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Russian Journal of Agricultural and Socio-Economic Sciences, No.

10 (10) / 2012

Sumit Goyal, Gyanendra Kumar Goyal, Researchers
National Dairy Research Institute, Karnal, India
Received September 26, 2012
Nanotechnology has an extremely high potential to benefit society through applications in food packaging. It can make the products cheaper and the production more efficient by producing less waste
and using less energy. However, any new technology carries an ethical responsibility for wise application and the recognition that there are potential unforeseen risks that may come with the tremendous
positive potential. The concept of nanocomposites represents a stimulating route for creating new and
innovative materials, also in the area of natural polymers. The use of protective coatings and suitable
packaging by the food industry has become a topic of great interest because of their potentiality for
increasing the shelf life of many food products. Research and development of bio-nanocomposite materials for food applications such as packaging and other food contact surfaces is expected to grow in
the next decade with the advent of new polymeric materials and composites with inorganic nanoparticles.
Nanotechnology; Food Packaging; Food Products.
The use of protective coatings and suitable
packaging by the food industry has become a topic of great interest because of their potentiality
for increasing the shelf life of many food products (Ahvenainen, 2003; Coles et al., 2003; Hernandez et al., 2000). By means of the correct selection of materials and packaging technologies,
it is possible to keep the product quality and
freshness during the time required for its commercialization and consumption (Brown, 1992;
Stewart et al., 2002). A big effort to extend the
shelf life and enhance food quality while reducing packaging waste has encouraged the exploration of new bio-based packaging materials, such
as edible and biodegradable films from renewable resources (Tharanathan, 2003). The use of
these materials, due to their biodegradable nature,
could at least to some extent solve the waste
problem. Nowadays, the largest part of materials
used in packaging industries is produced from
fossil fuels and are practically un-degradable. For
this, packaging materials for foodstuff, like any
other short-term storage packaging material,
represent a serious global environmental problem
(Kirwan & Strawbridge, 2003). Unfortunately, so
far the use of biodegradable films for food packaging has been strongly limited because of the

poor barrier properties and weak mechanical
properties shown by natural polymers. For this
reason natural polymers were frequently blended
with other synthetic polymers or, less frequently,
chemically modified with the aim of extending
their applications in more special or severe circumstances (Guilbert et al., 1997; Petersen et al.,
1999). However, like conventional packaging,
bio-based packaging must serve a number of important functions, including containment and protection of food, maintaining its sensory quality
and safety, and communicating information to
consumers (Robertson, 1993).
Nanotechnologies promise many stimulating
changes to enhance health, wealth and quality of
life, while reducing the environmental impact.
The application of nanocomposites promises to
expand the use of edible and biodegradable films
(Lagaron et al., 2005; Sinha Ray & Bousmina,
2005). It will help to reduce the packaging waste
associated with processed foods and will support
the preservation of fresh foods, extending their
shelf life (Labuza & Breene, 1988; Vermeiren et
al., 1999).In addition, inorganic particles may be
used to introduce multiple functionalities like
colour and odours but also to act as reservoirs for
the controlled release functions of drugs or fungi-


