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Oxygen and aroma barrier properties of edible films:

Review
Origin and definition of edible polymer films Foods such as fruit and nuts have natural built-in packaging protection in the form of skins and shells. These natural barriers regulate the transport of oxygen, carbon dioxide and moisture and also reduce flavor and aroma loss. However, processedfoods dominate todays diet; and no such natural barriers exist for processed foods. Humankinds instinct to cover food (perhaps stemming from a desire to hide this precious commodity) may have inadvertently led to the implementation of food packaging. The very first package probably consisted of leaves, animal skin or the shell of a nut or gourd. Around SOOOBC, the different types of packaging materialsthat were available included sacks,baskets and bagsmade from plant or animal material, as well as primitive pottery and ceramic vessels. By -15OOBC, hollow glass objects had begun to appear, but it was not until -AD~OO that the woven, pressedsheetsthat eventually became known as paper appearedr. Lard or wax was used to enrobe fruit and other food items in 16th-century England2. The first plastic, a cellulose-basedpolymer, was introduced in 1856; then in 1907, phenol formaldehyde plastic (Bakelite) was discovered. From then on, a series of discoveries and inventions led to todays multitude of primarily synthetic polymer packaging materials. Polymer scientists have produced a variety of synthetic polymers and polymer laminatesthat are excellent barriers to both oxygen and aroma compounds. However, despite the availability of these synthetic barriers, the food industry is now considering natural packaging biopolymers such as edible and biodegradable polysaccharide or protein films. Although these biopolymers share their origins with the early, all-natural packaging materials, they have many of the same properties and are as convenient as the synthetic polymers that they augment. Environmental and economic reasonsas well as product development and consumer trends have pushed food and packaging scientists along this cyclic path. Edible polymer films may be formed as either food coatings or stand-alonefilm wraps and pouches. These biopolymer films have potential for use with food as oxygen and/or aroma barriers2. This reduces the requirements of the synthetic polymer to the provision of a barrier to moisture loss and protection of the food from external contamination. Thus, the amount of synthetic packaging is reduced and recyclability is increasedbecausethe need for synthetic laminates, often usedto improve oxygen and aroma barrier properties, is diminished. Regardlessof whether it is a synthetic polymer or biopolymer, a polymers mass transport properties are influenced by similar factors; theseinclude composition and structure, which directly affect a films performance as a barrier to quality loss. For these reasons,environmental and processingconditions that affect the composition and structure of polymer films are of great interest to both food and polymer scientists.
Trends

A review
K.S. Miller and J.M. Krochta

Interest in maintaining

food quality while reducing packaging

waste has encouraged the exploration of the oxygen and aroma transport properties of edible films. This review article introduces the theoretical basis for oxygen and aroma barrier property determination and presents a brief historical perspective of the development of barrier polymers. The effects of structure and composition on mass transport in edible films are examined and compared with those of the more thoroughly investigated synthetic polymers. A survey of edible film oxygen and aroma barrier research is presented; areas requiring additional investigation are suggested, for applications as well as basic research. The potential of edible films and coatings to provide excellent aroma retention and superior oxygen barrier properties makes this quite a promising area of research for both food and packaging scientists.

Food quality is easily diminished by the deleterious transport of aroma compoundsand oxygen. Food is required to satisfy the biological need for a source of nutrition; however, it is the flavor and aroma of a food that provide the impetus for its consumption. In fact, a large segment of commercial manufacturing deals with the production of packaging that extends the shelf life of food by controlling oxygen and aroma transport. A foods characteristic flavor and aroma are the result of a complex construct of hundredsof individual constituent compounds interacting to produce a recognizable taste and aroma. Thus, if one or more flavor constituents are altered or diminished, food quality may be reduced. A reduction in food quality may result from the oxidation of aroma componentsdue to the ingressof oxygen, or it may be the result of the loss of specific aroma compounds to the packaging material or environment. Therefore, it is critical to identify both the oxygen and aroma masstransfer properties of food packaging.
K.S. Miller
Engineering, Frito-Lay, (corresponding Engineering CA 95616, (formerly University Inc., 7701 author] of the Legacy Department Davis, Plano, Drive, of Biological CA 95616, TX 75024, of Biological University and USA) USA. and Agricultural is now Agricultural Davis, at

of California,

J.M. Krochta

is at the Departments & Technology, e-mail:

and Food Science

of California,

USA (fax: +l-916-752-4759;

jmkrochta@ucdavis.edu).

228

Copyright 01997. Elsevw Science Ltd All rights resewed PI,: 50924.2244(97~01O51-0

0924.2244/97~$17.00

in Food Science

&Technology

July 1997 [Vol.

81

Box 1. Polymer

film mass transport

properties When S is independent of the sorbed permeant concentration and vapor pressure (i.e. at sufficiently low permeant concentrations), then the relationship between c and p becomes linear and S is referred to as the Henrys law solubility coefficient. This relationship is often used to calculate the solubility coefficient from sorption isotherms, which are plots of the permeant concentration in the headspace above a polymer versus the concentration of the permeant within the polymer. The permeability coefficient incorporates both kinetic and thermodynamic properties of the polymer-permeant system, and thus provides a gross mass transport property. The permeability coefficient, P, is most commonly related to D and S as: P=DS when both D and S are independent of concentration. Permeability is defined at steady state with D and S constant integrating Eqn 1 and combining it with Eqns 2 and 3 to obtain: (dM/dt) P=
;;$dy L

The diffusion coefficient describes the movement of permeant molecules through a polymer, and thus represents a kinetic property of the polymer-permeant system. Figure 1 shows the activated diffusion process used to describe permeant movement in a polymer. Activated diffusion is described as the opening of a void space among a series of segments of a polymer chain due to oscillations of the segments (an active state), followed by translational motion of the permeant within the void space before the segments return to their normal state3. DiBenedetto pointed out that both the active and normal states are long-lived, as compared with the translational rate of the permeant. Ficks first law in one dimension defines the diffusion coefficient: ,=-D$ (1)

(3) by

where / is the diffusive mass transfer rate of permeant per unit area, c is the concentration of permeant, x is the length and D is the diffusion coefficient. The solubility coefficient describesthe dissolution of a permeant in a polymer, and thus represents a thermodynamic property of the polymer-permeant system. The solubility coefficient may be defined by an adaptation of the Nernst distribution function as:

(4)

ASP
where M is the quantity of permeant (which can be expressed as either mass or volume), t is time, L is the polymer film thickness, A is the cross-sectional area of the polymer, Ap is the partial pressure difference across the polymer, and P is the permeability coefficient. The term (dM/dt) is the slope of the transmission curve and is required to be at steady state for the permeability coefficient calculation.

c=sp

(2)

where p is the vapor pressure of the permeant and S is the solubility coefficient. The solubility coefficient is a function of temperature and may be a function of the vapor pressure (or concentration of dissolved permeant).

