International Journal of Food Engineering

Volume 3, Issue 4 2007 Article 3

Improvement in Food Packaging Industry with Biobased Nanocomposites

Zahra Akbari Talat Ghomashchi Shahin Moghadam

Chemical Engineering Faculty, Amirkabir University, Tehran, Iran, zakbari@gmail.com Chemical Engineering Department, Faculty of Engineering, Tehran University, Tehran, Iran, talatgh@ut.ac.ir Department of Chemistry, Tarbiat Moallem University, Tehran, Iran, sh mogh@yahoo.com

Copyright c 2007 The Berkeley Electronic Press. All rights reserved.

Improvement in Food Packaging Industry with Biobased Nanocomposites

Zahra Akbari, Talat Ghomashchi, and Shahin Moghadam

Abstract
Nanotechnology will become one of the most powerful forces for innovation in the food packaging industry. One such innovation is biobased nanocomposite technology, which holds the key to future advances in exible packaging. Biobased nanocomposites are produced from incorporation of nanoclay into biopolymers (or Edible lms). Advantages of biobased nanocomposites are numerous and possibilities for application in the packaging industry are endless. A comprehensive review of biobased nanocomposite applications in food packaging industry should be necessary because nanotechnology is changing rapidly and the food packaging industry is facing new challenges. This provides a general review of previous works. Many of the works reported in the literature are focused on the production and the mechanical properties of the biobased nanocomposites. Little attention has been paid to gas permeability of biobased nanocomposites. In regard to extensive research on Edible lm, this article suggests investigating the replacement of biobased nanocomposites instead of Edible lms in different areas of food packaging. KEYWORDS: nanotechnology, food packaging, nanocomposite, permeability, edible lm

Akbari et al.: Biobased Nanocomposite for Food Packaging

1. INTRODUCTION Biobased nanocomposites are a new class of materials in food packaging industry with improved barrier and mechanical properties as compared to those of neat biopolymers. They are biodegradable and they are also produced from renewable resources. So, these make them environment friendly. It should be noted that barrier properties and especially mechanical properties of biobased nanocomposite films are stronger than Edible films and synthetic polymeric films. Unlike Edible films, they could not have been consumed as a part of food. Biobased nanocomposites can be used to extend the shelf-life of the fresh products such as fruits and vegetables by controlling of respiratory exchange. Also it can improve the quality of fresh, frozen, and processed meat, poultry, and seafood products by retarding moisture loss, reducing lipid oxidation and discoloration, enhancing product appearance, and reducing oil uptake by battered and breaded products during frying. Biobased nanocomposite is interface between two important subjects in food packaging industry, namely Edible films and nanocomposites. Therefore, this paper starts with short explanations about Edible films and nanocomposites. Furthermore, a literature review about biobased nanocomposites is presented. The last objective of this review is to explain a procedure for the replacement of biobased nanocomposites instead of Edible films in food packaging industry. 2. EDIBLE FILMS Edible films are defined as a thin layer of edible material formed on food as a coating. Additionally, Edible films can carry antioxidants (Han, 2001) and antimicrobials (Pena and Torres, 1991), while traditional packaging materials can not compete in these aspects. Edible films are used to extend the shelf life of food and maintain its quality by inhibiting the migration of moisture, oxygen, carbon dioxide, aromas and lipids (Quintavalla and Vicini, 2002). Other favorable aspects of Edible films are: completely biodegradable (Guilbert et al., 1996; Arvanitoyannis et al., 1996) can be a part of a food and can reduce the consumption of naphtha-based polymeric films (Parra et al., 2004). The properties of the edible films which have been mostly evaluated are mechanical properties and specially gas permeability properties (Robertson, 1993). A major component of Edible films is the plasticizer. The addition of a plasticizer agent to Edible films is required to overcome film brittleness, caused by high intermolecular forces. Plasticizers reduce these forces and increase the mobility of polymer chains, thereby improving flexibility and extensibility of the film. On the other hand, plasticizers generally decrease gas, water vapor and solute permeability of the film and can decrease elasticity and cohesion (Parra et al., 2004).
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Type of degradation reactions in food systems determines optimum gases composition in food packaging. For example, oxygen is involved in many degradation reactions in foods, such as fat and oil rancidity, microorganism growth, enzymatic browning and vitamin loss. Thus, many packaging strategies seek to exclude oxygen in packaging to protect the food product (Gontard et al., 1996). On the other hand, the permeability of Edible film to oxygen and carbon dioxide is essential for respiration in living tissues such as fresh fruits and vegetables. So, moderate barrier materials are more appropriate. If an Edible film with the appropriate permeability is chosen, a controlled respiratory exchange can be established and thus the preservation of fresh fruits and vegetables can be prolonged. So the main characteristics to consider in the selection of Edible film are their oxygen, carbon dioxide and water vapor permeability (Ayranci and Tunc, 2002). The success of Edible films for fresh products totally depends on the control of internal gas composition (Park, 1999). Semi-permeable coatings can create a modified atmosphere (MA) (Nisperos, 1990; Baldwin 1994) similar to controlled atmosphere (CA) storage, with less expense incurred. However, the atmosphere created by coatings can change in response to environmental conditions, such as temperature and humidity, due to combined effects on fruit respiration and coating permeability (Baldwin 1994; McHugh and Krochta, 1995). Types of deteriorative reactions, required gas composition and some case study have been summarized in Table 1 for important areas of food industry. Edible films have been prepared by casting solutions of proteins, carbohydrates and lipids, in different combinations and compositions (Kester and Fennema, 1986; Krochta, 1992). Edible films which are made of proteins are most attractive. Firstly, they are supposed to provide nutritional value (Gontard, and Guilbert, 1994). Secondly, protein-based films have impressive gas barrier properties compared with those from lipids and polysaccharides. For example, oxygen permeability of soy protein-based films (when they are not moist) was 500, 260, 540 and 670 times lower than that of low-density polyethylene, methylcellulose, starch and pectin, respectively. On the other hand, their mechanical properties are also better than those of polysaccharide and fat based films because proteins have a specific structure which confers a wider range of functional properties, especially high intermolecular binding potential. In addition, Proteins, such as casein, whey proteins and corn zein, have also been used in Edible film formulation as a moisture barrier since these proteins are abundant, cheap and readily available. Therefore, incorporation of nanoclay in Edible films, especially protein based, can greatly improve their properties.