2000. Steinbuchel. When starch is treated in an extruder by application of both thermal and mechanical energy. There are many opportunities for using starch as packaging material (Kim & Pometto. the most studied biodegradable nanocomposites suitable for packaging applications are starch and derivates. Trznadel. 2004). neurodegenerative diseases and cancer (Koo et al. Smits et al. high gas and vapour permeability. poly(butylene succinate) (PBS). temperature and oxygen availability. thermal. such as starch. polyhydroxybutyrate (PHB). Li et al. 1998. Neilsen. plasticizers are expected to efficiently reduce intra-molecular hydrogen bonds and to provide stability to product properties. Biodegradable plastics are polymeric materials in which at least one step in the degradation process is through metabolism in the presence of naturally occurring organisms. Kaplan. 2001. 1967). Owing to the nanometer-size particles obtained by dispersion.e. brit15 . several research groups started the preparation and characterization of various kinds of biodegradable polymer nanocomposites showing properties suitable for a wide range of applications (Sinha Ray & Bousmina. 1998). 2007). In particular. It is thought to provide significant health benefits. polylactic acid (PLA). 2005. Polymers produced by micro-organism or genetically modified bacteria (polyhydroxybutyrate. processing. The application of nanotechnology to these polymers may open new possibilities for improving not only the properties but also the same time the cost-price-efficiency. 1998). low heat distortion temperature. This review critically discusses use of nanocomposites for bio-based packaging.. So far. or nano-particles that release their contents on demand at targeted spots in the body.e. or chemically modified. these nanocomposites can exhibit markedly improved mechanical.. GOYAL. poor resistance to protracted processing operations have strongly limited their applications. it is converted to a thermoplastic material.S. 2003. Due to its hygroscopic nature.. they show great promise in providing excellent barrier properties. Although these factors are somewhat interrelated. tleness. polyethers. Under appropriate conditions of moisture. Mohanty et al. starch-based absorbent pads are expected to pro- BIODEGRADABLE NANOCOMPOSITES The extraordinary success of the nanocomposite concept in the area of synthetic polymers has stimulated new research on nanocomposites based on biodegradable polymers as matrix (Sorrentio et al. when compared with the starting polymers and conventional (microscale) composites. 2003. Common plasticizers for hydrophilic polymers. polynucleotides). stroke. Polymers produced by classical chemical synthesis using renewable bio-based monomers or mixed sources of biomass and petroleum (i. biodegradation leads to fragmentation or disintegration of the plastics with no toxic or environmentally harmful residue (Chandra & Rustgi. The problems associated with biodegradable polymers are threefold: performance. Although promising results were obtained. In the production of thermoplastic starches. (i) Starch and their derivates: Starch is a promising raw material because of its cyclic availability from many plants and excessive production with regard to current needs and its low cost (Gonera & Cornillon.. barrier and physico-chemical properties. problems due to ‘‘performance and processing’’ are common to all biodegradable polymers in spite of their origin (Scott. Recently. National Dairy Research Institute cides (Lee et al. Biodegradable polymers can be classified according to their source: 1. starch alone does not form films with appropriate mechanical properties unless it is first plasticized. In particular. proteins. 2007). Sorrentio et al. 2. Yan & Gilbert. urea and water... xanthan. 2007). are glycerol and other low molecular weight polyhydroxy compounds. due to the presence of the clay layers able to delay the molecule pathway making the diffusive path more tortuous (Bharadwaj. 2002. such as reduced risk of heart attack. 1994). pullan).K. As a packaging material. bacterial cellulose. 2005). 2005. 2004). It is known to be completely degradable in soil and water and can promote the biodegradability of a non-biodegradable plastic when blended.. Numerous food researchers are working with the aim to improve delivery of medicines or fragile micronutrients in the everyday foods by creating tiny edible capsules. 2002. and cost. Polymers directly extracted or removed from biomass (i. 1995). polylactic acid or bio-polyester) 3. polysaccharides. polypeptides. GOYAL. curdian. G. and aliphatic polyester as PCL. Description of biopolymers is available in literature (Doi & Steinbuechel. the road to successful bio-nanocomposites is still long (Sorrentio et al..