This article first reviews the parametersthat are used to characterize masstransport in polymer films, including the relationship between polymer structure and those masstransport parameters.The compositions and structures of edible films are then compared with those of synthetic polymers, and current researchon oxygen and aroma transport in edible polymers is summarized. Finally, potential applications for edible oxygen and aroma barrier films are examined, and corresponding basic and applied researchneedsare identified.

Structural influences on polymer masstransport properties A films mass transportpropertiesareoften described by three common coefficients: diffusion (the rate of movement of a permeantmoleculethrough the tangledpolymer matrix, basedon, for example, the size of the permeantmoleculeand the strucPermeant molecule ture of the polymer matrix), solubility Segments (the partitioning behavior of a permeant I I of polymer I molecule between the surface of the chains I polymer and the surroundingheadspace) I 4 2L andpermeability (the rate of transportof a permeantmolecule through a polymer =$x-I asa resultof the combinedeffects of difI Reference I I fusion and solubility). These are forI ----position mally defined in Box 1. Activated Normal Figure 1 depicts the activated diffustate state sion processand clearly showsthe importanceof polymer structurefor perme- F;n , ant transport. The ability of a segment @ of the polymer chain to relax and shift The activation process for diffusion. Adapted from Molecular Properties its structure, allowing the permeant An Interpretation of Gaseous Diffusion Through Polymers in). Polym. accessto newly formed void spaces,is A.T. DiBennedetto, and reproduced with permission from John Wiley

essentialfor activated diffusion. Factors affecting a polymers structure have a direct effect on segmental mobility and, therefore, influence its mass transport properties. Several polymer properties influence permeability: chemical structure, method of polymer preparation, polymer processing conditions, free volume, crystallinity, polarity, tacticity, ciosslinking and grafting, orientation, presence of additives, and use of polymer blends4. Researchers have shown that an increasein crystallinity, density, orientation, molecular weight or crosslinking resultsin decreased polymer permeability5x6. A barrier polymer inhibits permeantprogress,thereby presenting a greater barrier to mass transport than the permeant would otherwise meet in the absenceof the polymer. The necessary characteristics of a barrier polymer include: a degreeof polarity, high chain stiffness,inertness

I
I

gg%J-;

gg
I I I

Normal state one diffusional

after jump

of Amorphous SC;.: Part Al, & Sons, Inc.

High Polymers. Copyright 0 1963,

II.

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229

to permeants, high chain-to-chain packing, some intermolecular crosslinking and a high glass transition temperature. The effects of the previously mentioned polymer properties on mass transport have been defined primarily in terms of oxygen and moisture transport. The diversity of aroma compounds has impeded the thorough investigation of their myriad polymer-permeant interactions and of the associated effects on aroma permeability. Chemical structures Knowledge of the effects of differing chemical structures on a polymers mass transport properties is important for todays packaging industry. The types of substituent groups present in a polymer can have a tremendous effect on the variability of the permeability coefficient by influencing two main factors: how tightly the polymer chains are bound together and how much free volume exists between the chain9. Cohesive energy density Cohesive energy density is a measure of the polarity of a polymer and of the energy binding the polymer chains together. In general, the higher a polymers cohesive energy density, the more difficult it is for the polymer chains to open and allow a permeant to pass (highly polar permeants such as water being an exception to this rule). An empirical correlating parameter, dubbed the Permachor value, can be used to predict gas permeation, if free volume and cohesive energy density are known8. The effects of various substituent groups on polymer permeability are shown in Table 1. As increasingly polar substituents are added to the same carbon backbone (thus increasing the cohesive energy density), oxygen permeability decreases by five orders of magnitude. However, water, being highly polar, does not rely on the polymer chains to open and can force

them open to engage in hydrogen bonding even when the cohesive energy density is relatively high. In the case of a polymer with a simple carbon repeating unit, a hydrogen substituent results in an oxygen permeability coefficient that is 117500 times greater than that of the same backbone with a hydroxyl group substituent. One would also expect polymers with a higher cohesive energy density to be better barriers to nonpolar aroma compounds. Free volume Free volume is a measure of the degree of interstitial space between the molecules in a polymer. The diffusion coefficient and the permeability coefficient both decrease with a decrease in free volume for carbon dioxide, helium and methane in various polymers. Maeda and Paul pointed out that the addition of plasticizers to increase the free volume resulted in lower glass transition temperatures, whereas the addition of anti-plasticizers to decrease the free volume increased the glass transition temperature. Table 2 shows the dramatic effect of free volume on the permeability of oxygen. As the fractional free volume decreases from 0.204 for poly(4-methyl pentene-1) to 0.03 for poly(viny1 alcohol) (PVOH; see Box 2 for all polymer abbreviations), the oxygen permeability diminishes by six orders of magnitude. Stiff-chained polymers that have a high glass transition temperature generally have low gas permeability, unless they also have a high free volumea. These results suggest that nonpolar aroma compounds would also have low permeability coefficients in polymers with a low free volume.

Crystallinity Crystallinity is a measure of the degree of order of the molecules in a polymer. Polymer properties that affect crystallinity include the structural regularity of the poly, mer chains; polymer chain mobility, which allows variable conformation; Table 1. The effects of cohesive energy density on permeability the repeating presence of side chains, which engage in intermolecular bondBackbone: CCH,-CHj ing; and the absence of bulky side I chains, which interfere with the crystal X Permeability at 25Cb lattice formation. The mass transfer Substituent CED of a gas or aroma in a semi-crystalline (cal/cm3) Oxygen Water Polymer group C4 polymer is primarily a function of the 66 0.188 100 amorphous phase, because the crystal-H Polyethylene line phase is usually assumed to be Polystyrene 85 0.168 1100 impermeable. Table 3 illustrates the ef/ -0 \ fects of crystallinity on oxygen perme88 0.023 8500 -OCOCH, Polybinyl acetate) ability. As the percent crystallinity of a Poly(vinyl chloride) 94 0.0036 250 -Cl polymer increases, the oxygen perme-CN Polyacrylonitrile 180 0.000039 300 ability decreases. The degree to which d oxygen permeability is affected is highly Poly(vinyl alcohol) 220 0.0000016 (dry) -OH dependent on polymer structure. An increase in the crystallinity of polyethylAdapted from Ref. 8; reproduced with permission from Technomic Publishing Co., Inc. ene from 43% to 74% results in a fiveUnits for permeability are cm pm/(m? d.kPa), whereby a given volume of permeant (cm3) moves through a specified cross-sectional area @polymer (m), which is of a given thickness (km), in a certain time interval (d) fold decrease in oxygen permeability, with a defined pressure driving force (kPa) across that polymer thickness whereas an increase in the crystallinUnannealed film ity of poly(ethylene terephthalate) from dPoly(vinyl alcohol) is soluble in water ~10% to 45% yields a threefold deCED, Cohesive energy density crease in oxygen permeability. The low
230 Trends in Food Science & Technology July 1997 [Vol. 81