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Table 1. Basic information for design of edible packaging in different foods with some case study Food Degradation reaction Required gas composition Types of Edible film

Fruits

High respiration rate, water loss, Microbial growth

Oxygen (1-5%) CO2 (0-5%)

Mango(Polysaccharide) apple (whey,CMC), Cherry, Kiwi (CMC, soy protein), strawberry (Polysaccharide), Avacado(CMC), Apricot (MC) Carrot (starch), Mushroom(MC), green pepper and cauliflower (MC),

Vegetables

High respiration rate, water loss, Microbial growth Photooxidation of the pigment, Microbial growth Photooxidation of the pigment, Microbial growth Autolysis caused by intrinsic enzymes, metabolic activity of microorganisms, and oxidation Bacteria growth

Oxygen (1-5%) No CO2

Meat Red meat

Oxygen (70- Meat(corn zein, casein) 80%), CO2 pork(starch/alginate) (30-20%) Low oxygen, High CO2 poultry(corn zein, agar casein), chicken(CMC)

Other meat

Fish low fat

CO2 (40%), Oxygen (30%) CO2 (40-60%), Nitrogen (60-40%) ------

fish (carrageenan)

high fat

Egg

lipids

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Bread

Fungal growth, Low oxygen staling, and moisture absorption / desorption Low oxygen

Rice (Ethyl cellulose, pectin)

Frozen food Degradation of pigments and vitamins, oxidation of lipids, and destabilization of proteins. Fried foods Oxidative reaction

Frozen salmon (whey), Beef (colagen), meat (hydroxypropylated high amylose starch), frozen strawberries (chitosan) Fried potato (hydroxyl propyl methyl cellulose), Starchy product(corn zein), cereal (gelatine, gellan gum, and carrageenan)

