improved in food pakaging with biobased nanocomposites

8/13/2019 Improved in Food Pakaging With Biobased Nanocomposites

1/26

International Journal of Food

Engineering

Volume3, Issue4 2007 Article3

Improvement in Food Packaging Industry with

Biobased Nanocomposites

Zahra Akbari Talat Ghomashchi

Shahin Moghadam

Chemical Engineering Faculty, Amirkabir University, Tehran, Iran, [email protected] Engineering Department, Faculty of Engineering, Tehran University, Tehran, Iran,

[email protected] of Chemistry, Tarbiat Moallem University, Tehran, Iran, sh [email protected]

Copyright c2007 The Berkeley Electronic Press. All rights reserved.


2/26

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 pack-

aging industry. One such innovation is biobased nanocomposite technology, which holds the key

to future advances in flexible packaging. Biobased nanocomposites are produced from incorpora-

tion of nanoclay into biopolymers (or Edible films). 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 chal-

lenges. 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 nanocom-

posites. Little attention has been paid to gas permeability of biobased nanocomposites. In regard

to extensive research on Edible film, this article suggests investigating the replacement of biobased

nanocomposites instead of Edible films in different areas of food packaging.

KEYWORDS:nanotechnology, food packaging, nanocomposite, permeability, edible film


3/26

1. INTRODUCTIONBiobased nanocomposites are a new class of materials in food packaging

industry with improved barrier and mechanical properties as compared tothose 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 FILMSEdible films are defined as a thin layer of edible material formed on food as a

coating. Additionally, Edible films can carry antioxidants (Han, 2001) andantimicrobials (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).

1

Akbari et al.: Biobased Nanocomposite for Food Packaging

Published by The Berkeley Electronic Press, 2007


4/26

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, manypackaging 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 controlledatmosphere (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 impressivegas 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.

2

International Journal of Food Engineering, Vol. 3 [2007], Iss. 4, Art. 3

http://www.bepress.com/ijfe/vol3/iss4/art3


5/26

Table 1. Basic information for design of edible packaging in different foods

with some case study

Types of Edible filmRequired gas

composition

Degradation

reaction

Food

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),

Meat(corn zein, casein)

pork(starch/alginate)

poultry(corn zein, agar

casein), chicken(CMC)

fish (carrageenan)

lipids

Oxygen (1-5%)

CO2 (0-5%)

Oxygen (1-5%)

No CO2

Oxygen (70-

80%), CO2

(30-20%)

Low oxygen,

High CO2

CO2 (40%),

Oxygen (30%)

CO2 (40-60%),

Nitrogen

(60-40%)

------

High respiration

rate, water loss,

Microbial growth

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

Fruits

Vegetables

Meat

Red meat

Other meat

Fish

low fat

high fat

Egg

3




6/26

Rice (Ethyl cellulose,

pectin)

Frozen salmon (whey),

Beef (colagen), meat

(hydroxypropylated

high amylose starch),

frozen strawberries

(chitosan)

Fried potato (hydroxyl

propyl methylcellulose),

Starchy product(corn

zein), cereal (gelatine,

gellan gum, and

carrageenan)

Low oxygen

Low oxygen

Low oxygen

Fungal growth,

staling, and

moisture absorption

/ desorption

Degradation of

pigments and

vitamins, oxidation

of lipids, and

destabilization of

proteins.

Oxidative reaction

Bread

Frozen food

Fried foods

3. NANOCOMPOSITESThe 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 materialstoday. 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). Nano-

sized 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 abrasion-

resistant 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)

4




7/26

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):

X

CDJ

= .

(1)

Where, J is the flux (sm

gr

.2or

sm

ml

.2), D is the diffusivity coefficient (

s

m2

), C

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:

tA

Q

X

CCDJ

.. 12 =

=

(2)

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.

( )X

PP

X

PPSD

tA

Q =

=

..

.

12 (3)

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

5




8/26

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:

PtA

XQp

=

..

.

(4)

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 (Thomassinet 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).

