necessities and prolongs and implements the basic packaging functions – containment, protection and preservation, marketing and communications (Fig. 1).

2. Classification of composites materials Composites are categorized into three main types.1- Laminated composites; they are composed of layers of materials held together by the matrix binder. 2- Fibrous composites; they are composed of reinforcing fibers in a matrix. 3- Particulate composites; they consist of particles dispersed in a matrix. These particles are sometimes divided into two subclasses (I) skeletal, which consists of a continuous skeletal structure filled with one or more additional materials (II) flakes which consist generally of flat flakes oriented parallel to each other, particles may have any shape, configuration or size. These particulates may be powders, beads, rods, crystalline, amorphic, or whiskers. Fillers are added to the polymer matrix for a number of reasons. Fillers may reduce costs, lower the coefficient of linear expansion, decrease shrinkage, and reduce molding cycles, increase thermal conductivity and lower resistivity Fu and Qutubuddin, (2001). Mechanical properties of filled polymer are influenced by the shape, size, and orientation of the fillers. Shifts in glass transition temperature Tg to a higher temperature as a function of the concentration of the filler is existing. Relative density may be an important consideration in some application. Glass and plastic hollow spheres will lower composite density, which may be beneficial where mass savings are critical.

4.1. Packaging materials

3. Bionanocomposites

The utilization of plastics, glass, and metals in packaging applications as non-biodegradable and non-renewable materials has increased anxieties about environmental contamination and therefore present is a request for the safe administration of such waste materials. Huge quantities of materials were used for packaging applications are formed each year through the purpose of usage and throw. Old-fashioned approaches for treatment postconsumer plastic wastes consist of burning and landfilling which attitude a risk to our health and environment

Bionanocomposites are a novel type of materials with at least one ultrafine phase dimension, characteristically a few nanometers. Furthermore, nanocomposites have produced great attention in polymer science and engineering. The nanocomposite definition is material has enlarged considerably to cover a large diversity of systems for example one-dimensional, two-dimensional, three-dimensional and amorphous materials, prepared of definitely different components and mixed at the nanometer level. Bionanocomposites are common in two different areas of material science: ceramics and polymers. Bionanocomposites are usually based on biopolymer matrices reinforced by nanofillers (e.g., precipitated silica (Motomatsu, Takahashi, Nie, Mizutani, & Tokumoto, 1997), silica beads (Frisch & Mark, 1996), zeolites (Frisch & Mark, 1996) besides colloidal dispersion of rigid polymers. The interactions of polymer-clay nanocomposites have been studied through the sixties and the early seventies but it is only relatively recently that researchers from Toyota (Okada et al., 1990) discovered the probability to fashion a nanostructure materials from a polymer and organoclay. This novel material based on polyamide 6 and modified clay displayed great enhancements of mechanical, barrier properties and increase thermal stability by comparing with the original polymer and this was accomplished at low modified nano-clay ratio 4 wt% (Youssef, Bujdos et al., 2013; Youssef, Kamel et al., 2013).

Fig. 1. Packaging functions including its advanced packaging systems, active and intelligent packaging: adapted from (Yam et al., 2005). 20

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5. Types of packaging

(Davis & Song, 2006; Scott, 2000). Therefore, there is a consumer demand for products that are environmentally friendly, safe and nontoxic. On the other hand, the limitations in fossil oil resources have forced the economy to focus on alternative resources from forest and agricultural origins.

Modern packaging, conversely, must help as an effective way to keep the quality of food products as well as to rise product prices, supporting sales and communicating data (Han, 2005). Old-fashioned packaging technologies usage for packaging fresh meat also vacuum packaging, modified atmosphere packaging (MAP) mainly used for packaging processed meat products. In current periods, technological developments in materials science, methods and tools have improved the efficacy of the packing of foodstuffs. The properties of packaging materials have greatly affected on the quality of packaged foods. Usually, the films fashioned from plastic which used for MAP in addition vacuum packaging were recognized for increasing efficiency in their moisture, gas barriers, sealing characteristics, shrinking and a diversity of print besides color choices (Sebranek & Houser, 2006). The enhancements in shelf-life and quality of food products have been accomplished mostly through passive packaging that control gas permeability or water vapor permeability along with partially through the use of bioactive agents into or onto the materials which used for packaging. Cellulosic fibers have conventionally been used in packaging for a widespread variety of food kinds for example freezing or liquid foods, dry food products and fresh foods (Yousefi et al., 2013). The main roles of food packaging are for protecting besides preserve the foodstuff; maintain its value and safety, and reduction food residual (Bradley, Castle, & Chaudhry, 2011). Cellophane is the greatest universally used for food packaging, which is too recognized as renewed cellulose in the film. Cellophane based films were fabricated using cellulose derivatives for example hydroxyethyl cellulose and cellulose acetate. Fiber procedures packaging involves of 100% main fiber that provides good mechanical properties and elasticity, and its great purity are accepted for straight interaction with package materials (food), additionally, it may be treated with a varied choice of coatings layers to keep foods from moisture, light, bacteria as well as additional hazards.