Low oxygen

3. NANOCOMPOSITES The large industrial demand for polymers has lead to an equally large interest in polymer composites to enhance their properties. Clay-polymer nanocomposites are among the most successful nanotechnological materials today. This is because they can simultaneously improve material properties without significant trade-offs. Nanocomposites are polymer systems containing inorganic particles with at least one dimension in the nanometer range (Gilmer et al., 2002). Because the nanoparticles are so small and their aspect ratios (largest dimension/smallest dimension) are very high, even at such low loadings, certain polymer properties can be greatly improved without the detrimental impact on density, transparency, and processability associated with conventional reinforcements like talc or glass (Lei et al., 2006). Nanosized particles are carbon black, fumed silicate, nano-oxides, carbon nanotubes and nanoclays. Nanotube-based nanocomposites are used for electrostatic dissipation applications; nanoscale oxides and metals are used for abrasionresistant films; and nanoclay-based nanocomposites are used for barrier packaging applications (Scott and Wood, 2003). Some of the improved properties of nanoconposite are: Improved durability due to increased strength (Angles and Dufresne, 2001; Wang et al., 2003) Better barrier properties, e.g. for packaging (Alexandra and Dubois, 2000)
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Better optical properties due to extremely small size of nanoparticles (Wan et al., 2003) Easier processing due to lower viscosity (Schartel et al., 2005) Good recycling properties (McGlashan and Halley, 2003) Preparations methods of nanocomposite are solution included intercalation, in-situ Polymerization and melt processing. Melt processing is done simultaneously when the polymer is being processed through an extruder, injection molder, or other processing machine. The polymer pellets and clay are pressed together using shear forces to help with exfoliation and dispersion. With in-situ polymerization, clay is added directly to the liquid monomer during the polymerization stage. In the last method, clay is added to a polymer solution using solvents to integrate the polymer and clay molecules. 3.1. NANOCOMPOSITE PERMEABILITY Many factors should be taken into consideration in designing food packaging. One of the very important factors is gas permeability. Gases have different permeability which is determined by gas molecule dimension (dynamic diameter) and gas molecule shape. Nitrogen has the smallest permeability rate; oxygen has bigger while carbon dioxide has the biggest. The gas permeation can be described mathematically by Fick's first law. The flux (J), the net amount of gas that diffuses through unit area per unit time, which is proportional to the concentration gradient can be defined in one direction as follows (Park, 1999):

J = D.

C X

(1)

m2 gr ml or ), D is the diffusivity coefficient ( ), C s m 2 .s m 2 .s is the concentration gradient of the gas and X is the thickness of the neat polymeric film (m) (Crank, 1975; Jost 1960; Landrock and Proctor, 1952; Chang, 1981). With the two assumptions, (1) the diffusion is in steady state and (2) there is a linear gradient through the film, the flux (J) is given by: (2) C C1 Q = J = D. 2 X A.t Where, Q is the amount of gas diffusing through the film (g or ml), A is area of the film (m2) and t is the time (s). After application of Henry's law, the driving force is expressed in terms of partial pressure differential of gas and a rearrangement of terms yields the following equation in terms of permeability. (3) D.S (P2 P1 ) P.P Q = = A.t X X Where, S is the Henry's law solubility coefficient (mole/atm), p is partial pressure difference of the gas across the film (Pa) and P is the permeability of

Where, J is the flux (

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neat polymeric film ((ml or g) m/m2.s.Pa). Then, the permabilities of O2, CO2 and H2O vapor can be calculated from the following equation: (4) Q. X p= A.t.P The gaseous barrier property improvement that can result from incorporation of relatively small quantities of nanoclay materials is shown to be substantial. Further data reveals the extent to which both the amount of clay incorporated in the polymer (Thomassin et al., 2006; Kim et al., 2005) and the aspect ratio of the filler (Xu et al., 2006) contributes to overall barrier performance. As mentioned above, Nanocomposites are constructed by dispersing a filler material into nanoparticles that form flat platelets. Different types of fillers are utilized; the most common is montmorillonite, layered smectite clay. These platelets are then distributed into a polymer matrix creating multiple parallel layers which force gases to flow through the polymer in a torturous path, forming complex barriers to gases and water vapor. As more tortuosity is present in a polymer structure, higher barrier properties will result (Figure 1).

Figure 1. Definition of the tortuosity factor

Simple models (Yano et al., 1993; Liu et al., 2003) have been developed to predict the gas permeability through a polymer matrix in the presence of sheetshaped barriers such as nanoclays, which obstruct the passage of permeant through the matrix. Several important parameters were considered, including the volume fraction of nanocaly ( ) and the aspect ratio of the barrier (L/W), with higher aspect ratios providing greater barrier improvement according to the following equation (Kim et al., 2005): (5) P 1 = p 1 + (L / 2 W ) Where P and p are the permeability coefficients of the nanocomposite and the d' neat polymer, respectively. The term = = 1 + (L / 2 W ) is called the d
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tortuosity factor (Yano et al., 1993). L and W are length and thickness of the silicate layers respectively. The permeability coefficient of nanocomposite films is determined using two factors: diffusion and solubility coefficients. Effectively, more diffusion of nanoparticles throughout a polymer significantly reduces its permeability. The degree of dispersion of the nanoparticles within the polymer relates to improvement in mechanical and barrier properties in the resulting nanocomposite films over those of polymer films. Such excellent barrier characteristics have resulted in considerable interest in nanoclay composites in food packaging applications, both flexible and rigid. Specific examples include packaging for processed meats, cheese, confectionery, cereals and boil-in-the-bag foods.