Figure1.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 sheet-

shaped 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):

1

1 ( / 2 )

P

p L W=

+

(5)

Where P and p are the permeability coefficients of the nanocomposite and the

neat polymer, respectively. The term'

1 ( / 2 )d

L Wd

= = + is called the

6




9/26

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, morediffusion 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 FILMBiobased nanocomposites are composed of biopolymer, nanoclay and usuallycompatibilizing 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 mostfrequently 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) betweenthe 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

7




10/26

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 polysaccharide-amylose 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 canimprove 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. Thepreparation 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

8




11/26

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 variousmontmorillonite 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 beendeveloped 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 werefully 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 attemperatures 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 2.0106to 2.7010

6Pa 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

9




12/26

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 biobasednanocomposites 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 (2-

hydrpxyethl) 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 observedafter 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 microcrystallinecellulose 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/bentonitenanocomposite 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

10




13/26

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 andconventional synthetic polymer films

Ref

Unit

Permeability

(neat polymer/

nanocomposite)

Test

condition

Type of

polymer

)(Cebacedo,2004

(Ke , 2005)

)Maiti, 2003(

)Frunchi, 2006(

)Takahashi,2006(

)Guilbert, 1996(

)Guilbert, 1996(

)Guilbert, 1996(

)Guilbert, 1996(

5

2

3

10*6.3*

dayatmm

mcm

3

2

0.1cm mm

m d atm

Mpadaym

mmml

.

.2

218

*7.5*10.

m

s Pa

----

dayatmm

mmml2

.

dayatmm

mmml2

.

dayatmm

mmml2

.

dayatmm

mmml2

.

3.5/less than1

7.45/3.75

200/71

9.04/3.4

1.3/0.0247

57.5/---

4/---

190/---

91.4/---

45C,0%RH

---

STP

STP

30C

25C,27%RH

25C,42%RH

25C,92%RH

25C,91%RH

EVOH*

PET

PLA

PP

Butyl

rubber

Pectin

MC

Wheat

Gluten

Chitosan

*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

11




14/26

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 variousareas 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

Polysaccharide

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)

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,

12




15/26

Protein based

(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).

Collagen (Smits, 1985; Mullen, 1971;

Maser, 1987), Gelatin (Rice, 1994;

Harvard and Harmony, 1986; Morrisand 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 andWeller, 1992), soy protein isolate

(Stuchell et al., 1994; Roy et al.,

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)

Whey protein isolate

(Hedenqvist et al.,

2006),

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.

13




16/26


17/26

permeabilities of Edible films. Journal of Agricultural and Food

Chemistry, 1996, 44, 10641069.

9.

Ayranci .E, Tunc. S., A method for the measurement of the oxygenpermeability and the development of Edible films to reduce the rate of

oxidative reactions in fresh foods.Food chemistry, 2002, 80(3), 423-431.

10.Park, H.J., Development of advanced edible coating for fruits. Trends inFood Science & Technology,1999, 10, 254-260.

11.Nisperos-Carriedo, M.O., Shaw, P.E., Baldwin, E.A., Changes in volatileflavor components in Pineapple orange juice as influenced by the

application of lipid and composite films.Journal of Agricultural and Food

Chemistry, 1990, 38, 13821387.

12.Baldwin, E.A., Nisperos, M.O., Shaw, P.E., Burns, J.K., Effect of coatingsand prolonged storage conditions on fresh orange flavor volatiles, degreesBrix, and ascorbic acid levels. Journal of Agricultural and Food

Chemistry, 1995, 43, 13211331.

13.McHugh, T.H., Krochta, J.M., Permeability properties of Edible films. In:Krochta, J.M., Baldwin, E.A., Nisperos Carriedo, M.O. (Eds.), Edible

Coatings and Films to Improve Food Quality, 1994, Technomic

Publishing, Lancaster: Basel, pp. 139187.

14.Kester, J. J. and Fennema, O., Edible films and coatings: A review. FoodTechnology, 1986, 40 (12), 4759.

15.Krochta, J. M., Control of mass transfer in foods with edible coatings andfilms. In: Singh, R. P. and Wirakartakusumah, M. A. (Eds), Advances in

Food Engineering. Boca Raton, FL: CRC Press, Inc, 1992, 517538.