4.1.1. Biopolymers and paper as packaging materials The biopolymers have been increasingly introduced as renewable packaging materials and alternatives for petroleum-based polymers, including polysaccharides (starch and cellulose derivatives, chitosan, and alginates), lipids (bees and carnauba wax, and free fatty acids), proteins (casein, whey, and gluten), poly hydroxybutyrates (PHB),polylactic acid (PLA),poly caprolactone (PCL), polyvinyl alcohol (PVA), poly butylene succinate and their biopolymer blends. The poly glycolic acid (PGA) has received special attention because of its excellent barrier properties and production of its precursor, glycolic acid, via a natural metabolic route (Koivistoinen, 2013). Depending on successful compounding and processing, their mechanical strength together with oxygen and moisture barrier properties can be optimized for packaging applications (Tang, Kumar, Alaviand, & Sandeep, 2012). Some values for OTR (oxygen transmission rate, cm3 μm/m2 day bar) and WVTR (water vapor transmission rate, g/m2 day) of neat biopolymers, which are in between the values for traditional low density polyethylene (LDPE) and ethylene vinyl alcohol (EVOH). The problems in handling of most biopolymers may get up owing to the relatively high molecular weights and viscosity, hydrophilicity, crystallization behavior, brittleness or melt uncertainties that delay a full use at industrial scale. As a result, combination with additional biopolymers, plasticizers and compatibilizers is beneficial. However, the barrier properties and mechanical stiffness/strength of native biopolymer films are often inferior for packaging applications and they should be modified through physical cross-linking or surface modifications e.g., grafting or coating (Vartiainen, Vähä-Nissi, & Harlin, 2014). Alternatively, they are used for formation of multilayer packaging films or nanocomposites (Rhima, Parkb, & Ha, 2013). Paper is broadly used for packaging. Actually, the low price, low weight, extensive obtainability, printability and good mechanical properties reflect on the most benefits of paper as packaging materials. Its deficiency is sensitivity to water and moisture absorption (Miltz, 2011). The polymer is considering the greatest significant type of packaging materials, polymer materials are justly diverse and flexible. They can be rigid or flexible, thermosetting or thermoplastic, transparent or opaque, practically crystalline or almost amorphous. Polymers are able to be produced as films or as containers of many shapes and sizes. Interestingly, the paper materials have been increasingly processed in combination with a biopolymer coating layer to improve the barrier properties (Khwaldia, Arab-Tehrany, & Desobry, 2010). The surface treatment of nanofillers as well as the blending biopolymers could be used for fashion hierarchical structures which increase hydrophobicity, complete barrier protection and functionalities of coated papers (Abdelgawad, El-Naggar, Hudson, & Orlando, 2017).

