ARTICLE IN PRESS

FOOD
HYDROCOLLOIDS
Food Hydrocolloids 23 (2009) 125–131
www.elsevier.com/locate/foodhyd

Stability of the mechanical properties of edible films based on whey

protein isolate during storage at different relative humidity
Javier Osés, Idoya Fernández-Pan, Mauricio Mendoza, Juan I. Maté
Department of Food Technology, Public University of Navarra, Campus Arrosadı´a S/N, 31006 Pamplona, Spain
Received 17 April 2007; accepted 10 December 2007

Abstract

Formulations for whey protein isolate (WPI)-based films include low molecular weight plasticizers, which implies certain degree of
instability of films properties due to plasticizer migration. The aim of this work was to study the effect of storage time on the mechanical
properties of WPI films plasticized with two low molecular weight polyols: glycerol (Gly) and sorbitol (Sor). Films were stored inside
cabins at 50% or 75% relative humidity (RH) and at room temperature. Mechanical properties and moisture content were measured
at regular intervals for 30 weeks. The effect of plasticizer type and content and RH on mechanical properties right after equilibrium
(1 week) was also included in this study.
After equilibrium, Gly was found to be a more efficient plasticizer than Sor. Films plasticized with Gly were found to be more flexible
and weaker and to have higher moisture content than films with the same amount of Sor. There was a saturation value for plasticizer
content (40% for Gly and 50% for Sor), above which the film became weaker, but not more flexible.
Storage time did not affect either the appearance or the mechanical properties of films plasticized with Gly. However, films plasticized
with Sor became harder and less flexible with time likely due to Sor crystallization.
r 2008 Elsevier Ltd. All rights reserved.

Keywords: Whey protein isolate; Edible film; Mechanical properties; Storage time; Plasticizer

1. Introduction the migration of low molecular weight components, such as

Properties of edible films and coatings generally vary at
same degree with storage time, especially if compared with
those of synthetic films, due to the intrinsic instability of
their raw materials. These variations could affect their
functionality on foods, and, therefore, a high degree of
stability of film properties for a long time is generally
desired.
When films or coatings are exposed during storage
time to certain environmental conditions, it is possible to
observe both physical and chemical changes in their nature.
Chemical changes, such as oxidation of the protein
sulfhydryl groups could cause degradation of the polymeric
chains (Micard, Belamri, Morel, & Guilbert, 2000).
Physical changes include polymer recrystallization (as the
retrogradation produced in starch films) and those due to
Corresponding author. Tel.: +34 948 16 90 92; fax: +34 948 16 98 93.
E-mail address: juan.mate@unavarra.es (J.I. Maté).
plasticizers, used in film formulation (Anker, Stading, &
Hermansson, 2001). This migration of additives can be
considered the most important cause of physical instability
of edible films.
In order to diminish film fragility and increase film
flexibility and manageability, plasticizers are added into
film formulation (Guilbert, 1986). Glycerol (Gly) and
sorbitol (Sor) are the most commonly used plasticizers in
edible films. Water also acts as a plasticizer in hydrophilic
films (Arvanitoyannis & Biliaderis, 1998). Water content is
affected by plasticizer content and relative humidity (RH).
The plasticizing effect of Sor, Gly or water is based on
the weakening of hydrogen bonds and the dipole–dipole
intra and intermolecular interactions due to shielding of
these attractive forces by the plasticizer molecules. As a
consequence, free volume increases and glass transition
temperature decreases (Ashley, 1985; Lieberman, & Guil-
bert, 1973; Matveev, Grinberg, & Tolstoguzov, 2000),
which affects significantly their mechanical properties.