Table 2. The effects of free volume

on permeability Fractional free volumeb Oxygen permeability at 25C 1.56


0.17

diffusion coefficients for aroma compounds in glassy polymers suggest that the permeability coefficients for polymers with a high crystallinity would be correspondingly low. Orientation Orientation refers to the alignment of the polymer chains in the plane of the polymer backbone, and is a by-product of the processing operation. Sha and Harrison mentioned several mechanisms for these orientation effects. They reported that the decrease in the fractional free volume of the amorphous region with orientation correlated well with the decrease in permeability, solubility and diffusivity coefficients. However, others contend that the alignment of the polymers crystallites increases the tortuosity of the permeants path, thus significantly reducing the permeability only in the case of semi-crystalline polymer?. The minimal reduction in oxygen permeability following 300% orientation of completely amorphous polystyrene is cited in support of this observationx. Tacticity Tacticity refers to the stereochemical arrangement of the substituted groups in relation to the plane of the polymer backbone. Isotacticity occurs when all of the substituent groups lie on one side of the plane of the main chain. If substituent groups alternate on either side of the plane, the polymer is considered to be syndiotactic, and atactic if the substituent groups are randomly configured. Min and PaulI examined the influence of tacticity on the permeability of carbon dioxide, oxygen and nitrogen in poly(methy1 methacrylate) (PMMA). It was concluded that permeability increased as the percentage of syndiotactic substituents increased. Jasse et ~1.~ suggestedthat these results might be indicative of a more densely packed polymer structure for isotactically substituted polymers. Crosslinking Crosslinking is the formation of intermolecular bonds among the chains of a polymer. Researchhas examined
Box 2. Polymer CMC: EVOH: HDPE: HPC: HPMC: LDPE: MC: PEG: PMMA: PVDC: PVOH: VOH: abbreviations Carboxymethylcellulose Ethylene vinyl alcohol polyethylene copolymer

Polymer Poly(4-methyl Polystyrene Polycarbonate Poly(methyl Nylon methacrylate) pentene-1)

0.204 0.176 0.168 0.132 0.120 0.098 0.080

0.097 0.0065 0.0029 0.0019 0.000039 0.000016 0.0000016


from Technomic space behveen Publishing molecules

6 (a= 1 .O) fluoride)

(dry)

Poly(vinylidene Poly(acrylonitrile) Poly(acrylonitrile) Poly(vinyl


Adapted Fractional

(annealed) (a= 1)

0.050 0.030
with permission

alcohol)

(dry)
Co., Inc. to the

from Ref. 8; reproduced free volume

is the ratio of the interstitial

volume of the polymer -Units for permeability ~1, Amorphous amorphous volume

at a temperature of absolute zero are cm pm/(mVkPa) (see Table 1) fraction (the ratio of the volume to a crystalline of the polymer that exists in an of the polymer) state, to the total volume

state, as opposed

the effects on masstransport of polymer crosslinking induced by heat curing and irradiation of a variety of polymers and by enzymatic treatment of protein-based edible polymersI&-]. Heat curing of biopolymers resulted in decreasedwater vapor permeability for soy proteinI and whey protein isolate15. These effects were attributed to an increase in intermolecular crosslinking amongthe protein strandsduring heating. Polymer chemists have made great advances in producing synthetic polymers that have very specific properties and characteristics; however, predicting and controlling the structure of biopolymer films are both very difficult tasks. Food scientists have begun fleshing out the properties and characteristics of edible films, but many significant topics pertaining to the application of

Table 3. The effects of crystallinity

on permeability

! Polyethylene Polyethylene Poly(ethylene Poly(ethylene Poly(ethylene


Nylon 6

(d = 0.92) (d = 0.955) terephthalate) terephthalate) terephthalate)

43 74 40 30 45
0

0.19
0.038 0.0049 0.0024
0.0014

High-density

Hydroxypropylcellulose Hydroxypropyl Low-density Methylcellulose Poly(ethylene Poly(methyl Poly(vinylidene Poly(vinyl Vinyl glycol) methacrylate) chloride) methylcellulose polyethylene

0.0029

(dry)

Nylon

60 0 60
with permissron from Technomic 1)

0.00045 (dry)
0.97 0.27
Publishing Co., Inc.

Polybutadiene Polybutadiene
Adapted Units d, Density from Ref. 8; reproduced for permeability

alcohol)