16.Gontard, N., and Guilbert, S., Biopackaging: Technology and properties ofedible and/or biodegradable material of agricultural origin. In:

MATHLOUTHI, M. (Ed), Food Packaging and Preservation. London:

Blackie Academic & Professional, 1994, 159181.

17.Gilmer et al, Polymer/clay nanocomposite having improved gas barriercomprising a clay material with a mixture of two or more organic cations

and a process for preparing same, 2002, US patent:6486253.

18.S.G. Lei, S.V. Hoa, M. T. Ton-That., Effect of clay types on theprocessing and properties of polypropylene nanocomposites. Composites

Science and Technology, 2006, 66, 12741279.

15




18/26

19.Scott, A. and Wood, A., Big firms bulk up on nanoscale materials.Chemical Week. Retrieved February 16, 2004, from

www.findarticles.com.

20.Angles, M.N., Dufresne A., Plasticized starch/tunicin whiskersnanocomposite materials. 2. Mechanical behavior. Macromolecules, 2001,

34, 29212931.

21.Wang, K. K., Koo, C.M., Chung, I.J., Physical properties of polyethylene/silicate nanocomposite blown films, J. Appl. Polym. Sci, 2003, 89, 2131

2136.

22.Alexandra. M. and Dubois P., Polymer-layered silicate nanocomposites:preparation, properties and uses of a new class of materials. Mater Sci

Eng, 2000, 28, 163.

23.Wan. C., Qiao. X., Zhang. Y., Zhang. Y., Effect of different clay treatmenton morphology and mechanical properties of PVC-clay nanocomposites.

Polymer Testing, 2003, 22,453461.

24.Schartel. B., Potschke. P., Knoll. U., Abdel-Goad. M., Fire behavior ofpolyamide 6/multiwall carbon nanotube nanocomposites. Eur Polym J,

2005, 41(5), 10611070.

25.McGlashan. S. A. and Halley. P. J., Preparation and characterization ofbiodegradable starch-based nanocomposite materials. Polymer

International, 2003, 52, 17671773.

26.Thomassin. J.M., Pagnoulle. C., Bizzari. D., Caldarella. G., Germain. A.,Jrme. R., Improvement of the barrier properties of Nafion by fluoro-

modified montmorillonite. Solid State Ionics, 2006.

27.Kim. J.K., Hu. C., Ricky, Woo. S.C., LSham, M., Moisture barriercharacteristics of organoclayepoxy nanocomposites. Composites Science

and Technology, 2005, 65, 805813.

28.Xu. B., Zheng. Q., Song. Y., Shangguan, Y., Calculating barrier propertiesof polymer/clay nanocomposites: Effects of clay layers, Polymer, 2006,

47, 29042910.

29.Crank, J., The Mathematics of Diffusion. Oxford University Press, 1975,London.

30.Jost, W., Diffusion in Solids, Liquids, Gases. Academic Press Inc., 1960,Pub, New York.

16




19/26


20/26


21/26

54.Kampeerapappun, P., Ahtong, D., Pentrakoon, D., Srikulkit, K.,Preparation of cassava starch/ montmorillonite composite film.

Carbohydrate Polymers, 2006.

55.Gindl, W., Keckes, J., All cellulose nanocomposites. Polymer, 2005, 46,1022110225.

56.Liu, Z., Erhan, S.Z., Xu, J., Preparation, characterization and mechanicalproperties of epoxidized soybean oil/ clay nanocomposites, Polymer,

2005, 46(3), 10119-10127.

57.Chiou, B.S., Yee, E., Glenn, G.M., Orts, W.J., Rheology of starchclaynanocomposites. Carbohydrate Polymers, 2005, 59, 467475.

58.Wibowo, A.C., Misra, M., Park, H.M., Drzal, L.T., Schalek, R., Mohanty,A.K., Biodegradable nanocomposites from cellulose acetate: Mechanical,morphological, and thermal properties. Composites, 2005.

59.Mcgrath, E. P., Packaging costs cut, quality protected by wax-coatingfrozen meats.Food Engineering, 1955, 27 (8), 5051, 77.

