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Water Vapor Permeability of Starch Films

This document summarizes a study on the water vapor permeability of edible films made from high amylose corn starch. The researchers measured the water vapor permeability of the starch films at different temperatures, plasticizer contents, and film thicknesses. They found that water vapor permeability increased with temperature between 5 and 40°C, following an Arrhenius expression. Permeability also increased directly with plasticizer content and film thickness. The interactions between sorbed water molecules and the starch polymer structure affect permeability in a complex way.

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0% found this document useful (0 votes)
23 views7 pages

Water Vapor Permeability of Starch Films

This document summarizes a study on the water vapor permeability of edible films made from high amylose corn starch. The researchers measured the water vapor permeability of the starch films at different temperatures, plasticizer contents, and film thicknesses. They found that water vapor permeability increased with temperature between 5 and 40°C, following an Arrhenius expression. Permeability also increased directly with plasticizer content and film thickness. The interactions between sorbed water molecules and the starch polymer structure affect permeability in a complex way.

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© All Rights Reserved
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Journal of Food Engineering 80 (2007) 972–978

[Link]/locate/jfoodeng

Water vapor permeability of edible starch based films


M.A. Bertuzzi *, E.F. Castro Vidaurre, M. Armada, J.C. Gottifredi
Instituto de Investigaciones para la Industria Quı´mica (CONICET), Facultad de Ingenierı́a, Universidad Nacional de Salta,
Buenos Aires 177 (A4402 FDC) Salta, Argentina

Received 6 April 2006; received in revised form 6 July 2006; accepted 10 July 2006
Available online 9 October 2006

Abstract

Water transport in edible films of starch based products is a complex phenomenon due to the strong interaction of sorbed water mol-
ecules with polymeric structure of starch. Water sorption isotherms on high amylose starch based films are highly non linear in the range
studied (5–45 C). So permeability is usually affected by a number of parameters such as temperature, film thickness and plasticizer con-
tent. This knowledge is required to simulate and predict transport patterns. In the present contribution water vapor permeability (WVP)
of high amylose corn starch (HACS) films, prepared in our laboratory, was determined following ASTM E-96 procedure. WVP increases
as temperature increases between 5 and 40 C and observed results can be correlated with an Arrhenius-type expression. Activation
energy of WVP for the starch film investigated is 5.61 kJ/mol and values of WVP ranged between 2 · 1010 and 1 · 109 g m1 s1 Pa1.
It is also shown a direct relation between WVP with plasticizer content and film thickness. These observations could be explained in
terms of variations in the number of potential intermolecular interactions in the film structure.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Starch films; Sorption isotherms; Water vapor permeability; Glycerol; Film thickness

1. Introduction be an interesting solution since this polymer is abundant,


cheap, biodegradable and edible. Several studies have been
There has been a renewed interest in edible and biode- done to analyze starch based films properties (Arvanito-
gradable films. These films have the potential to replace yannis & Biliaderis, 1998; Arvanitoyannis & Biliaderis,
conventional packaging in some applications. Polysaccha- 1999; Mali, Grossmann, Garcı́a, Martino, & Zaritzky,
rides, such as starches, cellulose derivatives and plant 2002; Rindlav-Westling, Standing, Hermansson, & Gaten-
gums, have been reported as edible films and coatings in holm, 1998; Ryu, Rhim, Roh, & Kim, 2002).
food packaging and preservation (Debeaufort, Quezada- Water vapor permeability results can be useful to under-
Gallo, & Voilley, 1998; Donhowe & Fennema, 1994; Guil- stand possible mass transfer mechanisms and solute and
bert, 1986). They are known to be effective barrier to gas polymer interactions in edible films. According to the ther-
transport (O2, CO2), although they present high water modynamic of irreversible process, water chemical poten-
vapor permeability (Donhowe & Fennema, 1994; Forssell, tial difference is the driving force of the water transfer
Lahtinen, Lahelin, & Myllärinen, 2002; McHugh & Kro- through a film. When the process occurs at constant tem-
chta, 1994). Generally the main functional properties of perature and pressure, the water chemical potential differ-
these hydrophilic materials strongly depend on their water ence results proportional to water vapor concentration
content and therefore on the surrounding humidity difference between the two faces (Morillon, Debeaufort,
(Chang, Cheah, & Seow, 2000; Wiles, Vergano, Barron, Blond, & Voilley, 2000).
Bunn, & Testin, 2000). Particularly, the use of starch could Permeability can be defined as the product of diffusivity
and solubility only when Fick and Henry laws fully apply.
*
Corresponding author. Tel./fax: +54 387 4251006. For most edible films the water vapor strongly interacts
E-mail address: bertuzzi@[Link] (M.A. Bertuzzi). with polymer structure, which results in diffusion and solu-