are cm3 p,m/(md

kPa) (see Table

alcohol

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edible films remain unexplored. Examination of the influences of the composition of synthetic polymers on oxygen and aroma barrier properties suggests that the polar nature of edible polymer films should yield excellent oxygen and aroma barrier properties. Edible polymer film composition and structure Edible polymer films include polysaccharides and/or proteins. Kester and Fennema? have produced an excellent overview of the types, methods of preparation, properties and applications of all types of edible polymers, and pointed out the rationale for developing these films as packaging supplements. The authors noted that possible functional properties include the retardation of moisture migration, gas transport (oxygen and carbon dioxide), oil and fat migration and solute transport, as well as improved mechanical handling properties, additional structural integrity, use as a vector for food additives, and retention of volatile flavor compounds. Recently, Krochta and De Mulder-Johnston provided a synopsis of the research on edible polymer films and their potential applications. They also touched on nutritional, safety and health issues associated with edible polymers. Edible polymer films prepared from celluloses, starches, other polysaccharides (alginates, carrageenans and pectinates) and proteins (collagen, gelatin, zein, gluten, soy protein, casein and whey protein) were reviewed. Water-insoluble cellulose is brought into aqueous solution by etherification with methyl chloride, propylene oxide or sodium monochloroacetate to yield the non-ionic methylcellulose (MC), hydroxypropyl methylcellulose (HPMC) and hydroxypropylcellulose (HPC) films and the ionic sodium carboxymethylcellulose (CMC) filmst9. The degree of substitution that occurs during these etherification reactions affects the properties of a film such as water retention, sensitivity to electrolytes and other solutes, dissolution temperatures, gelation properties and solubility in non-aqueous systems. Cellulose ether films are resistant to fats and oils, and are therefore likely to be good aroma barriers. The cellulose ethers produce moisturesensitive films that are effective oxygen barriers, and when applied to various fresh commodities, they have been shown to retain flavor components during storage, thus indicating their potential aroma barrier properties. The linear starch polymer amylose produces a hydrophilic film with low oxygen permeability; hydroxypropylated amylose also yields films with very low oxygen permeability19. Plasticization, chemical crosslinking and esterification all affect the final structure of the starch film to varying degrees. Coating apple slices and dried apricots with starch hydrolysates resulted in a better flavor, indicating their potential aroma barrier properties. Alginate films are composed of polymer segments of pOly@-D-InaIIUUrOniC acid), poly(a-r.-guluronic acid) and of a segment of alternating D-mannuronic and L-guluronic acid residents2. Alginate films have been shown to reduce oxygen transport and aroma loss in various food products 19.Alginate film structure is affected by the concentration of polyvalent cations in the gel (such as calcium), rate of cation addition, time of cation exposure,
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pH, temperature and presence of other constituents such as hydrocolloids2. The calcium ions pull the alginate polymer chains together via ionic bonding and thus allow for increased hydrogen bonding. The same effect occurs with pectin films. Carrageenan films are thought to form a threedimensional polymer structure via the formation of a double-helix structure, which is also thought to be effected by inter-chain salt bridges. The oxygen and aroma barrier properties of films from pectins, carrageenans and other polysaccharides have not been examined in the literature. Krochta? discussed the effects of protein structure and composition on edible film barrier properties. The proteins must be in an open or extended form to allow the molecular interaction that is necessary for film formation. The extent of this interaction depends on the protein structure (degree of chain extension) and the sequence of hydrophobic and hydrophilic amino acid residues in the protein. Increased molecular interaction results in a film that is strong but less flexible and less permeable. The degree of hydrophilicity of the amino acid residues in a protein controls the influence of moisture on the protein films mass transport properties*. Most edible films are quite moisture sensitive, but this inherent hydrophilicity makes them excellent barriers to nonpolar substances such as oxygen and some aroma compounds. As mentioned previously, an increase in crystallinity, density, orientation, molecular weight or crosslinking results in a decrease in polymer permeability. Complicated protein structures make the control of these factors quite challenging. Researchers studying edible polymers have significant obstacles to surmount in simply producing a usable film. Only of late have investigations of edible polymers included the examination of barrier properties for permeants other than moisture. The promise of using a renewable resource to simplify packaging and extend food shelf life has encouraged researchers to explore the oxygen and aroma barrier properties of edible polymers. Oxygen and aroma barrier properties of edible polymer films Oxygen barrier properties Oxygen permeability is the next most commonly studied transport property of edible polymer films after water vapor permeability. Commercial data2 on MC and HPMC films indicate that they are moderate barriers to oxygen; their oxygen permeability is approximately an order of magnitude lower than that of low-density polyethylene (LDPE), but two to three orders of magnitude greater than that of poly(vinylidene chloride) (PVDC) and ethylene vinyl alcohol copolymer (EVOH) at -24C and 50% relative humidity (Table 4). Although cellulose ethers possess a chemical formula similar to that of EVOH, their repeating ring and side-group structures probably produce a smaller cohesive energy density, larger free volume and smaller crystallinity relative to those of the linear EVOH. The higher oxygen permeability of HPMC compared with that of MC can probably be attributed to the larger HPMC side group, which results in HPMC having a smaller cohesive energy density, larger free volume and
Trends in Food Science & Technology July 1997 [Vol. 81

Table 4. Comparison polymer films

of the oxygen

permeability

of edible polymer

films and conventional

synthetic

lower crystallinity than MC. Donhowe Film type Test conditions Permeabilityb and FennemaZ2 found that compared with other water or water-ethanol solCellulose-based: vents, oxygen permeability was miniMC 24C, 50% RH 97 mized when an MC film was formed HPMC 24C, 50% RH 272 from a water-ethanol solvent in the ratio of 75% : 25% at elevated temperaMC 25C, 52% RH 90 ture (Table 4). Films formed in this manner also had greater crystallinity, Starch-based: lower water vapor permeability, higher Amylomaize starch 25C, <lOO% RH <65 tensile strength and higher elongation. Hydroxypropylated amylomaize starch 25C, ~78% RH -0 Donhowe and Fennema31 found that glycerol, added at 30% (w/w), was a Protein-based: more effective plasticizer than propylCollagen ene glycol in decreasing the tensile RT, 0% RH <0.04-0.5 strength and increasing the elongation Collagen RT, 63% RH 23.3 of MC films. Both approximately douCollagen RT, 93% RH 890 bled the oxygen permeability at -25C and 50% relative humidity. Lower Zein : PEG t glycerol (2.6 : I) 25C, 0% RH 38.7-90.3 molecular weight (molecular weight Gluten :glycerol (2.5 : 1) 25C, 0% RH 6.1 of 400 and 1450) poly(ethylene glySoy protein isolate : glycerol (2.4 :l) 25C, 0% RH 6.1 ~01)s (PEGS) were also good plasticizers but increased oxygen permeability Whey protein isolate : glycerol (2.3 : 1) 23C, 50% RH 76.1 by a factor of 4-5. Park et aL3? found Whey protein isolate : sorbitol (2.3 : 1) 23C, 50% RH 4.3 that at 0% relative humidity, the oxygen permeability of MC and HPC films Synthetic: increased as their molecular weight inLDPE 23C, 50% RH 1870 creased. Propylene glycol was shown to be a relatively poor plasticizer and HDPE 23C, 50% RH 427 produced a large increase in oxygen Polyester 23C, 50% RH 15.6 permeability at 0% relative humidity. 23C, 0% RH EVOH (70% VOH) 0.1 Interestingly, although glycerol and PEG-400 were found to be good plas23C, 95% RH 12 EVOH (70% VOH) ticizers for MC and HPC, they had litPVDC-based films 23C, 50% RH 0.4-5.1 tle effect over a range of concentrations on oxygen permeability at 0% See Box 2 for polymer abbreviations relative humidity. On the other hand, hUnits for oxygen permeability are cm~~m/(m*~d kPa) (see Table 1) Park and Chinnan found that the Based on a percentage of the oxygen permeability of PVDC-based film; Ref. 6 quantity of PEG-400 greatly affected RT, Room temperature the oxygen permeability of MC and RH, Relative humidity HPC at 0% relative humidity. RicoPeiia and Torres3 found that oxygen acid composite Butler et al.36 found that glycerol-plasticized chitosan transmission through an MC-palmitic film increased rapidly with relative humidity >57%, films had extremely low oxygen permeability at 0% relacorrelating well with moisture content. Park et al.35 tive humidity. Increasingthe plasticizer content increased studied MC films laminated with a corn zein-fatty acid the oxygen permeability. Wong et aL3 found that adding layer. They found that oxygen permeability increased lauric acid to a chitosan film more than doubled the oxyrate. However, pahnitic acid or acetylated as the concentration and chain length of the fatty acids gentransmission monoacylglycerol reduced the oxygen transmissionrate increased. High-amylose amylomaize starch films are moderate by an order of magnitude. As a group, protein films appearto have lower oxygen to good oxygen barriersz3,with an oxygen permeability that is lower than that of the cellulose ethers, even at permeabilitiesthan non-ionic polysaccharide films. This higher relative humidity (Table 4). Oxygen permeability may be related to their more polar nature and more linear is even higher for high-amylose films than for PVDC or (non-ring) structure, leading to higher cohesive energy EVOH films. However, hydroxypropylated starch films density and lower free volume. At 0% relative humidity, may have even lower oxygen permeability24.Apparently collagenfilm hasan oxygen permeability similarto that of the starch structures in these films produce a combi- PVDC and EVOH filmsZ. However, collagenfii is more nation of higher cohesive energy density, lower free sensitive to relative humidity; at -50% relative humidity, volume and higher crystallinity than occurs in cellulose its oxygen permeability is one to two ordersof magnitude greater than that of PVDC or EVOH films (Table 4). ethers.