6. Nanomaterials and packaging applications 6.1. Inorganic nanoparticles and packaging applications In last few years, nanotechnology can be used to meet the requests of consumers in proving food's value and by using antimicrobial agents for increasing the shelf life of foods during storage and distribution. Food productions should select the packaging materials that are appropriate for their food (Youssef, 2014). Furthermore, modern nanotechnology helps to reproducibly fabrication a range of precise nanoparticles in harmony through their differences in specific size, shape and surface structure properties (El-Naggar, Shaarawy, El Shafie, & Hebeish, 2017; El-Naggar, Abdelgawad, Tripathi, & Rojas, 2017; JuNam & Lead, 2008). Among these metals, zinc, iron, copper, gold, aluminum, nickel, and silver. It is also probable to yield metallic oxides as nanoparticles. These include oxides of titanium, iron, zirconium and zinc, or silicate minerals such as talc and mica. For the duration of manufacturing of metal nanoparticles, particularly of noble metal nanoparticles, predominantly two aspects should be considered. The first aspect is the controlled growth of metal nanoparticles in terms of particle size, particle size distribution, and structure because these characteristics impact the material properties (Jiang, Oberdörster, & Biswas, 2009). The other important aspect is the stabilization because properties such as durability in catalytic reactions depend upon the stability of the nanoparticles (Ju-Nam & Lead, 2008). Interactions between the nanoparticles happen to reduce the high surface energy, which usually results in agglomeration. To prevent these interactions, the surface can be protected by stabilizers, so-called capping agents. Capping agents can be organic or biological molecules or polymers, which prevent agglomeration either by charge or by steric stabilization mechanisms. For instance, the fabrication of zinc oxide nanoparticles resulted in

4.1.2. Glass and metals as packaging materials Metals and glass are practically resistant to gasses and vapors; consequently they deliver an effective barrier in contrast to material exchange between the air inside the package and the atmosphere outside (Robertson, 1993). Gases and vapors might travel throughout packaging materials either via molecular diffusion or by run through pores and holes. Therefore, the barrier properties for bio-based packaging materials can be improved by coatings using atomic layer deposition (Hirvikorpi, Vähä-Nissi, Mustonen, & Karppinen, 2010). The resistance against moisture should be improved by increasing the hydrophobicity by surface treatments. While fluorides are generally offering highest hydrophobic protection, alternative routes for environmentally-friendly modifications have been developed in recent decade, using chemical routes or physical techniques. 21

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Cellulose microfibrils consist of crystalline and amorphous areas that are arbitrarily dispersed beside their length. In the previous, cellulose chains are full strictly, while the final is supplementary vulnerable to chemical or enzymatic strike. The mechanical treatment of cellulose fibers under grinding or homogenization allows the fibrillation of native cellulose fibers to different degrees depending on the intensity of the processing, resulting in microfibrillated cellulose (MFC) or nanofibrillated cellulose (NFC). The nanocrystalline cellulose (NCC) or cellulose nanowhiskers (CNW), is cellulose pure in crystalline shape by nanoscal dimensions, might be managed from various resources of biomass, using enzyme hydrolysis or in moderate conditions of acid hydrolysis, for producing gel, liquid or powder forms through the elimination of the amorphous areas. The resultant NCC has a rigid rodshaped construction, 1–100 nm in diameter and 10–100 nm in length (De Souza Lima & Borsali, 2004). NCC one of the strongest and inflexible natural existing materials, NCC displays amazing properties such as great tensile strength (7.5 × 103 MPa), high stiffness, large surface area (150–250 m2/g),high aspect ratio (70)in addition displaying fascinating optical and electrical properties (Revol, Godbout, & Gray, 1998). The eco-friendly green material has been encouraged for expanded utilization, for example, possible nanofillers for the preparation of industrial composites. Utilization of cellulosic nanofibers in packaging applications will reduce the prices of packaging products because of their extensive obtainability. Also, the use of nanocellulosic materials will protect the environment due to its reusability and recyclability (Kalia et al., 2011) NFC mainly contains cellulose fiber fixed into a polymeric matrix, hence, these nanofibrillated cellulose might deliver greater rigidity, tensile and flexural properties. In particular, the fibrillated cellulose materials are known for their intrinsically good oxygen barrier resistance, as the dense network of cellulose fibrils hinder the penetration of gas molecules through the structure (Nair, 2014). Thus, an advanced method with nanofibrillated cellulose may be a valuable way for the progress of maintainable packaging with enhanced properties and for qualitative eco-friendly managing of materials used for packaging. Besides, designing cellulosic nanofibers for sustainable packaging will make a good knowledge for the end user in addition to let for wellorganized manufacturing systems. Nanofibrillated cellulose is designated to be an encouraging natural material and therefore NFC is used for smart food packaging, pharmacological products and medical as well for other developed applications. Furthermore, the utilization of nanocellulosefiber in packaging has the affinity to overcome of means effective challenges via decreasing packaging waste residual generation as a result of its sustainability and reusability (Marsh & Bugusu, 2007).