0260-8774/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/[Link].2006.07.016
M.A. Bertuzzi et al. / Journal of Food Engineering 80 (2007) 972–978 973

bility coefficients dependent on driving force (Gennadios, Table 1


Bradenburg, Park, Weller, & Testin, 1994a; Morillon, Water activity values of saturated salt solutions at different temperatures
Debeaufort, Blond, Capelle, & Voilley, 2002). Salt aw (5 C) aw (25 C) aw (35 C) aw (45 C)
In the present study, starch based films, were prepared LiCl 0.129 0.114 0.108 0.103
from high amylose corn starch using procedures deemed CH3COOK 0.292 0.237 0.216 0.198
to be practical and economical at large scales. The films MgCl2 0.354 0.329 0.318 0.308
K2CO3 0.459 0.443 0.436 0.430
were targeted as packaging material for foods, which Mg(NO3)2 0.584 0.536 0.516 0.497
require controlled water vapor transport to extend the shelf NaBr 0.682 0.653 0.638 0.624
life of products. The scope of this contribution is to inves- NaCl 0.805 0.762 0.743 0.726
tigate the effect of temperature, glycerol content and film KCl 0.934 0.855 0.821 0.791
thickness on water vapor permeability (sorption and diffu-
sion phenomena) of high amylose corn starch based film. contain the saturated salt solutions and then the sorbostats
were sealed. The sorbostats were kept inside an environ-
2. Material and methods mental chamber maintained at constant temperature. Film
samples were equilibrated in the sorbostats for 4 days
2.1. Film preparation and casting before their weights were recorded. The weights of the sam-
ples were checked during 3 days more. Equilibrium was
High amylose corn starch (Sigma Chemical Co., St. judged to have been attained when the difference between
Louis, MO., USA) with an amylose content of about two consecutive sample weightings was less than 1 mg/g
70% and native lipid content of 1.2%, was used. Film-form- dry solid. Results at equilibrium were reported for each rel-
ing dispersion consisted of 1 g of starch, 10 mL 0.25 N ative humidity as gram water sorbed/100 g dry film.
sodium hydroxide and 10 mL distilled water. Film-forming Absorption tests were done in triplicate at each aw. The
dispersion was maintained 60 min under magnetic stirring. moisture sorption determination was done at 5. 25, 35
After that, the dispersion was gelatinized in a shaker water and 45 C. Experimental sorption data were fitted using
bath at 78–80 C during 10 min. This procedure ensures the BET equation. The heat of sorption (DHs) was deduced
disintegration of starch granules to form a homogeneous from the sorption isotherm data at a number of tempera-
dispersion. Glycerol (Merck, Whitehouse Station, NJ, tures by applying Clausius–Clapeyron equation (Al-Muh-
USA.) was added as plasticizer. When starch solution tem- taseb, McMinn, & Magee, 2002; Mulet, Garcı́a-Reverter,
perature was around 50 C, solution was poured on plastic Sanjuán, & Bon, 1999; Viollaz & Rovedo, 1999).
Petri dishes. Dishes were placed in an air-circulating oven
at 35 C and 50% of RH until films were dry. After 15 h, 2.4. Water vapor permeability (WVP) determination
the dishes were removed from the oven and the films were
peeled off. Films present excellent transparency. Films of The apparatus and methodology described in the ASTM
various thicknesses were prepared by pouring different E96 (ASTM, 1995) were used to measure the WVP of the
amounts of starch solution onto the dishes. film. Film specimens were conditioned for 48 h in a cham-
ber at 25 C and 52% relative humidity (Mg(NO3)2 satu-
2.2. Film thickness measurement rated solution) before being analyzed. Films were sealed
on cups containing distilled water. Test cups were placed
The thickness of film was measured with an electronic in a desiccator cabinet maintained at temperature and rel-
micrometer (0.001 mm accuracy, Fowler, Cole-Parmer ative humidity (LiCl saturated solution) controlled. To
Instruments Co.). Reported thickness was the mean value determine film thickness and plasticizer effect on WVP,
of five measurements and it was used as the specimen thick- tests were done at 30 C. To study temperature influence
ness for water vapor permeability calculations. on WVP, samples were analyzed in a temperatures range
between 5 and 40 C. A fan was used to maintain uniform
2.3. Determination of moisture sorption conditions at all test locations over the specimen. Periodi-
cal weightings monitored the weight changes. Weight loss
Constant relative humidity environments were estab- was plotted over time and when steady state (straight line)
lished inside sorbostats, glass jars, using salt solutions. was reached 6 h more were registered. The WVP was calcu-
The salts used (LiCL, CH3COOK, MgCl2, K2CO3, lated from the slope (G) of a linear regression of weight loss
Mg(NO3)2, NaBr, NaCl, KCl) were the different salts rec- versus time.
ommended by COST-90 project (Argaiz & López-Malo,
Gx
1994), to cover a water activity range from 0.10 to 0.90. WVP ¼ ð1Þ
A  Dp
Table 1 shows water activity for all saturated salt solutions
at different temperatures. All salts used were analytical where x is the film thickness; A is the area of exposed film
grade. Film samples were cut into pieces approximately and Dp is the differential water vapor partial pressure
2 cm2. Samples were weighed and placed on a stainless steel across the film. This method uses Fick’s first law and
lattice by holding it on a tripod inside the sorbostats that Henry’s law to calculate film WVP and assume that film
974 M.A. Bertuzzi et al. / Journal of Food Engineering 80 (2007) 972–978