4. BIOBASED NANOCOMPOSITE FILM

Biobased nanocomposites are composed of biopolymer, nanoclay and usually compatibilizing agents. Major component of biobased nanocomposites is biopolymers. Biopolymers have great commercial potential for bioplastic and Edible films, but some of the properties such as brittleness, low heat distortion temperature; high gas permeability and low melt viscosity for further processing restrict their use in a wide range of applications (Sinha and Bousmina et al., 2005). As mentioned before, modification of biopolymers with nanotechnology is an effective way to improve their properties. Biopolymers derived from renewable resources are broadly classified according to method of production. This gives the following three main categories (Petersen et al., 1997): 1. Biopolymers directly extracted/removed from natural materials (mainly plants) such as hydrocolloids (polysaccharides and proteins). The most frequently utilized polysaccharides were cellulose and starch (and their derivatives), chitosan, seaweed extracts (carrageenans and alginates), exudate (arabic gum), seed (guar gum), xanthan and gellan gum and pectin. Proteins include collagen, gelatin, casein, whey proteins, corn zein, wheat gluten and soy proteins. 2. Biopolymers produced by classical chemical synthesis from renewable bioderived monomers like polylactate (PLA). 3. Biopolymers produced by microorganisms or genetically transformed bacteria like Polyhydroxyalkanoates. Hence, biopolymers which can be used in biobased nanocomposites formulation are numerous. The utilization of special compatibilizing agents (modifier) between the two basic materials (biopolymer and nanoclay) for the preparation of biobased nanocomposite is necessary. Layered silicates are characterized by a periodic stacking of mineral sheets with a weak interaction between the layers and a strong interaction within the layer. The space in-between the layers is occupied by cations. By cation exchange reactions between the clay and
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organic cations (such as alkyl ammonium salts), the layered silicate can be transformed into organically modified clay. The inter-layer distance will increase by using voluminous modifiers. If this modifier is compatible with biopolymer as well, a homogeneously and nanoscaled distribution (exfoliation) of the clay sheets can be effected in the polymer matrix. The pure clay shows an interlayer distance of 1.26 nm. It has been proven by XRD analysis that most of the layers are indeed swollen after the modification reaction. The inter-layer distance changes to 2.34 nm, an increase of nearly 100% compared to the pure clay. A comprehensive review of biobased nanocomposite film applications in food packaging industry is necessary. Therefore, continuing this section, several studies which are concentrated on biobased nanocomposites have been presented. Avella (2005) investigated on mechanical properties of biodegradable starch/clay nanocomposite films for food packaging applications. Starch is composed of a mixture of two substances, an essentially linear polysaccharideamylose and a highly branched polysaccharide-amylopectin. Both forms of starch are polymers of a-D-Glucose. Starch/clay nanocomposite films were obtained by homogeneously dispersing montmorillonite nanoparticles in different starch-based materials via polymer melt processing techniques. The results show that in the case of starch/clay material, a good intercalation of the polymeric phase into clay interlayer galleries, together with an increase of mechanical parameters, such as modulus and tensile strength. Biopolymers like starch present some drawbacks, such as the strong hydrophilic behavior (poor moisture barrier) and poorer mechanical properties than the conventional non-biodegradable plastic films used in the food packaging industries (McGlashan and Halley, 2003; Park et al., 2003; Park et al., 2002). So, Incorporation of nanoclay in biopolymers like starch can improve its properties such as barrier and mechanical properties (Vaia, 2000). The most commonly used nanoclays include montmorillonite, a 2:1 phyllosilicate (Chiou et al., 2005). Kampeerapappun et al (2006) investigated on preparation of cassava starch/ montmorillonite composite film. Cassava is an abundant and cheap agricultural source of starch. This research was focused on the exploitation of chitosan as a compatibilising agent in order to homogeneously disperse the clay particles in a starch matrix. Mixtures of cassava starch, montmorillonite (MMT), chitosan, glycerol as a plasticizer, and distilled water adjusted to pH 3 by acetic acid addition was well mixed with a homogenizer and gelatinized by heating to temperatures of 7080 C. The obtained homogeneous starch solution was cast onto an acrylic mold and allowed to dry in open air. The preparation of starch/montmorillonite composite film also achieved an improvement in the physical properties including reduced surface wettability, a decrease in water vapor transmission rate (WVTR) and moisture absorption. The WVTR value of the biobased nanocomposite film is decreased from 2000 g m-2 day-1 (0 % wt MMT) to 1082 g m-2 day-1 (10 % wt MMT). At a fixed