60.Perez gago, M.B., Serra, M., Alonso. M., Mateos, M., del Ro.M.A., Effectof whey protein- and hydroxypropyl methylcellulose-based edible

composite coatings on color change of fresh-cut apples. Postharvest

Biology and Technology,2005, 36, 7785.

61.Baldwin, E.A., Burns, J.K., Kazokas, W., Brecht, J.K., Hagenmaier, R.D.,Bender, R.J., Pesis, E., Effect of two edible coatings with different

permeability characteristics on mango (Mangifera indica L.) ripening

during storage.Postharvest Biology and Technology, 1999, 17, 215226.

62.Mcnally, E.H., A comparison of methods to prevent weight loss in frozenpoultry.Poultry Science, 1955, 34, 12101211.

63.Sleeth, R.B., and Furgal, H. P., Method of coating freeze-dried meat. 1965,U.S. Patent 3,165,416.

64.Brissey, G. E., and Hill, R.C., Prevention of casing sticking to meat. 1961,U.S. Patent 2,982,660.

65.Schneide, J., Process for preserving meat. 1972, U.S. Patent 3,667,970.66.Woodmansee, C.W., and Abbott, O. J., Coating subscalded broiler parts in

order to afford protection against dehydration and skin darkening in fresh

storage.Poultry Science, 1958, 37, 13671373.

19




22/26

67.Ayres, J.C., Use of coating materials or film impregnated withchlortetracycline to enhance color and storage life of fresh beef. Food

Technology, 1959, 13, 512515.

68.Dawson, L. E., Zabik, M., Sobel, N., An edible coating for poultry meatpreservation.Poultry Science, 1962, 41, 1640.

69.Zabik, M.E. and Dawson, L.E., The acceptability of cooked poultryprotected by an edible acetylated monoglyceride coating during fresh and

frozen storage.Food Technology, 1963, 17, 8791.

70.Stemmler, M., and Stemmler, H., Method for preserving freshlyslaughtered meat. 1974, U.S. Patent 3,851,077.

71.Heine, C., Wust, R., Kamp, B.,1979, U.S. Patent 4,137,334.72.Hirasa, K., Moisture loss and lipid oxidation in frozen fish: Effect of a

casein-acetylated monoglyceride edible coating. M.S. thesis, University of

California Davis, 1991, CA.

73.Stuchell, Y.M., and Krochta, J. M., Edible coatings on frozen Kingsalmon: effect of whey protein isolate and acetylated monoglycerides on

moisture loss and lipid oxidation.Journal of Food Science, 1995, 60, 28

31.

74.Jokay, L., Nelson, G.E., POWELL, E. L., Development of edibleamylaceous coatings for foods.Food Technology, 1967, 21, 10641066.

75.Roth, W.B., and Mehltretter, C. L., Some properties of hydroxypropylatedamylomaize starch films.Food Technology, 1967, 21, 7274.

76.Allen, L., Nelson, A. I., Steinberg, M. P., Mc Gill, J.N., Edible corn-carbohydrate food coatings. I. Development and physical testing of a

starchalgin coating.Food Technology, 1963, 17, 14371442.

77.Berlin, A., Calcium alginate films and their application for meats used forfreezing. Chemical Abstracts, 1957, 51, 17007.

78.Mountney, G. J., and Winter, A. R., The use of a calcium alginate film forcoating cut-up poultry.Poultry Science, 1961, 40, 2834.

79.Allen, L., Nelson, A. I., Stenberg, M. P., Mc Gill, J.N., Edible corn-carbohydrate food coatings. II. Evaluation on fresh meat products. Food

Technology, 1963, 17, 14421446.

20




23/26

80.Hartal, D., The development and evaluation of carbohydrate- alginate foodcoatings. M.S. thesis, 1966, University of Illinois, Urbana, IL.

81.Stoloff, L. S., Puncochar, J. F., Crowther, H. E., Curb mackerel filletrancidity.Food Industries, 1948, 20, 11301132, 1258.