solubility and diffusivity are constant. WVP measured val- tı́n-Polo, 2001). Adsorption and mixing processes are exo-
ues were corrected for air gap distance between water level thermic since the moisture content decreases with
and the film position according to procedures outlined in increasing temperature at a given value of water activity.
Gennadios, Weller, and Gooding (1994b). This behavior is usual for most dehydrated food materials,
such as corn protein, starch and gelatin gels, fish muscle,
3. Results and discussion meat products and also for gluten and myofibrillar protein
based films (Al-Muhtaseb et al., 2002; Cuq et al., 1997;
3.1. Factors affecting permeability Gontard, Guilbert, & Cuq, 1993; Viollaz & Rovedo,
1999). The heat of sorption (DHs) was obtained from sorp-
3.1.1. Effect of temperature tion isotherms by applying Clausius–Clapeyron equation.
The diffusion and solubility coefficients of permeants are Changes in enthalpy provide a measure of the energy
affected by temperature. The temperature dependence on changes occurring on the condensation and mixing of
solubility obeys the Van’t Hoff law, while diffusion obeys water molecules within the film during sorption process,
Arrhenius law. Usually, over small temperature ranges, wherefore is a function of water content. Enthalpy change
the temperature dependence of permeability also can be of film sorption process as a function of water content is
represented by an Arrhenius type equation (Arvanitoyan- shown in Fig. 2. As water vapor is brought in contact with
nis, Nakayama, & Aiba, 1998; Chinnan & Park, 1995; the film surface, where active sites of different energy are
Donhowe & Fennema, 1994; McHugh & Krochta, 1994; present, the most active sites are those first sorbed by water
Morillon et al., 2002, 2000). molecules followed by those less active until film satura-
  tion. So a decaying function of DHs against moisture con-
DH s
S ¼ S 0 exp ð2Þ
RT
 
ED 60
D ¼ D0 exp ð3Þ
RT
 
Moisture content (g/100g d.b.)