Instead. because of the hydrophilicity of the starch the performance changes during and after processing. In addition. 2003. McGlashan & Halley. and rather moderate improvements in properties have been reported in the case of PHB as matrix material (Maiti et al. Mechanical characterization results show an increase of modulus and tensile strength. The major drawback for the commercial use of the PHB homopolymer is represented by an unfavorable ageing process. 10 (10) / 2012 vide a potential alternative to conventional absorbent for meat exudation (Smith et al. 2006). fresh meat products and ready meals.. and whey. oxygen and moisture protection is needed. 2003. the monomer of PLA.. The carbohydrate feedstock may be agricultural products such as maize.. the formation of nanocomposite materials from PHB seems to be difficult. The properties of the PLA material are highly related to the ratio between the two forms (L or D) of the lactic acid monomer. beverage. In addition. In particular. PLA is the polymer with the highest potential for a commercial major scale production of renewable packaging materials. a strong tendency of tactoids formation was observed. 2004.. Wilhelm. 1995). As a matter of fact. the decomposition temperature was increased while the relative water vapour diffusion coefficient of TPS was decreased (Park et al. prepared by simple melt extrusion. Starch/clay nanocomposite films were obtained by dispersing montmorillonite nanoparticles via polymer melt processing techniques. 2003). due to the water content changes. whereas a mixture of D.. starch could be employed as packaging for fruits and vegetables. 2002. Park et al. the glass transition temperature increases only slightly with increasing clay content. 2003.. Solvent casting of mixtures of PLA and organophilic clay in chloroform resulted in materials with an enhanced crystallization tendency and increased Young’s modulus (Ogata et al. Maiti et al. 2002. Lactic acid. PLA) as packaging material is hampered by their high cost as well as their low performances. 2005). 2005. This may be due to the microcomposite structure rather than nanocomposite structure. No. (1999) reported the preparation of PLA-clay nanocomposites with much improved mechanical and thermal properties. exhibited remarkable improvement of material properties in both solid and melt states compared to the matrix without clay (Sinha Ray et al.. they are compatible with many foods. 1997. such as dairy products... Paul et al. many different routes have been reported. Films or bag. L-PLA is a material with a very high melting point and high crystallinity.. 2003). Due to its biodegradability and biocompatibility this biopolyester may easily find industrial applications (Van der Walle et al. (iii) Polyhydroxybutyrate (PHB): PHB is accumulated by a large number of bacteria as energy and carbon reserves. 2001. 2003. 2002). So far. 1997. Clay. In addition.. (ii) Polylactic acid (PLA): The use of conventional chemical synthesis for the production of polymers gives a wide spectrum of possible biopolyesters... the use of nanometric filler promises to expand its application. snacks or dry products. wheat.... PLA and PHB offer numerous opportunities in packaging applications. PHB is a typical highly crystalline thermoplastic with a very low water vapour permeability which is close to that of low density polyethylene (LDPE). De Carvalho et al. efficient mechanical. Many papers (Chang et al. 1997). To overcome this drawback. Liu et al.. 2000). Yoon & Deng. 2001.. Bandyopadhyay et al. Sinha Ray et al. 2007) report the use of PHB and PLA for the preparation of polymer/clay nanocomposite materials. In these applications... 2003. Nanocomposites of the PLA and PLA/PCL blends were obtained by 16 . molasses..and L-PLA results in an amorphous polymer with a low glass transition temperature. Sinha Ray et al.Russian Journal of Agricultural and Socio-Economic Sciences. Ogata et al. in this case. The PLA/layered silicate nanocomposites. Chen et al. however. However. may easily be produced by fermentation of carbohydrate feedstock. 2002. Pluta et al. They can be formed into films or used to make moulded objects. as potential filler. Sierakowski et al. Thermoplastic starch (TPS) alone often cannot meet all these requirements. Choi et al. the large-scale use of biodegradable polyesters (PHB.. has been chosen for improving the properties of TPS in such applications (Chen & Evans. 2002). the conformity of the resulting material samples with actual regulations and European directives on biodegradable materials was verified by migration tests (Avella et al. 2003. Also. To date. It has been shown that both the tensile strength and the elongation at break of TPS were increased with the presence of small amounts (less than 5%) of sodium montmorillonite (Park et al. Sorrentio et al. Potentially.