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amount of MMT (10 wt%), the moisture absorption values decrease significantly from 125% to 95%, 83%, 74%, and 61% with respect to the chitosan contents of 0, 5, 10, 15, and 20 wt%, respectively. Chiou et al (2005) has examined the effects of incorporating various montmorillonite nanoclays into starch by rheology. The nanoclays included the hydrophilic Cloisite NaC clay as well as the more hydrophobic Cloisite 30B, 10A, and 15A clays. Frequency sweep and creep results for wheat starchnanoclay samples at room temperature indicated that the Cloisite NaC samples formed more gel-like materials than the other nanoclay samples. When the various wheat starchnanoclay samples were heated to 95 0C, the Cloisite NaC samples exhibited a large increase in modulus. In contrast, the more hydrophobic nanoclay samples had comparable modulus values to the neat starch sample. One of the major problems with granular starch composites is their limited processability, due to the large particle sizes (5100 lm). Therefore, it is very difficult to make blown thin films of starch for packing applications. For this reason, thermo plastic starch (TPS) has been developed by gelatinizing granular starch with 610 wt% moisture in the presence of heat and pressure (Sinha and Bousmina, 2005). Park et al (2003) has shown that the tensile strength of TPS was increased from 2.6 to 3.3 MPa with the presence of 5 wt% sodium montmorillonite, while the elongation at break was increased from 47 to 57%. Also the relative water vapor diffusion coefficient of TPS was decreased to 65% and the temperature at which the composite lost 50% mass was increased from 305 to 336 0C. Huang et al (2006) investigated on preparation of high mechanical performance MMT urea and formamide-plasticized thermoplastic cornstarch (UFTPCS) biodegradable nanocomposites. It was revealed that UFTPCS were intercalated into the layers of MMT successfully, and layers of MMT were fully exfoliated and so formed the exfoliated nanocomposites with MMT. This manufacturing process is simple and environmentally friendly. Song et al (2006) studied compressive properties of epoxidized soybean oil/clay nanocomposites by. Strain-rate and nanoclay weight effects on the compressive properties of the nanocomposites were experimentally determined. A phenomenological strain-rate-dependent material model was presented to describe the stressstrain response. The model agrees well with the experimental data at both large and small strains as well as high and low strains rates. Zengshe et al (2005) prepared epoxidized soybean oil (ESO)/clay nanocomposites with triethylenetetramine (TETA) as a curing agent. Results have shown that the ESO/clay nanocomposites are thermally stable at temperatures lower than 180 C, with the maximum weight loss rate after 325 C. The nanocomposites with 510 wt% clay content possess storage modulus ranging from 2.0106 to 2.70106 Pa at 30 C. The Young's modulus (E) of these materials varies from 1.20 to 3.64 MPa with clay content ranging from 0 to 10 wt%. The ratio of epoxy (ESO) to hydrogen (amino group of
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TETA) greatly affects dynamic and tensile mechanical properties. At higher amount of TETA, nanocomposites exhibit stronger tensile and dynamic properties. Miyagawa et al (2005) reported the preparation of novel biobased nanocomposites from functionalized vegetable oil and organically-modified layered silicate clay. They used anhydride-cured epoxidized linseed oil / or octyl epoxide linseedate /diglycidyl ether of bisphenol epoxy matrix for the preparation of nanocomposites. MMT is modified by methyl, tallow, bis (2hydrpxyethl) quaternary ammonium. It could be concluded from both the TEM micrographs and XRD data that clay nanoplatelets were completely exfoliated. Homogeneous dispersion and complete exfoliation result in the excellent improvement for elastic modulus of clay nanocomposites. Wibowo et al (2005) have investigated on cellulose acetate (CA) nanocomposites. They were fabricated using extrusion followed by compression molding or injection molding. Improvements in tensile strength by approximately 38%, tensile modulus by approximately 33%, were observed after adding (5 wt %) clay to fabricated CA plastic matrix. Incorporating a small amount of appropriate compatibilizer is expected to enhance miscibility of CA matrix and clay nanofillers and thus further improve mechanical and thermal properties of the nanocomposites. Edible films or biobased nanocomposites based on cellulose have been extensively applied to delay loss of quality in fresh products such as tomatoes, cherries, fresh beans, strawberries, mangoes and bananas. Cellulose derivatives such as hydroxyl propyl cellulose, methylcellulose, carboxyl methyl cellulose and ethyl cellulose are widely reported as Edible films and coatings in the scientific literature. Gindl et al (2005) produced cellulose based nanocomposite films with different ratio of cellulose by means of partial dissolution of microcrystalline cellulose powder in lithium chloride/N,N-dimethylacetamide and subsequent film casting. Mechanical and structural properties of the biobased nanocomposites were measured. The films are isotropic, transparent to visible light, highly crystalline. Results have shown that, by varying the cellulose ratio, the mechanical performance of the nanocomposites can be tuned. Depending on the composition, a tensile strength up to 240 MPa, an elastic modulus of 13.1 GPa, and a failure strain of 8.6% were observed. Petersson et al (2006) compared the mechanical and barrier properties of two different types of biopolymer based nanocomposites. The two nanoreinforcements chosen for this study were bentonite a layered silicate and microcrystalline cellulose (MCC). The polymer matrix was poly lactic acid (PLA). PLA is linear aliphatic thermoplastic polyester. The PLA/bentonite nanocomposite showed a 53% increase in tensile modulus and a 47% increase in the yield strength compared to pure PLA. The PLA/S-MCC system on the other hand showed no increase in tensile modulus and only a 12% increase in yield strength compared to pure PLA. These results were lower than expected. Also, the bentonite nanocomposite is able to reduce the oxygen permeability
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of the PLA while the MCC nanocomposite drastically increased the oxygen permeability of the PLA.