50
EP
WVP ¼ WVP0 exp ð4Þ
RT 40

where ED and EP are the apparent activation energies for


30
diffusion and permeation phenomena (kJ mol1), respec-
tively, DHs is the enthalpy change of sorption (kJ mol1),
20
R is the gas constant (8.314 kJ mol1 K1) and T is the
25 ˚C
absolute temperature (K). From permeability definition, 10 45 ˚C
the relationship between energies is:
EP ¼ ED þ DH s ð5Þ 0
0.0 0.2 0.4 0.6 0.8 1.0
Usually, an increase in temperature causes a slight Water activity
decrease in the solubility and an increase in the diffusion
Fig. 1. Experimental data and isotherms curves predicted by BET
of water vapor through edible films. The increase in diffu-
equation for moisture sorption of high amylose corn starch based films.
sivity with increasing temperature is due to the enhanced
motion of polymer segments and to increased energy levels
of the permeating molecules. As a result, permeability 47
increases with increasing temperature.
Temperature and relative humidity effects on water
vapor solubility in the polymer can be deduced from water
46
sorption isotherm. On other hand, influence of temperature
-ΔH (KJ/mol)

and water content on diffusivity is much more difficult to be


established. Experimental data of moisture sorption at 25
and 45 C for high amylose corn starch films as a function 45
of water activity are shown in Fig. 1. Isotherms at 5 and
35 C are not shown for sake of clarity. Sorption data at
all temperature were adequately fitted by BET equation 44 λ at 25 ˚C
(r2 > 0.99). Sorption curves are typical of water vapor sen-
sitive polymers, and sorption levels are within the range
reported for autoclaved high amylose corn starch (Bader 0 10 20 30 40
& Göritz, 1994), cellulose films and protein based films Moisture content (g/100g d.b.)
(Chinnan & Park, 1995; Cuq, Gontard, Cuq, & Guilbert, Fig. 2. Enthalpy change of water sorption for high amylose corn starch
1997; Gennadios et al., 1994a; Velázquez, Torres, & Mar- based films and latent heat of water condensation at 25 C.
M.A. Bertuzzi et al. / Journal of Food Engineering 80 (2007) 972–978 975