Ref.

21 21 22

23 24

25 25 25 26 27 28 29 29

6 6 30 6 6 6

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Films that are based on corn zein, wheat gluten, soy protein or whey protein appear to possess an oxygen permeability that is greater than that of collagen-based films (at 0% relative humidity)hm29. This is probably due to the fact that these globular proteins have a less linear structure and a greater percentage of larger amino acid side groups than collagen, resulting in a smaller cohesive energy density and larger free volume. However, proper selection of plasticizer appears to reduce the oxygen permeability while maintaining the mechanical properties, presumably by affecting the polymer free volume (Table 4)29. Gennadios et aL2 investigated the effect of temperature on the oxygen permeability of corn zein, wheat gluten and wheat gluten-soy protein isolate films at 0% relative humidity. Results showed good agreement with the Arrhenius activation energy model. Based on the lack of breaks in the Arrhenius plots, no structural transitions were identified in the 7-35C temperature range. Brandenburg et af.8 discovered that the oxygen permeability of soy protein films decreased as the pH of the film solution preparations increased from 6 to 12. Gennadios et al. found that replacing glycerol plasticizer with triethylene glycol in wheat gluten films produced a large increase in oxygen permeability. This effect was attributed to the larger size and less polar nature of triethylene glycol, which would also correlate with an increased free volume and reduced cohesive energy density. McHugh et aL4 studied the properties of films made from fruit purCes. Peach puree films were found to be better oxygen barriers than MC and other polysaccharide films and comparable to whey-protein-based films. In general, the oxygen permeability of edible polymer films, especially protein films, appears to be quite low. Optimization of polymer structure by increasing crystallinity, orientation or crosslinking in pre-processing steps or during film formation may result in further reductions in the oxygen permeability of a film. Modification of polymer structure combined with optimized selection of plasticizer may produce edible films with oxygen barrier properties that are as good as those of PVDC and EVOH films.

(wheat protein) films. An isostatic gas chromatograph technique was used with a dual-detection scheme for measuring moisture and aroma transport simultaneously. The gluten film was a better barrier to 1-octen-3-01 than either the LDPE or MC film, but not as good a barrier as the cellophane film. Continuing this work, Debeaufort et al. attempted to explain the differences in l-octen-3-01 transport among LDPE, cellophane, MC and gluten films. However, they were unable to correlate aroma flux to the amount of aroma absorbed, the hydrophobicity of the polymer, or to trends in the diffusion coefficient. It was concluded that the sorption-diffusion model, alone, cannot describe the aroma or moisture permeability in edible films. Furthermore, it was suggested that the variations in aroma permeability were due to a moisture plasticization phenomenon and the sweeping action of water vapofls. Whey protein films have excellent oxygen barrier propertiesz9. However, DeLassus has shown that a polymers oxygen barrier properties are not necessarily a reliable indicator of its aroma barrier properties. The author cautioned that oxygen and aroma compounds behave quite differently in glassy versus rubbery polymers. Glassy polymers have medium to high oxygen diffusion coefficients but very low aroma diffusion coefficients (at low permeant concentrations) rl. Rubbery polymers exhibit diffusivities for oxygen and aroma compounds that are of the same order of magnitude (i.e. permeant size is not as influential a factor). DeLassus stated that trends in oxygen and aroma permeability are comparable within the rubbery or glassy polymer categories, but not between them. Recent work by Miller et a14 indicates whey protein isolate films to be excellent barriers to d-limonene. Miller and Krochta47 found whey protein isolate films containing 25% glycerol (dry basis) plasticizer to be comparable to EVOH films as a barrier to d-limonene under similar temperature and humidity conditions. Additionally, d-limonene permeability in 25% glycerol whey protein isolate films was found to be significantly affected by temperature and relative humidity but not by permeant concentrations in the range of 62-226 ppm (v/v). Existing commercial applications of edible films include Aroma barrier properties Although a significant body of work concerned with the collagen as a casing for sausages and a wrap for smoked oxygen barrier properties of edible films exists, the aroma meats, and gelatin and corn zein as encapsulating agents for food ingredients and pharmaceuticals20. Evaluation of barrier properties of edible films have not been thoroughly the basic barrier properties of edible polymers will pave examined. Recent reviews of the use of proteins as edible the way for additional applied research dealing with spefilms and coatings indicate that the literature is somewhat cific food applications. Such applied studies of the oxylacking in research pertaining to the aroma barrier properties of edible films20s4. However, reviews of the literature gen and aroma barrier properties of edible polymers will on synthetic polymers are valuable resources to the re- aid in defining the limits of specific food applications. searcher studying the aroma transport properties of edible Current research on edible biopolymers allows for speculation on several food-polymer applications. films [Refs 42 and 43, and K.S. Miller (1997) Physical Properties of Whey Protein Isolate Films: d-Limonene Gas and aroma barrier food applications of edible films Permeability, Water Vapor Permeability and Mechanical Oxygen barrier applications Properties (PhD thesis), University of California, Davis, Applications that take advantage of the beneficial oxyCA, USA]. In fact, Debeaufort and Voilley4 were the first to ex- gen barrier properties of edible polymer films have been amine aroma permeability in edible polymers. They explored for many years. Ganz4x found that HPC film coatings provided peanuts with some protection from oxyexamined the co-permeation of moisture and l-octen-3-01 (mushroom aroma) in LDPE, cellophane, MC and gluten gen, but the effect wasnot well quantified. MC andHPMC
Trends in Food Science & Technology July 1997 [Vol. 81