Table 2. Comparison of the oxygen permeability of nanocomposite films and conventional synthetic polymer films
Type of polymer Test condition Permeability (neat polymer/ nanocomposite) 3.5/less than1 7.45/3.75 200/71 9.04/3.4 1.3/0.0247 57.5/--4/--ml.mm m 2 dayatm

Unit

Ref

EVOH* PET PLA PP Butyl rubber Pectin MC Wheat Gluten

45C,0%RH --STP STP 30C 25C,27%RH 25C,42%RH 25C,92%RH

cm 3 m * 3.6 * 10 5 m dayatm
2

(Cebacedo,2004) (Ke , 2005) (Maiti, 2003) (Frunchi, 2006) (Takahashi,2006) (Guilbert, 1996)

cm 3 mm m 2d 0 .1atm

ml.mm m 2 day.Mpa
m2 *7.5*1018 s .Pa

---ml.mm m 2 dayatm

(Guilbert, 1996) (Guilbert, 1996)

ml.mm m 2 dayatm

190/--91.4/---

Chitosan 25C,91%RH
*

ml.mm m 2 dayatm

(Guilbert, 1996)

EVOH: Ethylene vinyl alcohol copolymer, PLA: Polylactide, PET: Poly ethylene terephthalate, MC: Methyl cellulose, HDPE: High Density, poly ethylene, PP: Polypropylene

In spite of the fact that exact determination of gas permeability through a biobased nanocomposite film is critical for food packaging industry, but many of the researches reported in the literature indicated that there are a few documents about measurement of gas permeability and effect of nanoclay on it. Results illustrated in Table 2 reveal this fact. In regard to extensive
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researches on Edible films in different areas of food packaging industry, therefore there is more information about most kinds of biopolymer which have been used in formulation of Edible films. Table 3 indicates that many papers have been published about the utilization of Edible films in various areas of food packaging industry. But little attention has been paid to application of biopolymers for production of biobased nanocomposites.