Messersmith & Giannelis. in contrast. Many research groups worked on the preparation of PCL/organically modified layered silicate (OMLS) nanocomposites with better physical properties (Gorrasi et al. Park et al. They essentially differ in the mode of formation and application to foods.. the barrier properties of crystalline lipids are highly dependent on the intercrystalline packing arrangement. Suitable polysaccharides include cellulose derivatives. 1997).. 1993. However.. 1989) and for extending the shelf life of apples (Drake et al.. formed and then applied to foods. They are formed by casting or by traditional plastic processing techniques. 1985. 1987).. chitosan and other polysaccharides (El Ghaouth et al. 1991). 1970. edible coatings form an integral part of the food product and hence should not impact the sensory characteristics of the food (Baldwin et al. 2002. pectins. Since the permeate can pass between crystals. Utracki et al. technology and applications of the water-soluble polysaccharides often referred to as gums or hydrocolloids is available (Aspinall. It is a semicrystalline polymer with a high degree of crystallinity (around 50%). Sometimes. Edible films. 1997). (iv) Polycaprolactone (PLC): PCL is linear polyester manufactured by ring-opening polymerization of 3-caprolactone.. Many lipid compounds such as animal and vegetable fats have been used to make edible films and coatings. Messersmith & Giannelis. freestanding structures.. their fragility requires their use in conjunction with a supporting matrix. Guilbert et al.. 1996. Acetylated monoglycerides are frequently added to wax formulations to add pliability to the coating (Avena. 1984. all nanocomposites showed an improvement in the gas barrier.. alginates. 2002. PCL is also interesting for applications in the medical and agricultural areas (Nakayama et al. 2002. 1993. Bender et al. in this case. 2002). In other words. Hydrocolloids serve numerous diverse roles such as providing hardness. Due to its low melting point. NANOCOMPOSITE-BASED EDIBLE MATERIAL Edible films and coatings are defined as thin. starches. mechanical and thermal properties with regard to the polymers and blends without clay. by spraying. 1994). 1984). (2003) reported the preparation of melt PCL/OMLS nanocomposites using two different types of OMLS. Its physical properties and commercial availability make it very attractive as a material for commodity applications. Banks. 1995.. Usuki et al. acylglycerols. in conventional applications it must be blended with other polymers (Ishiaku et al. thickening quality.. Many lipids exist in a crystalline form and their individual crystals are highly impervious to gases and water vapour (Greener & Fennema. Lim et al.. 1997). viscosity.. Coatings to sucrose fatty acid esters are effective moisture barriers for maintaining the crispness of snack foods (Kester & Fennema. Bharadwaj et al.. 1996). 1989a. 1984).Bustillos et al. 1997).S. Components of edible films and coatings can be divided into two categories: water-soluble polysaccharides (hydrocolloids) and lipids. 1993).. such as extrusion (Baldwin. and fatty acids. Di Iannace et al. Tortora et al.. Also. 2002. 1989b. National Dairy Research Institute melt-mixing with a properly modified kaolinite (Cabedo et al. 1986). Although fatty acids and fatty alcohols are effective barriers to water vapour. 2006). Suitable lipids include waxes. Gorrasi et al. are 17 . Lipid films have excellent moisture barrier properties or as coating agents for adding gloss to confectionery products. They may be applied with a paintbrush.K. PCL exhibits high elongation at break and low modulus. 1994). Waxes are commonly used for coating fruits and vegetables to retard respiration and lessen moisture loss (Avena-Bustillos et al. GOYAL.. Wurzburg. 1994. compactness. 1997.. Lee et al. 1993. crispness.. 1990).. The information with regard to diverse capabilities and the huge chemistry. gel-forming ability and mouth-feel (Whistler & Daniel. 2003. composite films can be formulated to combine the advantages of the lipid and hydrocolloid components and lessen the disadvantages of each (Greener & Fennema.. 2002. continuous layers of edible material used as a coating or as a film placed between food components to provide a barrier to mass transfer (Balasubramaniam et al. Edible coatings are applied and formed directly on the food product either by addition of a liquid filmforming solution or by molten compounds. great differences exist in how easily these substances can form films of good integrity (Park et al.. Kamper & Fennema.. Glicksman. Kamper & Fennema. The thermal and rheological behaviour of the prepared nanocomposites was investigated and analyzed in terms of processing conditions and types of OMLS. GOYAL. dipping or fluidizing. adhesiveness. Kesel et al. Kojima et al. G. 2004.