coatings are commonly used for pharmaceutical tablets, providing protection from oxygen, aroma and moisture transport. Several researchers have found that CMC-based coatings can delay ripening and improve the quality of fresh fruit and vegetables by retarding the transport of oxygenJ9-5. Park et al.s investigated the application of MC film laminated with a corn zein-stearic acid-palmitic acid blend for the packaging of potato chips. Acceptable chip quality was maintained for up to 25 d at 25C. The composition of the corn zein-stearic acid-palmitic acid blend layer had no effect on the results. Jokay et aL5 concluded that sensory tests on stored almond nut meats coated with hydroxypropylated highamylose starch indicated considerable protection against the development of oxidative rancidity. However, quantitative data were not presented. Murray and Luft5s found that starch hydrolysate coating applied to apple slices before drying maintained whiteness more effectively than 2% ascorbic acid solution, but not as effectively as sulphur dioxide. However, slices coated with starch hydrolysate were judged superior in flavor. Murray and Luft5s also reported that almonds coated with the starch hydrolysate had improved flavor and shelf life, indicating oxygen barrier attributes for the coating; however, they did not present any data. Wanstedt et a1.j found that coating ground pork patties with calcium alginate either before or after precooking improved the quality of the final cooked product, as measured by the development of oxidative rancidity. Earle and Snyder 57 found that an alginate coating improved the flavor and color of frozen shrimps, probably because of a reduction in rancidity. Earle and McKeej8 developed an alginate-based coating with oxygen barrier properties for breaded and filled-dough food products. Meyer et a1.s9 found that carrageenan coatings extended the shelf life of poultry pieces by acting as an oxygen barrier. Chitosan coatings were found to be effective in extending the life of fresh fruit by modification of oxygen and carbon dioxide transfer60.h. Collagen casings for sausages are known to provide some protection from oxygen:. Gelatin coatings have been found to be effective in protecting several meat products from oxygen h3.M . Zein-based coatings have been used to reduce rancidity in nuts and confections65,6h. Corn zein films were also shown to affect oxygen and carbon dioxide exchange in fresh tomatoes, as evidenced by a delay in color change, firmness loss and weight loss during storage6. The result was an extension of shelf life by 6d. Coatings based on whey protein were shown to reduce the oxygen uptake by dry-roasted peanuts68, delaying oxidative rancidity, as measured by the peroxide value and hexanal content of the peanuts6. Aroma barrier applications Edible films can be used as flavor carriers in addition to providing a barrier to aroma 10~s~~~.AndresO also pointed out that flavor quality deterioration can include the loss of characteristic flavor owing to oxidation or poor oxygen barrier properties. Thus, an edible film can
Trends in Food Science & Technology July 1997 [Vol. 81

assist in retaining the characteristic food flavor via its aroma barrier properties and also limit quality deterioration due to oxidation via its oxygen barrier properties. Researchers have examined the ability of edible coatings applied to harvested fruit to prevent the loss of characteristic flavor. The use of edible coatings on citrus fruit resulted in an increase in desirable flavor compounds after storage, as compared with uncoated fruits2. Cellulose-based composite films including wax seemed to provide the best balance between flavor retention and the prevention of weight loss due to moisture transport5. Pervaporation, the removal of organics from an aqueous solution through a separating membrane, has been successfully utilized to enrich and recover flavor volatiles. Understanding the behavior of flavors in aqueous solutions, such as the systems used in these pervaporation studies, provides insight into the potential applications for edible films in environments with a high water activity. The sorption characteristics of edible films may allow the incorporation of desirable flavors and aromas into a coating for delayed release, thereby enhancing the foods flavor profile. Encapsulated flavors and aromas could be released by heating and/or rehydration, as well as by mastication. Hydrophilic edible films can be applied to any low-moisture food with a sensitive characteristic flavor to aid in aroma retention. An example would be fruit-flavored chewing gums, which often lose their characteristic aroma with time. Dry, fruit-flavored cereal would be another potential application for edible films to prolong a products shelf life by limiting aroma transport. Basic and applied research needs The effects of factors, identified by Banker?, that influence film mass transport - polymer structure and orientation, salt concentration, ion ratios, polymer-permeant interactions, acid and base concentrations, addition of dispersed solids, and permeant boundary layer thickness - provide the edible film researcher with boundless avenues of research. Specifically, no work has been done to optimize the influences of free volume, crystallinity or orientation on the oxygen and aroma barrier properties of edible polymers. Before a packaging specialist can take advantage of an edible polymers barrier properties, the polymer must be successfully applied to the desired food system. Guilbert examined the factors influencing the food film coating operation and concluded that the degree of cohesion (interactions among the polymer molecules) and the degree of adhesion (interactions between the polymer and the food molecules) are of critical importance to the successful application of an edible packaging. The author mentioned several formulation and processing parameters that influence cohesion and adhesion, including solution temperature, solvent evaporation rate, solvent characteristics and the concentration of the film-forming polymer molecules in the solution. Few researchers have focused on the effects of these parameters on both the degree of
235

adhesion and the degree of cohesion during food film coating. Understanding these basic effects is critical to the successful application of an edible coating to a food. Gaseous diffusion through polymers has long been studied by polymer scientists. DiBenedetto3 concluded that models of such diffusion depend on knowledge of the physical properties of the polymer and the geometry of the permeant. Lack of knowledge about these polymer and permeant properties restricts the applicability of many of the models that have been proposed to predict oxygen and aroma transport. Knowledge about the physical properties of edible films is even more limited. Kester and Fennema* concluded that much of the edible film and coating work reported in the literature is of limited value owing to the lack of quantitative data on barrier characteristics of the coatings. It is only through the compilation of barrier properties and their correlation with edible polymer structure and composition that it will be possible to apply generalized theories explaining oxygen and aroma mass transfer behavior to solve food packaging problems. Finally, microbial stability is an area that will become more important as more edible polymers approach commercial viability. This will be especially important for higher-water-activity applications. The addition of antimicrobial agents and their migration in MC and HPMC multi-layer polysaccharide films have been examined with respect to their effect on oxygen permeability34*73. However, other antimicrobial agents and their effects on both aroma and oxygen permeability in edible polymers have not been examined. References
1 Soroka, W. (1995) Fundamentals of Packaging Technology, institute of Packagmg Professionals, Herndon, VA, USA 2 Kester, J.J. and Fennema, O.R. (1986) Edible Films and Coatings: A Review in Food Jechnol. 40,47-59 3 DiBenedetto, A.T. (1963) Molecular Properties of Amorphous High Polymers. Il. An Interpretation of Gaseous Diffusion Through Polymers in 1. Polym. SC;.: Part A 1, 3477-3407 4 Jasse, B., Seuvre, A.M. and Mathloutht, M. (1994) Permeability and Structure in Polymeric Packaging Materials in Food Packaging and Preservation (Mathlouthr, M., ed.), pp. l-22, Blackie 5 Cuilbert, S. 11986) Technology and Application of Edrble Protective Films in food Packaging and Preservation: Theory and Practice (Mathlouthi, M., ed.), pp. 371-394, Elsevier 6 Salame, M. (1986) Barrier Polymers in The Wiley Encyclopedia of Packaging Technology (Bakker, M., ed.). pp. 48-54, John Whey & Sons 7 Robertson, C.L. (1993) Permeability oiThermoplastic Polymers in Food Packaging: Principles and Practice, pp. 73-110, Marcel Dekker 8 Salame, M. 11989) The Use oi Barrier Polymers in Food and Beverage Packaging in Plastic Film Technology (Vol. 1) (Finlayson, K.M., ed.). pp. 132-145, Technomic 9 Maeda, Y. and Paul, D.R. (1987) Effect of Antiplasticization on Gas Sorption and Transport. III. Free Volume Interpretation in 1. Polym. SC;., Polym. Phys., Ed. 25, 1005-l 016 10 Mark, H.F. and Atlas, S. (1977) Introduction to Polymer Science in lntroductron to Polymer Science and Technology (Kaufman, H.S., ed.), Wiley Interscience 11 Detassus, P.T. (1994) Permeation of Flavors and Aromas Through Glassy Polymers in Tappi). 77, 109-l 13 12 Sha, H. and Harrison, I.R. (1992) CO, Permeabtlity and Amorphous Fractional Free-volume in Uniaxially Drawn HDPE in 1. Polym. SC;.: Part 5: Polym. Phys. 30.915-922 13 Min, K.E. and Paul, D.R. (1988) Effect oi Tacticity on Permeation Properties of Polyfmethyl methacrylate) in I. Polym. SC;.: Part 6: Polym. Phys. 26. 1021-1033