Table 3. Different type of biopolymer for preparation of Edible films and Biobased nanocomposites in various areas food packaging industry
Type of biopolymer Edible film Biobased nanocomposite

Lipid and oil based

Carnauba wax (Mcgrath et al., 1955; Gago et al., 2005; Baldwin, 1999), Bees wax (Mcgrath et al., 1955; Gago et al., 2005), Paraffin wax (Mcgrath et al., 1955). Mineral oil (Mcnally, 1955), Vegetable oil (Seleeth et al., 1965). Monoglycerides (Brissey et al., 1961; Schneide, 1972), diglycerides (Brissey et al., 1961; Schneide, 1972) triglycerides (Schneide, 1972), acetoglycerides (Woodmansee and Abbott, 1958; aykes, 1959; Dawson et al., 1962; Zabic et al., 1963; Stemmler et al., 1979; Hirasa, 1991), acetylated glycerol monostearate (Stuchell and krochta, 1995; Jokay et al., 1967; Roth and Mehltretter, 1967). Starch and starch derivative: Hydroxy propylated starch (Jokay et al., 1967; Roth and Mehltretter, 1967) Alginates (Berlin, 1975; Mountney and Winter, 1961; Nelson 1963; Hartel, 1966), Carragineen (Stoloff et al., 1948; Allinaham, 1949; Pearce and Lavees, 1949; Meyer et al., 1959), Dextran (Toulmin, 1959 a,b), Cellulose ethers: Methylcellulose

Epoxidized soy bean oil/OMM (Song et al., 2006), Vegetable oil / modified layered silicate (Miyagawa et al., 2005)

Polysaccharide based

Chitosan/glassy carbon electrode (Lu et al., 1999; Misra et al., 2006), Chitosan /layered silicate (Hedenqvist et al., 2006), Cellulose/ organoclay (Misra et al., 2006; Gindl and Keckes,

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(Nelson and Fennema, 1991; Bauer and Neuser 1969), hydroxypropyl cellulose, hydroxylpropylmethyl cellulose (Balasubramaniam 1994; Anon, 1993), and carboxymethyl cellulose [Baldwin, 1994; Funk et al., 1971), Agar (Ayres, 1956; Nateajan and Sheblon, 1995).

2005; Wibowo et al., 2005; Petersson et al,. 2006), starch /MMT (Park et al., 2003; Chen and Evann, 2005; Huang et al., 2006; Park et al., 2002, 2003; Avella et al., 2005)

Protein based

Collagen (Smits, 1985; Mullen, 1971; Whey protein isolate Maser, 1987), Gelatin (Rice, 1994; (Hedenqvist et al., Harvard and Harmony, 1986; Morris 2006), and parker, 1895; Klose et al., 1952; Childs, 1957). Milk protein: whey (Takahashi et al., 2006; Heine et al., 1979; Keil et al., 1960; Chen, 1995; Mate and Krochta, 1995; Morean and Rosenberg, 1993; Rosenberg and young, 1993; Young et al., 2003, Sheu and Rosenberg, 1994), casein (Stemmler M and H, 1974). Cereal protein: Corn zeins (Hargen, 1995; Clark and Ralow, 1949; Herald, 1996), Wheat gluten (Gennadois and Weller, 1992), soy protein isolate (Stuchell et al., 1994; Roy et al., 1995).

As mentioned before, to select biobased nanocomposite packaging materials, it is very important to know deteriorative reactions in food products. Deteriorative chemical changes in foods include nonenzymatic browning, lipid hydrolysis, lipid oxidation, protein denaturation, protein cross linking, hydrolysis of proteins and oligo and polysaccharides, polysaccharide synthesis, degradation of natural pigments and glycolytic changes. After recognition of degradation reaction in food product (refer to Table 1), required gas composition is determined approximately. Then, optimum rate of gas permeability can be calculated. So, base on this information, type of biopolymer will be selected (Table 3). In regard to type of biopolymer, amount of nanoclay, optimum thickness of biobased nanocomposite film, type of compatibilizing agents and also preparation method should be determined.
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5. CONCLUSION
Packaging has developed into an essential technology in the handling and commercialization of foodstuffs to provide, by maintaining or even increasing, the required levels of quality and safety. There are high hopes in food and packaging: longer shelf life, safer packaging, better traceability of products and healthier food is only a few of the expected improvements. This paper gathers a number of significant results where nanotechnology was satisfactorily applied to improve packaged food quality and safety by increasing the barrier and mechanical properties of biopolymer based nanocomposite. Also researches on biobased nanocomposites have been published indicating that the science of biobased nanocomposites for food packaging industry is still in its infancy.

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