tent is observed. There is a continuous decrease of the affin- Bustillos, & Krochta, 1993; Park & Chinnan, 1995) of non
ity between film sorbed structure with water molecules as ideal behavior. In this study it was observed that WVP of
moisture content increase. Heat of sorption data obtained high amylose corn starch films increased linearly with film
from Clausius–Clapeyron equation, have been reported in thickness over the range of thickness studied (Fig. 4). The
the literature for several foods and food components (Al- linear fittings of the experimental values display a regres-
Muhtaseb et al., 2002; Mulet et al., 1999; Viollaz & Rov- sion coefficient (R2) of 0.98. This positive deviation from
edo, 1999). However no data were reported for edible films. the ideal behavior indicates that starch films have an affin-
In this work, film WVP were measured at different tem- ity for moisture that is not taken into account in Fick’s and
peratures in a range of 5–40 C. Temperature dependence Henry’s laws as can be seen in Fig. 1 (non linear isotherms).
of WVP of films is shown in Fig. 3. Results were fitted with Previous studies have indicated similar relationships in
an Arrhenius type expression (Eq. (4)). Activation energy hydrophilic film systems: amylose films (Rankin, Wolff,
for permeation process was determined from the slope of Davis, & Rist, 1958), cellulose derivatives films (Hagenma-
ln (WVP) versus 1/T (R2 = 0.92). The activation energy ier & Shaw, 1990); protein and other edible films (Genna-
of high amylose starch films was 5.611 kJ/mol. Activation dios et al., 1994a; Longares, Monahan, O’Sullivan, &
energy values of water vapor permeation in cellophane O’Riordan, 2004; McHugh et al., 1993; Park & Chinnan,
reported by Rogers, Fels, and Li (1982) was 1.67 kJ/mol. 1995; Park, Weller, Vergano, & Testin, 1993; Sobral,
Chinnan and Park (1995) observed activation energies of 2000). Several explanations for thickness effects on edible
hydroxypropyl cellulose and methyl cellulose were 14.56 films have been reported. McHugh et al. (1993) observed
and 16.43 kJ/mol, respectively. Due the hydrophilic nature that, as film thickness increased, the film provided an
of these materials, the energy barrier of water vapor perme- increased resistance to mass transfer across it; conse-
ation phenomenon is lower than energy barrier of hydro- quently, the equilibrium water vapor partial pressure at
phobic films. Packaging synthetic films such as inner film surface increased. Other authors attributed
polyvinylidene chloride (61.9 kJ/mol), polypropylene thickness effect to film swelling as a result of attractive
(42.2–65.3 kJ/mol), polyethylene (33.4–61.7 kJ/mol) (Rog- forces between polymer and water (Park et al., 1993). Film
ers et al., 1982) present higher activation energies. Kester swelling could result in varying film structures.
and Fennema (1989) observed a rather large activation From Eq. (1) and experimental data it becomes quite
energy values (59.4 kJ/mol) for waxed laminated cellulose clear that water vapor flux through the film (G/A)
films. Gennadios, Weller, and Testin (1993) reported pro- (g s1 m2) remains independent of film thickness, which
tein films activation energies ranging from 46 to 50 kJ/mol. would imply that flux in this type of edible films does not
According to the obtained results, in the light of Eq. (5), depend on x in the range of film thickness studied (40–
diffusion is the preponderant mechanism of the moisture 150 lm). Due to the strong hygroscopic nature of starch
transfer. ED and EP are both positives, i.e., diffusion and films and the influence of glycerol it could be possible that
permeation increase with increasing temperature. during permeation process the film matrix, exposed to the
high relative humidity side, sorbed enough water that
3.2. Effect of thickness desorption rate becomes independent of thickness resis-
tance. As a whole the film behaves as only a thin portion
In ideal polymeric structures gas and vapor permeabili- of it, at the low relative humidity side, which is responsible
ties are independent of film thickness (Schwartzberg, 1986). of the mass transfer resistance. Under these conditions the
However, there is experimental evidence (McHugh, Avena-

-21. 75
10.0

7.5
gs-1 m-1 Pa-1)

-22. 00
ln WVP

WVP

5.0
-10

-22. 25
(10

2.5

-22. 50 0.0
3. 2 3. 3 3. 4 3. 5 3. 6 0.00 0.05 0.10 0.15 0.20
-1
1000/T (K ) Film thickness (mm)

Fig. 3. Temperature dependence of water vapor permeability of high Fig. 4. Effect of film thickness on water vapor permeability for high
amylose starch film. amylose corn starch based films.
976 M.A. Bertuzzi et al. / Journal of Food Engineering 80 (2007) 972–978