14 Cennadios, A., Ghorpade, V.M., Weller, C.L. and Hanna, M.A. (1996) Heat Curing of Soy Protein Films in Trans. ASAE 39, 575-579 15 Miller, KS., Krochta, J.M. and Chiang, M.T.E. Heat Curing of Edible Whey Protein Films in 1. Food Sci. fin press) 16 Matsui, T., Ono, A., Shimoda, M. and Osajima, Y. (1992) Thermodynamic Elucidation of Depression Mechanism on Sorption of Flavor Compounds into Electron Beam Irradiated LDPE and EVA Films in 1. Agric. Food Cbem. 40,479-483 17 Stuchell, Y.M. and Krochta, J.M. (1994) Enzymatic Treatments and Thermal Effects on Edible Soy Protein Films in 1. Food SC;. 59, 1332-l 337 18 Krochta, J.M. and De Mulder-Johnston, C.L C. (1997) Edible and Biodegradable Polymer Films: Challenges and Opportunities in Food Techno/. 51,61-74 19 Nisperos-Carnedo, M.O. (1994) Edible Coatings and Films Based on Polysaccharides in Edible Coatings and Films to /mprove Food Quaky (Krochta, J.M.. Baldwin, E.A. and Nisperos-Carriedo, M., eds), pp. 305-336, Technomic 20 Krochta, J.M. 119971 Edible Protern Films and Coatings in FoodProteins and Their Applications in Foods, pp. 529-550, Marcel Dekker 21 Anon. (199oi A Food Technologists Guide to Methocel Premium Food Gums, The Dow Chemical Co., Midland, Ml, USA 22 Donhowe, LG. and Fennema, 0. (1993) The Effects oi Solutton Composition and Drying Temperature on Crystallinity, Permeability and Mechamcal Properties of Methylcellulose Films in I. FoodProcess. Preserv. 17. 231-246 23 Mark, A.M., Roth, W.E., Mehltretter, C.L. and Rist, C.E. (1966) Oxygen Permeability of Amylomaire Starch Films in Food Techno/. 20, 75-77 24 Roth, W.B. and Mehltretter, C.L. (1967) Some Properties of Hydroxypropylated Amylomaire Starch Films in Food Technol. 21, 72-74 25 Lieberman, E.R. and Gilbert, SC. (1973) Gas Permeation of Collagen Films as Affected by Cross-linkage, Moisture, and Plasticizer Content in /. Polym. Ser. 41,33-43 26 Butler, B.L. and Vergano, P.J. (1994) Degradation of Edible Films in Storage (Paper No. 9465511, ASAE, St Josephs, MI. USA 27 Gennadios. A., Weller, CL. and Testm, R.F. (1993) Temperature Efiect on Oxygen Permeabrlity of Edible Protein-based Films in 1. FoodSo. 58, 212-214 28 Li, H., Ghorpade, V. and Hanna, M.A. (1993) Effects of Chemical Modrfications on Soy and Wheat Protein Films (Paper No. 936529), ASAE, St Josephs, Ml, USA 29 Habig McHugh, T and Krochta, J.M. (1994) SorbitolVersus Glycerolplasticized Whey Protein Edible Films: Integrated Oxygen Permeabrhty and TenslIe Property Evaluation in /. Agric. Food Chem. 42, 841-845 30 Hanlon, J.F., ed. (1992) Films and Foils in Handbook ofPackage Engrneering, pp. 3.1-3.59, Technomic 31 Donhowe, LG. and Fennema, 0. 11993) The Effects of Plasticizers on Crystallinity, Permeability and Mechanical Properties of Methylcellulose Films in J. Food Process. Preserv. 17, 247-257 32 Park, H.J., Weller, C.L., Vergano, P.J. and Testin, R.F. (1993) Permeability and Mechanical Properties of Cellulose-based Edible Films in /. Food Ser. 58, 1361-1364, 1370 33 Park, H.J. and Chinnan, M.S. (1995) Gas and Water Vapor Barrier Properties of Edible Films From Protein and Cellulosic Materials in 1. Food Eng. 25, 497-507 34 Rico-PeAa, D.C. and Torres, J.A. 11990) Oxygen Transmission Rate of an Edible Methylcellulose-Palmitic Acid Frlm rn 1. Food Process. Preserv. 13,125-l 33 35 Park, J.W., Testin, RF. Vergano, P.J., Park, H.J. and Weller, CL. (19961 Fatty Acrd Distribution and Its Effect on Oxygen Permeability in Laminated Edible Films in 1. Food Sci. 61,401-406 36 Butler, B.L., Vergano, P.J., Testin, R.F., Bunn, J.M. and Wiles. J.L (1996) Mechanical and Barrier Properties of Edible Chitosan Films as Affected by Composition and Storage in ). Food Sci. 61, 953-955, 961 37 Wong, D.W.S., Gastineau, F.A., Gregorski, K.S., Tillin, S.J. and Pavlath, A.E. (1992) Chitosan-Liprd Films: Microstructure and Surface Energy in I. Agric. Food Chem. 40,540-544 38 Brandenburg, A.H., Weller, C.L. and Testin, R.F. (1993) Edible Films and Coatings From Soy Protein in 1. Food Sci. 58, 1086-l 089 39 Gennadios, A., Weller, CL. and Testin, R.F. 11993) Property Mocifrcation of Edible Wheat Gluten-based Films in Trans. ASAE36, 465470 40 McHugh, T.H., Huxsoll, C.C. and Krochta, J.M. (1966) Permeability Properties of Fruit Puree Edtble Films in 1. FoodSci. 61, 88-91 41 Torres, ].A. (1994) Edible Films and Coatings From Proteins in Protein functionality in food Sysfems (Hettiarachchy, N.S. and Zeigler, C.R., eds), pp. 467-507, Marcel Dekker 42 Felder, R.M. and Huvard, C.S. (1980) Permeation, Diffusion, and Sorption of Gases and Vapors in Methods of Experimental Physics (Fava, R.A., ed.), pp. 315-377, Academic Press