smaller particles (mean size 12 nm) when a thiol capping agent was added, compared to the synthesis of zinc oxide nanoparticles without capping agent (mean size 47 nm) (Padmavathy & Vijayaraghavan, 2008). If the preparation route permits the introduction of surface molecules before agglomeration occurs, particles can continue dispersible in certain media. Furthermore, surface molecules may be improved by chemical synthesis after formation of the particle. This postsynthesis route opens a variety of possible surface modifications, which can be adjusted to different applications (Borm et al., 2006). Therefore, inorganic/organic composite materials are prepared with many structures whereby merging organic and inorganic materials, the result composites may have advantages of both organic and inorganic materials, thus creating various usages in many applications. Zinc oxide is one of the most important types of nanoparticles that are used in improving the packaging materials properties because of its good antibacterial activity, high stability, photocatalytic activity. ZnO-NPs can be obtained by a thermal method using zinc acetate (Li, Wang, Liu, Zhang, & Li, 2005). Attributable to its good thermal and chemical stability and tunable optical and electrical properties (Tripathi & Rath, 2013), ZnO-NPs might be used in several applications for instance coatings for papers, pigments, optical material and cream lotions to protect against sunburn (Prabhu, Rao, Kumar, & Kumari, 2013). Moreover, ZnO-NPs have various important applications in the biomedical area, as a food additive, in catalysis and other important applications (Youssef, El-Nahrawy, & AbouHammad, 2017). Silver nanoparticles are used in a rising range of products, comprising fibers, washing machines, polymers, medical applications, sinks and hygienic ceramics and many consumer requests for example antiseptics and cleaning agents (Buzea, Pacheco, & Robbie, 2007). Additionally, the antimicrobial properties are browbeaten by the cosmetics industry, for instance, in deodorants, and by the textile industry in sportswear and protective clothing (Duran, Marcato, De Souza, Alves, & Esposito, 2007; El-Newehy et al., 2016; Kokura et al., 2010).Silver ions have a bactericidal influence by blocking the enzymes necessary for the oxygen metabolism of the cells, therefore inhibiting their core metabolic functions. They also destabilize the cell membrane and disrupt cell division and thus the reproduction of bacteria (Pal, Tak, & Song, 2007). The utilization of nanoparticles increases the size of the silver surface in contact with its surroundings with the other advantage of significantly reducing the amount of silver required to attain the same antiseptic effect. Furthermore, silver nanoparticles have the benefit that they can also be combined into a large number of materials. Also, silver nanoparticles show an antifungal activity (Esteban-Tejeda, Malpartida, Esteban-Cubillo, Pecharroman, & Moya, 2009). The mode of action seems similar to the mechanism of the antimicrobial activity because silver nanoparticles cause the death of fungi through the destruction of membrane integrity. Such unique attitude to develop novel nanoparticles-based antifungal is largely required, owing to an upward trend in fungal infections (Kim et al., 2008; Youssef, Bujdos et al., 2013; Youssef, Kamel et al., 2013). Gold nanoparticles were also used as antimicrobial agents against Gram-negative and Gram-positive bacteria. Also Rai, Prabhune, and Perry (2010) studied the antimicrobial of gold contrary to Gram-negative and Gram-positive bacteria. Biosynthesized gold nanoparticles were revealed to have high antimicrobial activity in contrast to numerous G+ and G- pathogenic bacteria and yeasts (Das, Das, & Guha, 2009).

7. Bionanocomposites and packaging applications Regardless the enhancement of the material properties, the incorporation of nanomaterials into the food packaging materials has caused anxieties amongst the consumers around the effects resulting from the ingestion of these nanomaterials. For that reason, it is crucial to control the possible migration to food matrices and its toxicity by understanding the action dynamics of these nanoparticles (NPs) inside the human body as also their metabolization and elimination mechanisms, besides the description of monitoring issues (Azeredo, Mattoso, & McHugh, 2011). Alternative important anxiety when discussing the utilizing of nanofillers into biodegradable polymers is the repairs of its biodegradability (Paul, Delcourt, Alexandre, Monteverde, & Dubois, 2005). Scientists have started to statement a great and growing number of questions concerning the human and environmental safety of using different nanomaterials especially regarding the use of nanoparticles in the food packaging (Klaine et al., 2012). For achieving the biodegradation of polymers, the micro-organisms first essential to cut the polymer chains in order to decrease its molecular weight creating possible its transportation into the cells, the most of the biochemical processes occur. For breaking down the polymeric materials,