82.Allingham, W. J., Preservative coatings for foods. 1949, U.S. Patent2,470,281.

83.Pearace, J.A., and Lavers, C.G., Frozen storage of poultry. V. Effects ofsome processing factors on quality. Canadian Journal of Research, 1949,

27, 253265.

84.Meyer, R.C., Winter, A.R., Weiser, H. H., Edible protective coatings forextending the shelf life of poultry.Food Technology, 1959, 13, 146148.

85.Toulmin, H. A., JR, Method of preserving shrimp. 1959, U.S. Patent2,758,929.

86.Toulmin, H. A., JR. Method of preserving shrimp. 1956, U.S. Patent2,758,930.

87.Novak, L. J., Food preservation. 1957, U.S. Patent 2,790,720.88.Toulmin, H. A., JR. Method of preserving food products. 1957, U.S.

Patent 2,790,721.

89.Nelson, K. L., and Fennema, O. R., Methylcellulose films to prevent lipidmigration in confectionery products. Journal of Food Science, 1991, 56,

504509.

90.Bauer, C.D., and Neuser, G. L., Edible meat coating composition. 1969,U.S. Patent 3,483,004.

91.Anon, Food gums stick it out in dry mix glazes. Prepared Foods, 1993,162 (1), 53.

92.Balasubramaniam, V. M., Chinnan, M. S., Malkiarjunan, P., Phillips, R.D.,Role of Edible films in oil penetration and moisture retention during deep-fat frying of foods. Presented at the International Winter Meeting of the

American Society of Agricultural Engineers, 1994, Paper No. 94-6550.

Atlanta, GA.

21




24/26

93.Baldwin, E. A., Edible coatings for fresh fruits and vegetables: Past,present, and future. In: Krochta, J. M., Baldwin, E.A. and Nisperos -

Carriedo, M. (Eds), Edible Coatings and Films to Improve Food Quality.

Lancaster, PA: Technomic Publishing Company, 1994, Inc., 2564.

94.Funk, K., Yadrick, M.K., Conklin, M. A., Chicken skillet-fried or roastedwith and without an edible coating.Poultry Science, 1971, 50, 634640.

95.Natrajan, N., and Sheldon, B.W., Evaluation of bacteriocin- basedpackaging and Edible film delivery systems to reduce Salmonella in fresh

poultry.Poultry Science, 1995, 74 (Suppl. 1), 31.

96.Smits, J.W., The sausage coextrusion process. In: Krol, B., Van Roon, R.S., Houben, J. H., (Eds), Proceedings of the International Symposium on

Trends in Modern Meat Technology. 1985, Wageningen, the Netherlands:Centre for Agricultural Publishing and Documentation, 6062.

97.Mullen, J.D., Film formation from nonmeat coagulable simple proteinswith filler and resulting product. 1971, U.S. Patent 3,615,715.

98.Maser, F., Essbare Folie aus Kollagen mit einem an Gluten, insbesondereWeizen-gluten. Verfahren zu ihrer Herstellung und Verwendund der Folie

zur Umhullung von Lebensmitteln., 1987, European Patent O 244 661.

99.Rice, J., Whats new in Edible films?Food Processing, 1994, 55 (7), 6162.

100. Harvard, C., and Harmony, M. X., Improved process of preservingmeat, fowls, fish. 1986, U.S. Patent 90,944.

101. Morris, A., and Papker, J. A., Preservative coating for foods. 1895,U.S. Patent 556,471.

102. Klose, A. A., Mecchi, E. P., Hanson, H. L., Use of antioxidants in thefrozen storage of turkeys.Food Technology, 1952, 6, 308311.

103. Childes, W. H., Coated sausage and method of preparing same. 1957,U.S. Patent 2,811,453.

104. Keil, H. L., Hagen, R. F., Flaws, R.W., Coating composition method ofapplying same to a food and coated food product. 1960, U.S. Patent

2,953,462.

22




25/26

105. Chen, H., Individually quick packaging of particulate foods using milkprotein based coating formulations. Presented at the Annual International

Meeting of the American Society of Agricultural Engineers, Chicago, IL,

1995, ASAE Paper No. 95-6168.