flux can become thickness independent and permeability Autio, Myllärinen, & Poutanen, 1996). The addition of a
will increase linearly with x. plasticizing agent to edible films is required to overcome
Fig. 5 shows the thickness resulting values as function of film brittleness caused by extensive intermolecular forces.
film-forming gel amount poured in Petri dishes. Films were Plasticizers reduce these forces, thereby improving flexibil-
conditioned at different relative humidity (varying between ity and extensibility of the films (Forssell et al., 2002; Gon-
11% and 100%) during 72 h before measuring film thick- tard et al., 1993; Koskinen et al., 1996). Since plasticizers
ness. It can be clearly seen that mean film thickness extend, dilute and soften the structure effectively, the chain
increases linearly with the amount of gel poured mobility is increased and diffusion coefficients for gas or
(R2 > 0.97). This confirms that the retraction rate during water markedly increase (Guilbert, 1986).
drying is constant and homogeneous whatever the initial Jangchud and Chinnan (1999) found glycerol was the
poured amount of film-forming gel. best plasticizer for water soluble polymers among several
However the observed variation of film thickness with studied in their work. Based on this finding, glycerol was
relative humidity is congruent with sorption data shown used as plastificant. The WVP of high amylose corn starch
in Fig. 1. Below 60% RH, thickness values are independent films as a function of glycerol content is presented in Fig. 6.
of relative humidity conditioning. A single line could As can be seen, WVP increased linearly as the concentra-
approximate all experimental data. In Fig. 1 curves pre- tion of glycerol increased in the range of glycerol content
sented a relative slight slope at low values of aw, but take studied (R2 = 0.90) . These results could be related to struc-
an exponential course at high relative humidities (above tural modifications of the starch network produced by the
0.60). When aw > 0.60 film thickness shows significative plasticizer and to the hydrophilic character of glycerol,
increase dependence with relative humidity and with the which favors the absorption and desorption of water mol-
original film thickness. Thus under these conditions high ecules. Plasticizer causes a greater flexibility in polymeric
amylose corn starch film, full of almost liquid water, offers structure, which increases water sorbed mobility within
a great water molecule mobility resulting in a dramatic the structure. As a result WVP increases with plasticizer
increase in the rate of diffusion. Since ASTM E-96 method film content.
implies the presence of high relative humidity conditions in This behavior is common with hydrophilic edible films
one side of the film, the observed behavior of Fig. 5 could and was reported by several authors (Cuq et al., 1997; Gen-
explain the anomalous dependence of WVP with film thick- nadios et al., 1994a; Nazan Turhan & Sahbaz, 2004;
ness presented in Fig. 4. Sothornvit & Krochta, 2001). Park and Chinnan (1995)
observed similar trends on cellulose films in the range of
3.3. Effect of plasticizer plasticizer composition used in our study. Ryu et al.
(2002) reported high amylose corn starch films, without
Amylose is responsible for the film-forming capacity of plasticizer, WVP as large as 117 · 1010 g m1 s1 Pa1,
starch based films. In the absence of plasticizers, films made increasing up to 147 · 1010 g m1 s1 Pa1 when glycerol
from starch or amylose are brittle (Koskinen, Suortti, concentration was increased to 100 g/100 g of starch. Their
reported values are one order of magnitude larger than
0.28
those observed in this contribution. Such deviation can
only be explained by procedure differences on preparing
films.

0.23

10
Thickness (mm)

0.18
8
gm-1 s -1 Pa-1)

6
WVP

0.13

100% RH
-10

4
(10

75% RH
0.08 52% RH
2
11% RH

0
0.03
0 10 20 30 40 50 60 70
5 10 15 20
Gel (mL) Glycerol content (g/100 g starch)

Fig. 5. Film thickness as a function of volume of gel poured onto Petri Fig. 6. Effect of glycerol content on water vapor permeability for high
dishes conditioned at different relative humidity (RH). amylose corn starch based films.
M.A. Bertuzzi et al. / Journal of Food Engineering 80 (2007) 972–978 977

4. Conclusions Arvanitoyannis, I., & Biliaderis, C. G. (1998). Physical properties of


polyol-plasticized edible films made from sodium caseinate and soluble
starch blends. Food Chemistry, 62(3), 333–342.
HACS based film characterization requires the knowl- Arvanitoyannis, I., & Biliaderis, C. G. (1999). Physical properties of
edge of barrier properties as well as their dependence with polyol-plasticized edible blends made of methylcellulose and soluble
temperature, relative humidity gradients, film thickness starch. Carbohydrate Polymers, 38, 47–58.
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perature seriously affects both equilibrium (solubility) and from hydroxypropyl starch and gelatin and plasticized by polyols and
water. Carbohydrate Polymers, 36, 105–109.
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Water vapor sorption experimental data shows an exo- Society for Testing and Materials, Philadelphia.
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Chang, Y. P., Cheah, P. B., & Seow, C. C. (2000). Plasticizing–
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