6.2. Organic nanoparticles and packaging applications The nanoparticles were used as a coating onto paper for evaluating the chemical and morphological properties in relative with good ink reception, hydrophobicity (Schoukens, Vonck, Stanssens, & Van den Abbeele, 2011), and optical properties (gloss) of coated papers. In latest years, the nanocellulosic materials have concerned the attention of researchers for taking full advantage of the mechanical and barrier properties of using packaging materials. 22

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Fig. 2. General mechanism of plastic biodegradation (Souza, 2015).

at the designated composite ratios, demonstrating a respectable miscibility. Also, TGA examination recommended that low loadings% of modified lignin around (3 wt%) can meaningfully change the thermal temperature decay of poly (vinyl alcohol). Really, lignin nanoparticles (LNP) extracted from original alkali lignin by hydrochloric acidolysis, have revealed to have extra notable influence than the big particles at inferior concentration in polymeric bionanocomposites (Yang, Kenny, & Puglia, 2015). Nair et al. (2014) described that nanosized lignin particles were further active than pure lignin in raising the thermal properties while using polyvinyl alcohol. The effect of adding cellulose nanocrystals (CNC) on the barrier properties as well as the immigration performance of pure PLA and its bionanocomposites were studied in view of the promising participation in food packaging applications (Fortunati, Peltzer et al., 2012; Fortunati, Puglia et al., 2012). Besides, the efficiency of cellulose nanocrystal extraction from Phormium Tenax leaf natural fibers (Fortunati, Peltzer et al., 2012; Fortunati, Puglia et al., 2012) orokr abahmiabast fibers as reinforcement phase in poly (vinyl alcohol) decomposable medium were examined by Fortunati et al. (2013). Also, Fortunati et al. (2013) successfully prepared PVA bionanocomposites reinforced with CNC extracted from commercial microcrystalline cellulose (MCC). It was too explained that the prepared nanocomposites from PVA and CNC stay transparent owing to the dispersion of CNC at the nano-scale in the PVA matrix. The microfibrillated cellulose (MFC) and nanofibrillated cellulose (NFC) has been considered used as fillers in PLA (Fukushima, Abbate, Tabuani, Gennari, & Camino, 2009), resulting in improved oxygen barrier properties owing to the intrinsic properties of the dense network of MFC and NFC fibers. The nanocomposites of MFC with micro- to nanosize structured PHB particles for barrier coatings have been fabricated through a solvent exchange process, resulting in good dispersion of the fibers and improving hydrophobic protection of the cellulosic nanofibers. Polymer bionanocomposites with antimicrobial activity are extremely suitable to reduce the growth of post-processing pollutant microorganisms, increasing the shelf life of food products as well as enhancing the food safety. Through the growing sustainability tendency with packaging materials, paper and polymer nanocomposites present a novel class of packaging materials. Youssef, EL-Sayed, Salama, EL-Sayed, & Dufresne (2015), Youssef,

the microorganisms defecate extracellular enzymes which depolymerize the polymers external the cells (Fig. 2). Formerly, the aerobic or anaerobic deterioration happen being the material biodegraded (Mueller, 2006). Bionanocomposites display improved in mechanical strength, barrier properties, and enhanced heat resistance related to their pure polymers and its composites (Sinha Ray, Easteal, Quek, & Chen, 2006; Thostenson et al., 2005). A typical model is the usage of modified nanoclay for increasing mechanical properties and thermal stabilities of nylon (Cho & Paul, 2001). While using of polymer nanocomposites in packaging applications, Bionanocomposites are predictable for tolerating the anxiety of thermal food treating, shipping, and storage (Giannelis, 1996). Moreover, due to their enhanced mechanical properties, polymer nanocomposites might let down evaluating, accordingly decreasing basis materials. Polymer nanocomposites offered an increase to an extraordinary attention since the 1950s, once they performed for the first time (Carter, Hendricks, & Bolley, 1950). The material act evicted to count on the amount of clay exfoliation, numerous approaches have been reflected for fabricating PNCs described using wide distribution of the nanofiller into the polymer matrix (Meera, Thomas, & Thomas, 2012). In parallel with that, the exfoliation and stabilization of the nanoclay is improved after surface modification forming organoclay nanocomposites, or after deposition of nanoparticles onto the individual clay platelet layers. Lately, some researchers were fabricated and characterized many types of bio-based polymer nanocomposites, which presenting properties appropriate for a varied kind of applications (Singh & Singh, 2005). Bio and synthetic polymers have been filled with modified clay (layered silicate) so that improve their required properties though retentive the bionanocomposites degradability in a moderately economic approach. In specific, bionanocomposites display high possibilities in offering outstanding barrier characteristics, attributable to the existence of the individual clay platelet layers which capable of interruption the molecule path producing the diffusive pathway more tortuous (Fig. 3). Hu, Ye, Tang, Zhang, and Zhang (2016) examined the preparation of PVA/modified lignin composites and displayed that microsized lignin was homogeneously distributed in a polymeric matrix of PVA, as a result of the strong interactions between modified lignin and PVA functions group. From the DSC data displayed only one Tg may be detected 23