better surface properties and recyclability. This is not only due to their availability and low cost but also due to their significant enhancements and relative simple processability. good flow. Two major steps are involved in solid layered dispersion in polymers: intercalation and exfoliation. and texture and to control microbial growth (Siragusa & Dickson. 2004). improvements are obtained at very low filler contents (generally lower than 5%). The enhancement of many properties resides in the fundamental length scales dominating the morphology and properties of these materials. 2003). there is sufficient evidence to establish the beneficial effects of inorganic nanofiller on these materials. i. Nanocomposites also offer extra benefits like low density.e. Wei et al. spheres or particulates. 1996. This control can be especially important for long-term storage of foods or for imparting specific desirable characteristics. the synthetic polymer nanofibres. such as flavour to a food system. 1998). These characteristics include the nature of the polymer as well as the type. the spacing between individual layers.. 2000. called d-spacing. The research of Mangiacapra et al. 1992). increases from its intrinsic value as polymer chains or monomer molecules diffuse into the clay galleries. (2005) demonstrated the possibility to lower the diffusion of oxygen by adding clay montmorillonite into pectins. 2004). dimensional stability and solvent or gas resistance with respect to the pristine polymer. among which there are improved retention of flavour. Studies have demonstrated their ability to stabilize the additives and efficiently control their diffusion into the food as well as between different regions. Additionally. bulk of a food system. Despite the lack of specific literature data. improved appearance and reduced spoilage. Nano-particles can be used as carrier of antimicrobials and additive. the individual clay particles are separated from the intercalated tactoids and are dispersed in the matrix polymer with no apparent interparticle interactions. flakes. Giannelis. (2002) reported a considerable improvement of the physical properties in nanocomposites prepared by gelatine and montmorillonite. Various inorganic nano-particles have been recognized as possible additives to enhance the polymer performance. and the size of the PROPERTIES & APPLICATIONS OF NANOCOMPOSITES Nanocomposites are mixtures of polymers with inorganic or organic additives having certain geometries like fibres.Russian Journal of Agricultural and Socio-Economic Sciences. 2003). Whether a mixture of polymer and organic modified nano-particles produces an exfoliated or intercalated nanocomposite critically depends on the characteristics of the polymer matrix and the organic modifiers. up to now only the layered inorganic solids like clay have attracted some attention by the packaging industry. It is worth noting that these 18 . 10 (10) / 2012 Even if edible films have been extensively studied and applied. No. Similarly. The use of nanoscale fillers is leading to the development of polymer nanocomposites and represents a radical alternative to these conventional polymer composites (Alexandre & Dubois. developed at Toyota Central Research Laboratories in 1986 was a nylon-clay hybrid (Kawasumi.. 1999. surface vs. edible coatings and films are a viable means for incorporating food additives and other substances to enhance product colour. The inorganic particles have at least one dimension in the nanometer (from 1 to 100 nm) range. Some examples of these particles are represented by the solid layered.. The first successful example of a polymerclay hybrid. Sinha Ray & Okamoto. An appreciable increase in stability of chitosan/layered nanocomposites was also reported (Darder et al. packing density. increased stability during shipping and storage. In an intercalated state. In the intercalation step. texture and colour. acids. The characteristic feature of clay minerals is the stacked arrangement of negatively charged silicate layers with a thickness of about 1 nm and lateral extensions of about 100 µm. Among these.. This new generation of composites exhibits significant improvements in modulus. up to now only few research works indicate the possibility of incorporation nano-particles in order to improve the physical properties of these materials. sugars. Layered double hydroxides (LDHs) represent another interesting class of capable nano-fillers for polymers (Fischer et al. the inorganic layers remain parallel to each other. transparency. the cellulose nano-whiskers and the carbon nanotube. in exfoliation. In contrast to layered silicates the hydroxide layers display a positive surface charge which is counterbalanced by anions located in the domains between adjacent layers (De Roy. flavour. LDH particles are constituted by magnesium-aluminium hydroxide layers. Zheng et al.