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&Technology

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43 Hernandez, R.J., Ciacin, J.R. and Baner, A.L. (1986) The Evaluation of the Aroma Barrier Properties of Polymer Films in /. Plast. Film Sheeting 2, 187-211 44 Debeaufort, F. and Voilley, A. (1994) Aroma Compound and Water Vapor Permeability of Edible Films and Polymeric Packagings in J Agric. Food Chem. 42,2871-2875 45 Debeaufort, F., Tesson, N. and Voilley, A. (1995) Aroma Compounds and Water Vapour Permeability of Edible Films and Polymeric Packagings in F&s and Packaging Materials - Chem& Interactions (Ackermann, P.. lAgerstad, M. and Ohlsron, T., eds), pp. 169-l 74, The Royal Society of Chemistry, Cambridge, UK 46 Miller. K.S., Krochta, J.M., and Upadhyaya. S.K. Aroma Permeability in Whey Protein Films in 1. FoodSci. (in press) 47 Miller, K.S. and Krochta, J.M. Measuring Aroma Transport in Polymer Films in Trans. ASAE (in press) 48 Canz, A.J. (1969) CMC and Hydroxypropyl Cellulose-versatile Gums for Food Use in Food Prod. Dev. 3, 65-74 49 Meheriuk, M. and Lau, O.L. (1988) Effect of Two Polymeric Coatings on Fruit Quality of Barlett and dAnjou Pears in I. Am. Sot. Horfic. Sci. 113. 222-226 50 Santerre, CR., Leach, T.F. and Cash, J.N. (1989) The Influence of the Sucrose Polyester, Semperfresh, on The Storage of Michigan Grown Mcintosh and Golden Delicious Apples in 1. food Process. Preserv. 13, 293-305 51 Nisperos-Carriedo, M.O., Shaw, P.E. and Baldwin, E.A. (1990) Changes in Volatile Flavor Components of Pineapple Orange Juice as Influenced by the Application oi Lipid and Composite Films in 1. Agric. FoodChem. 38, 1382-l 387 52 Baldwin, E.A., Nisperos-Carriedo, M., Shaw, P.E. and Burns, J.K. (1995) Effect of Coatings and Prolonged Storage Conditions on Fresh Orange Flavor Volatiles, Degrees Brix, and Ascorbic Acid Levels In 1. Agric. Food Chem. 43, 1321-1331 53 Park, J.W., Testin, R.F., Vergano, P.]., Park, H.J. and Weller, CL. (1966) Application of Laminated Edible Films to Potato Chip Packaging in I. Food SC;. 61, 766-768. 777 54 Jokay, L., Nelson, C.E. and Powell, E.L. (1967) Development of Edible Amylaceous Coatings for Foods in Food Technof. 21, 1064-1066 55 Murray, D.G. and Luft. L.R. (1973) Low-D.E. Corn Starch Hydrolysates in Food Technol. 27, 32-40 56 Wanstedt, K.G., Seideman. S.C., Donnelly, L.S. and Quenzer, N.M. (19811 Sensory Attributes of Precooked, Calcium Alginate-coated Pork Patties in 1. Food Protect. 44, 732-735 57 Earle, R.D. and Snyder, C.E. (19661 Method of Preparing Frozen Seafood, United States Patent US 3 255 021

58 Earle, R.D. and McKee, D.H. (1985) Coated Food Product and Method of Making Same, Umted States Patent US 4 504 SO2 59 Meyer, R.C., Winter, A.R. and Weiser, H.H. (1959) Edible Protective Coatings for Extending the Shelf Life of Poultry in Food Technol. 13, 146-148 60 Elson, CM. and Hayes, E.R. (1985) Development of the Differentially Permeable Fruit Coating Nutri-Save@ for the Modified Atmosphere Storage of Fruit in Proceedings of the Fourth National Controlled Atmosphere Research Conierence: Controlled Atmospheres for Storage and Transport of Perishable Agricultural Commodities, North Carolina State University, Raleigh, NC, USA 61 Davies, D.H., Elson, C.M. and Hayes, E.R. 11989) N,O-Carboxymethyl Chitosan. a New Water Soluble Chitin Derivative in Chitin and Chitosan: Sources, Chemistry, Biochemistry, Physical Properties, and Applications (Skjak-Braek. C., Anthosan, T. and Sandford, P., eds), pp. 467-472. Elsevier 62 Baker, R.A., Baldwin, E.A. and Nisperos-Carriedo. M.O. (1994) Edible Coatings and Films for Processed Foods in Edible Coafings and Films to improve Food Quality (Krochta, J.M., Baldwin, E.A. and Nisperos-Carriedo, M.O., eds), pp. 89-104, Technomlc 63 Klose, A.A., Mecchi, E.P. and Hanson, H.L. (1952) Use of AntioxIdants in the Frozen Storage of Turkeys in Food Technol. 6, 308 64 Whitman, C.R. and Rosenthal, H. (1971) Process of Coating Food, United States Patent US 3 556 814 65 Alikonls, 1.1. (19791 Candy Technology, AVI Publishing, Westport. CT, USA 66 Andres, C. (1984) Natural Edible Coating Has Excellent Moisture and Grease Barrier Properties in food Process. 45, 48-49 67 Park, H.J.. Chinnan, MS. and Shewfelt, R.L. (1994) Edible Coating Effects on Storage Liie and Quality oi Tomatoes in 1. Food Sci. 59, 568-570 68 Mate, 1.1, and Krochta, J.M. (1996) Whey Protein Coating Effect on the Oxygen Uptake of Dry Roasted Peanuts in I. Food Sci. 61, 1202-l 206, 12 10 69 Mate, ].I., Frankel, E.N. and Krochta, J.M. (1996) Whey Protein isolate Edible Coatings: Effect on the Rancidity Process of Dry Roasted Peanuts in I. Agric. Food Chem. 44,1736-l 740 70 Andres, C. 11985) Edible Films Have Potential for Significantly Improving Aesthetic and Nutritional Content of Foods in Food Process. July, 102-l 06 71 Karlsson, H.O.E. and Tragardh, C. (1993) Pervaporatlon of Dilute Organic-Waters Mixtures. A Literature Review on Modelling Studies and Application to Aroma Compound Recovery in 1. Membr. Sci. 76, 121-146 72 Banker, G.S. (19661 Film Coating Theory and Practice in /. Pharm. Sci. 55,81-89 73 Rico-Peiia, D.C. and Torres, J.A. I1 991) Sorbic Acid and Potassium Sorbate Permeability of an Edible Methylcellulose-Palmitic Acid Film: Water Activity and pH Eifects in 1. Food Sci. 56, 497-499

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