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Fig. 3. Schematic illustration of the overall procedure for the preparation of nanocomposites and improvement of the barrier properties (Mihindukulasuriya & Lim, 2014).

conductive paper sheets comprising PANI and, PANI/PS composites. As well, silver nitrate (Ag-NO3) was used in different concentrations during the oxidative polymerization of aniline to produce silver nanoparticles (Ag-NPs) into the conducting paper sheets. The prepared sheet displayed good mechanical properties as a result of addition of PS and Ag-NPs. Moreover, the electrical conductivity also enhanced by the addition of PANI and Ag-NPs also the prepared paper sheet revealed good antibacterial properties contrary to G+ve and G−ve bacteria. Therefore, the prepared paper sheet might be used as new materials for packaging applications.

Abou-Yousef, El-Sayed, and Kamel (2015) estimate the possible accomplishment of another sustainable material as antimicrobial packaging application. Paper sheets from rice straw (as waste agriculture materials) coated with 5 or 10% polystyrene (PS) nanocomposites using titanium dioxide nanoparticles (TiO2-NPs) containing or not comprised silver nanoparticles (Ag-NPs) were prepared. The inhibitory influence of modified paper sheets contrary to Pseudomonas, Staphylococcus aureus, Candida, and Staphylococcus was studied. Also, polymer nanocomposites and paper create a novel class of packaging materials. Nassar and Youssef (2012) studied the preparation of silver nanoparticles through new technique as an antibacterial additive, where, synthesis occurred with theassistance of an innovative, non-toxic, and eco-friendly biological materials specifically rice straw (RS) powder. The Ag-NPs were then inserted into commercial polystyrene matrix with different concentrations. The recycled carton paper was coated via the polystyrene nanocomposites. The prepared carton sheet displayed good mechanical properties, water vapor permeability and antibacterial activity. Moreover, conducting polymers have created a great consideration as a result of their physical and chemical properties in addition to their possible application in an industry predominantly in packaging applications. But, one of the little developments of the greatest conducting polymer is that they are frequently fashioned as intractable films that are hard to process. The combination of conducting polymer in the prepared paper sheet was performance to overcome this difficulty and to generate novel composite materials which including the common properties of paper sheet with the chemical and electrically conducting properties of the using polymer. Paper/conducting polymer composite was prepared using aniline monomer directly on the prepared paper sheet by utilize ammonium peroxidisulfate (APS) as oxidizing agent at different reaction temperatures. The thermal stability and electrical conductivities results of the prepared composites were meaningfully improved over those of the blank paper sheet (Youssef, El- Samahy & Abdel Rehim, 2012). In addition, Youssef, El-Sayed, El-Sayed, Salama, and Dufresne (2016) studied the preparation and characterization of paper sheet containing polyaniline (PANI) and polystyrene (PS), in the presence of dispersed baggase pulp fibers through the oxidative polymerization reaction using polymerizing aniline monomer to yield