The ability to assess the toxicity of intentionally produced nano-materials by extrapolating from the current particle toxicological database was examined by several reports (Dreher. Pantoustier et al. ball milling has the considerable advantage of not requiring the use of high temperature or solvent treatments. 2007). GOYAL. The surface of the silicate or hydrotalcite layers. Derfus et al. In the second approach. 2004). solid layered dispersion was promoted by the energy transfer between milling tools (generally balls) and polymer/inorganic particles mixture. Except for specific product developed 19 ... either in the melt or in solution is an accessible manufacturing possibility. 2003). The organic component of the organo-clay or modified hydrotalcite increases significantly the compatibility between the polymer and the filler. particle size does not play a role for the registration of new substances. any new technology carries an ethical responsibility for wise application and the recognition that there are potential unforeseen risks that may come with the tremendous positive potential. limited eco-toxicological data for nano-materials precludes a systematic assessment of the impact of nano-particles on ecosystems (Colvin. also identified as ‘‘insitu polymerization’’. In addition. Wilson et al. 2003. National Dairy Research Institute organic modifiers on the inorganic surface (Alexandre & Dubois. it is important to point out that the majority of the works present in literature make use of additives and surfactants in order to increase the compatibility between the polymer and the filler. European NanoSafe. 2005) was proposed. With respect to nano-fillers discussed in this review. Also in the frame of chemical legislation. 2006. the nano-filler is swollen within the liquid monomer so as the polymer formation can occur between the intercalated sheets..S. by the diffusion of a suitable initiator. Polymerization can be initiated by heat or radiation. Gaskell et al. therefore. the polymer can crawl into the interlayer space and form either an intercalated or an exfoliated nanocomposite. 2004). A lot of new knowledge has to be generated on how nano-material based processes and products may interfere with human health before any regulation in this field can be established (Borm et al. the layered inorganic is mixed with the polymer matrix in either the molten state or a solvent in which the polymer is soluble. becomes accessible to the polymer chains and intercalation or full delamination (exfoliation) of the filler particles can occur during the mixing of the filler with the polymer.K. 2004. Hoet et al. 2004). In the first approach. It can make the products cheaper and the production more efficient by producing less waste and using less energy. Their findings indicated a high degree of uncertainty in the prediction of the toxicity of such nanomaterials. 2004... Generally. or by an organic initiator or catalyst fixed through cationic exchange inside the interlayer before the swelling step by the monomer (Sinha Ray & Okamoto. 2001). which in turn results grinded and intimately mixed. However. 1997. specifically referring to the production and application of nano-particles. In the case of the natural polymers the choice of the suitable method for the preparation of nanocomposites is limited by the processing possibilities of the natural materials. In this case. only blending/compounding with suitable inorganic particles. Oriakhi et al. G. 1998. it is expected that there will be new regulatory directives and guidelines to accommodate nanotechnology based products (Sorrentio et al. 2003. 2004. which involves a solid-state mixing at room temperature (ball milling) (Mangiacapra et al. 1999). Since nature itself produces the possible matrix polymers. 2002). widely used for the synthesis of double-layer hydroxide-based nanocomposites (De Roy.. 2000.. In parallel to the technical evolution of nanotechnologies. However. a new alternative method for the preparation of nanocomposites. An alternative route is represented by the template method. Under these conditions. GOYAL. and if the layer surfaces are sufficiently compatible with the chosen polymer. LEGAL AND ETHICAL BARRIERS Nanotechnology has an extremely high potential to benefit society through applications in food packaging. a handful of food and nutrition products containing invisible and un-labeled nanoscale additives are already on supermarket shelves (Mazzola. At present no government has developed any regulatory regime. intercalation of polymer chains into the inorganic galleries is done by using one of the following two approaches: insertion of suitable monomers in the galleries and subsequent polymerization or direct insertion of polymer chains into the galleries from either solution or the melt. Oberdorster.. Lepoittevin et al. it is less developed for layered silicates. Despite this lack in knowledge. Among the available techniques used for nanocomposites preparation. Recently...

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