106. Mate, J. I., and Krochta, J. M., Effect of WPI coatings on the oxygenuptake of dry roasted peanuts. Paper No. 12E-5. Presented at the Annual

Meeting of the Institute of Food Technologists, 1995, Anaheim, CA, 156.

107. Moreau, D. L., and Rosenberg, M., Microstructure and fatextractability in microcapsules based on whey proteins or mixtures of

whey proteins and lactose.Food Structure, 1993, 12, 457468.

108. Rosenberg, M., and Young, S.L., Whey proteins as microencapsulatingagents. Microencapsulation of anhydrous milkfat structure evaluation.

Food Structure, 1993, 12, 3141.

109. Young, S. L., Sarda, X., and Rosenberg, M., Microencapsulatingproperties of whey proteins. 1. Microencapsulation of anhydrous milk fat.

Journal of Dairy Science, 1993, 76, 28682877.

110. Young, S. L., Sarada, X., Rosenberg, M., Microencapsulatingproperties of whey proteins. 2. Combination of whey proteins with

carbohydrates.Journal of Dairy Science, 1993, 76, 28782885.

111. Sheu, T.Y., and Rosenberg, M., Microencapsulation by spray dryingethyl caprylate in whey protein and carbohydrate wall systems.Journal of

Food Science, 1995, 60, 98103.

112. Hargens-Madsen, M. R., Use of edible coatings and tocopherols in thecontrol of warmed-over flavor. M.S. thesis, University of Nebraska,

Lincoln, NE, 1995.

113. Herald, T. J., Hachmeister, K. A., Hunang, S., Bowers, J. A., Corn zeinpackaging materials for cooked turkey.Journal of Food Science, 1996, 61,

415417, 421.

114. Clark, R. L., Ralow, R.C., Zein: versatile packaging resin. ModernPackaging, 1949, 22, 122125, 154, 156.

115. Gennadios, A., and Weller, C.L., Tensile strength increase of wheatgluten films. Presented at the International Winter Meeting of the

American Society of Agricultural Engineers, Nashville, TN, 1992, Paper

No. 92-6517.

23




26/26

116. Stuchell, Y.M., and Krochta, J. M., Enzymatic treatments and thermaleffects on edible soy protein films. Journal of Food Science, 1994, 59,

13321337.

117. Roy, S., Weller, C. L., Zeecc, M.G., Testin, R. F., Effect of heat on thephysical and molecular properties of wheat gluten films. Presented at the

Annual Meeting of the Institute of Food Technologists, Anaheim, CA,

1995, Paper No. 12E-14.

118. Song, B., Chen, W., Liu, Z., Erhan, S., Compressive properties ofepoxidized soybean oil/clay nanocomposites. International Journal of

Plasticity, 2006, 22(8), 1549-1568.

119. Miyagawa, H., Misra, M., Drazal, L.T., Mohanty, A.K., Novelbiobased nanocomposites from functionalized vegetable oil and

organically modified layered silicate clay.Polymer, 2005, 46, 44553.

120. Xin, Y., Xiaogang,G., Tong, Z., Studies on electrochemical behaviorof bromide at a chitosanmodified glassy carbon electrode.Electroanalysis,

2001, 13,923926.

121. Lu, G., Yao, X., Wu, X., Zhan, T., Determination of the total iron bychitosan-modified glassy carbon electrode.MicrochemJ, 2001, 69, 8187.

122. Pan, J.R., Huang, C., Chen, S., Chung, Y.C., Evaluation of a modifiedchitosan biopolymer for coagulation of colloidal particles. Colloids

Surface, 1999, 147,35964.

123. Misra, M., Park, H., Mohanty, A.K., Drzal, L.T., Injection moldedgreen nanocomposite materials from renewable resources. Paper presented

at GPEC-2004.

124. Hedenqvist, M.S., Backman, A., Gallstedt, M., Boyd, R.H., Gedde,U.W., Morphology and diffusion properties of whey/montmorillonite

nanocomposites. Composites Science and Technology, 2006.

24



improved in food pakaging with biobased nanocomposites

Documents