8. Nanotechnology in food packaging applications Utilization of nanotechnology in packaging applications is an emergent area in that packaging materials could be employed for enhancing the barrier and mechanical properties as well as biodegradability, heat-resistance and antifire properties related to the pure polymer. Besides opportunities for improving active antibacterial, antifungal surfaces and identifying in addition to sign microbiological and biochemical modifications were obtained (Moustaf, Youssef, & Nour, 2016). The most encouraging improvements launched in the market place equal to the present time are probable to develop the shelf-life as well the quality of packaged meat foodstuffs meaningfully, by enhancing the barrier characteristic and integrating bioactive nanomaterials incorporated into the prepared polymer nanocomposites as packaging materials. Youssef et al. (2016) prepared a new polymer bionanocomposites as packaging material by utilize chitosan, carboxymethyl cellulose, and ZnO-NPs, which was fabricated through casting technique. The fabricated polymer bionanocomposites displayed better thermal and mechanical properties compared with CH/CMC blend. Also, the Egyptian soft white cheese was prepared and packaged by the prepared novel bionanocomposites sheet and stored at 7 °C for 4 weeks. The influence of bionanocomposites films on packaged soft white cheese such as rheological properties, color measurements, moisture, pH and titratable acidity was evaluated and displayed insignificant change after storage period. Additionally, the bionanocomposite as packaging material showed good properties against total bacterial counts, mold &yeast and 24

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9. Bionanocomposites and safety

coliform in the packaged cheese. Combination of chitosan (CH), polyvinyl alcohol (PVA) and titanium oxide (TiO2) nanoparticles has been used to prepare nano-biocomposite film for packaging of soft brined cheese (Youssef, AbouYousef et al., 2015; Youssef, Bujdos et al., 2013). PVA has been used for its high hydrophilic and bio-inert properties, physical and chemical characteristics, while TiO2 has been used for its antimicrobial activity and providing mechanical robustness to the formed film (Youssef, Abou-Yousef et al., 2015; Youssef, EL-Sayed et al., 2015). The application of polymer nanocomposites in the food packaging application is to reduce food losses and deliver safe and healthy foodstuffs. As a result of the enhanced act in the properties of polymer nanocomposite as packaging materials for example (oxygen, carbon dioxide and water vapor permeability) better mechanical properties, recyclability, biodegradability, fire retardant, good thermal stability optical clarity, and increasing smart antibacterial and antifungal surfaces, as well as detecting and indicating biological and chemical alterations, thus food packaging has been unique of the greatest focused polymer bionanocomposites technology improvement (Johansson, 2011). To meet consumer needs for natural, possibly environmental and biodegradable food packaging materials, scientific investigation has focused on the combination of natural antibacterial agents for example plant extracts into the biopolymer films as packaging materials as an alternative of films fabricated from plastic films (Cutter, 2006). Inside the bio-based packaging materials, edible films and coatings have more attention in recent years because of their several advantages (Beverly, Janes, Prinyawiwatkul, & No, 2008).The capability of essential oils (EOs) to keep food products contrary to gram positive and gram negative pathogenic bacteria and decay microorganisms have been described by many scientists. In order to accomplish active antibacterial activity in food uses, the addition of high loading of EOs are commonly required, that could influence the odors and flavors of the packaged products (Gutierrez, Barry-Ryan, & Bourke, 2009). Consequently, modern study must emphasis on the combination of essential oils to edible films as an additional application in food packing (Seydim & Sarikus, 2006). Amongst the best active EOs, thyme and oregano EOs have been keen out for keeping the higher antimicrobial activity for meat packaging, which might be attributed to the existence of phenolic compounds, mainly thymol and carvacrol (Solomakos, Govaris, Koidis, & Botsoglou, 2008). The optimization of synthesis conditions for organic nanoparticles filled with vegetable oils for water repellency and protective barrier coatings on cellulose fibers or paper substrates has been presented, followed by the controlled thermal release of the encapsulated oils. In parallel, the hydrophobicity of microfibrillated cellulose was tuned by the in-situ surface deposition of wax-filled nanoparticles and release upon further processing in combination with a biopolymer (El-Naggar, Abdelgawad et al., 2017; El-Naggar, Shaarawy et al., 2017; El-Newehy, El-Naggar, & Alotaiby, 2018). Youssef, Abdel-Aziz, and El-Sayed (2014) reported the preparation of Chitosan–silver (CS–Ag)and Chitosan–gold (CS–Au) bionanocomposites films through a green methodology procedure, then the prepared nanoparticles were incorporated into chitosan matrix with diverse loadings, the fabricated chitosan nanocomposites films were displayed good antmicrobial activity in contrast to G+ve (Staphylococcusaureus) and G−ve bacteria (Pseudomonas aerugenosa), fungi (Aspergillusniger) and yeast (Candida albicans).The mechanism and influence of nanosized clay made it promising for the formation of intelligent materials using the clay with the functionality of organic components. Coatings by sol–gel process for hybrid organic–inorganic nanocomposite offer high barrier (Garland, 2004) which established for oxygen permeability for plastics films like PET and LDPE. Special plasma technology using dielectric barrier discharges was used for coating process.Also, coatings process have been described effective oxygen permeability and retentive CO2, as well may competing traditional smart packaging technologies for example oxygen scavengers (Fig. 4).

The safety of using bionanocomposites materials in packaging applications, insufficient scientific research have been lead to measure the risks related to the occurrence of tremendously small particles such as nanomaterials, several of nanoparticles biologically effective into human body otherwise distributed in the surroundings. Nanomaterials normally display dissimilar activity from which present at the macrolevel, as the nanomaterials which have very small particle size, in opinion, could let nanomaterials transfer throughout the human body more easily owing to very small particles compare to the bigger particles size, although nanomaterials have great surface area which raises their activity then permits larger interaction through cell membranes, besides better ability for absorption and migration (Li & Huang, 2008). The migration of nanoparticles from the package to the food was studied in the literature (Simon, Chaudhry, & Bakos, 2008). The consumers of food packaged products which composed of polymer nanocomposite as packaging materials the main worry is to prove the level of passage of nanomaterials from the film to the packaged products then if the immigration occurs, the influence of the digestion of nanomaterials inside the human organs beginning of the mouth to the last gastrointestinal region (Silvestre, Duraccio, & Cimmino, 2011). There is a critical requirement for understanding in what way the nanomaterials drive performance during they present in the human body. The occurrence nanocomposite based on polymer and nanomaterials was establish to delay the speed of movement of certain potentially hazardous chemicals for example triclosan and caprolactam from the nanocomposites films based on polyamide into the food equal to six times (De Abreu, Cruz, Angulo, & Losada, 2010). 9.1. Impact of using bionanocomposites on human health Usually, advantageous properties of polymer nanocomposite are known very well, nevertheless the perspective (eco-) toxicological belongings besides the influences on the health of human body, nanomaterials have up to now established little consideration. The major problem for using the nanocomposites is the great speed of diffusion of nanomaterials based consumer products convey approximately the necessity for an improved thoughtful around the possible effects that nanomaterials could have on biological systems (Bouwmeester et al., 2009). The impacts of using nanoparticles on the body as well as the atmosphere are growing lately. The anxieties of utilization of nanomaterials can cause novel allergens, diverse poisonous strains, also increasing adsorption degrees of nanomaterials by the surroundings. 10. Future trends and conclusion Bionanocomposites represent an inspiring route for creating new and innovative packaging materials. By adding appropriate nanoparticles such as montmorillonite (MMT) and kaolinite, zinc oxide (ZnO-NPs), titanium dioxide (TiO2-NPs), and Gold silver nanoparticles (Au-NPs & Ag-NPs), it will be probable for fabricating films for packaging have good mechanical, barrier and thermal performance. They can reduce flammability significantly and maintain the transparency of the polymer matrix. Inserted nanomaterials into packaging materials as nano-sensors will alert the customer if a food has gone bad. Bionanocomposites are a viable technology for “new” materials for near-future packaging applications, especially for flexible, fire resistance, antimicrobial and transparent barrier packaging films. In conclusion, the area of bionanocomposites as packaging materials still need scientific research and improvement in order to develop the shelf life, quality and marketability of diverse packaging materials. What can be in the near, design and incorporate multiple desired functionalities. For example antimicrobial, antibiotic, biodegradable, and combine responses to environmental or chemical changes. Moreover, it can be in the not-so-near future, fabricate bioinspired 25

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Fig. 4. Schematic representation of typical application structures of multilayer nanocomposite gas barrier packaging materials (Rhima et al., 2013).

nanostructure polymers nanocomposites. Look at nature’s examples of packaging, skins, structures with specific processes, and imagine if we could make synthetic equivalents.

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