0268-005X/$ - see front matter r 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodhyd.2007.12.003
 ARTICLE IN PRESS
126 J. Osés et al. / Food Hydrocolloids 23 (2009) 125–131
Previous studies on additive migration have shown that,
under certain storage conditions, plasticizers are highly
susceptible of migration from the polymeric matrix to the
surface (Startin et al., 1987). Park, Bunn, Weller, Vergano,
and Testin (1994) reported that films based on wheat gluten
and maize zein plasticized with Gly and polyethylenglycol
increased their fragility during the first 20 days of storage.
The authors concluded that despite that the plasticizers
were well dispersed within the polymeric matrix, they
would migrate from the matrix to the surface, due to the
limited bonds existing between protein molecules and Gly.
The rate of migration depended on the type of functional
groups, polarity and structure of the film matrix. Similar
results were reported by Park, Weller, Vergano, and Testin
(1992), who stated that the loss of flexibility in maize zein
films was an indicative of Gly migration. Moreover, they
observed that the film surface presented a sticky appear-
ance in a few hours, which was apparently due to
plasticizer migration.
Similarly, Viroben, Barbot, Mouloungui, and Guéguen
(2000) studied the aging of gluten films plasticized with 1,2
or 1,3-propanediol, and related a tensile strength (TS)
increase in accordance with the diffusivity of the plasticizers
towards film surface. Gueguen, Viroben, Barbot, and
Subirade (1998) reported similar results for the same type
of films. The effect of storage time on the functional
properties of glutenin films plasticized with Gly, Sor and
triethanolamine was studied by Hernández, Rubio, Del
Valle, Almenar, and Gavara (2004). They concluded that
both water vapour permeability and mechanical properties
of films plasticized with Gly changed drastically with
time due to Gly migration, while the properties of films
plasticized with Sor or triethanolamine remained stable
during storage time. Somanathan, Narres, Arumugan,
Ranga-Nathan, and Sanjeevi (1992) have also used trietha-
nolamine to plasticizer casein films. Contrary to the results
reported by Hernández et al. (2004) for glutenin films, they
observed that the films changed their colour and became less
flexible after 1 year of storage at 25 1C and 65% RH.
On the other hand, other authors have proved that
functional properties of many types of films with plastici-
zers remain stable during storage. Butler, Vergano, Testin,
Bunn, and Wiles (1996) did not find any significant
differences in the mechanical properties of chitosan films
plasticized with Gly after 9 weeks of storage at 23 1C and
50% RH. Caner, Vergano, and Wiles (1998) did not find
any significant differences in the TS of chitosan films
plasticized with polyethylenglycol after a 12-weeks storage
period at 23 1C and 50% RH. Cuq, Gontard, Cuq, and
Guilbert (1996) observed that water vapour permeability
and the mechanical properties of films based on myofibril
protein plasticized with saccharose remained constant for 8
weeks at 20 1C and 58.7% RH. However, those films
turned yellowish and discoloured due to non-enzymatic
browning.
Much attention has been lately paid to whey protein
isolate (WPI) films because they are transparent with
excellent barrier properties to oxygen, flavours and lipids
(Maté & Krochta, 1996; McHugh & Krochta, 1994; Miller
& Krochta, 1997). In order to be functional, WPI films
need the addition of plasticizers, which could migrate
during storage and as a consequence films properties could
be affected. However, works related to the stability of
functional properties of WPI-based films during storage
are limited. Anker, Stading, and Hermansson (2001)
observed changes in the mechanical properties and
moisture content of WPI-based films plasticized with Gly
during their storage at 50% RH. These changes resulted in
stiffer and less flexible films due to Gly migration to the
film surface. Nevertheless, properties of WPI-based films
with Sor remained stable.
Preliminary experiments conducted in our research lab
showed that mechanical properties of WPI-based films
plasticized with Gly were apparently much more stable
than those plasticized with Sor. Therefore, our working
hypothesis addressed by this work was whether the
mechanical properties of WPI-based films plasticized with
Gly or Sor were stable with time. In order to answer this
question, mechanical properties of films were measured
during a 6-month storage period at room temperature and
under controlled RH. In addition, the effect of type and
plasticizer content and RH on mechanical properties right
after equilibrium (1 week) was also analysed to have a
better insight of the problem.
2. Materials and methods
2.1. Materials
Davisco Foods International (Le Sueur, MN, EEUU)
provided WPI. Panreac Quı́mica S.A. (Barcelona, Spain)
supplied Gly and Sor. Magnesium nitrate and sodium
chloride used to control RH were also obtained from
Panreac Quı́mica S.A.
2.2. Film formation
The method developed by McHugh, Aujard, and
Krochta (1994) to obtain WPI edible films has been
followed. WPI aqueous solutions at 10% (w/w) were
prepared. Then Gly or Sor were added as plasticizers with
relative weights of 30%, 40%, 50% or 60% with regard to
the film total dry weight. The resultant solution was heated
at 90 1C during 30 min in a water bath. After that, the
solutions were cooled until they reached room temperature
and then degassed by means of a vacuum pump to
eliminate non-condensable gases that could affect final
film properties. The solution was poured over polyethylene
Petri dishes (14.7 cm in diameter) and it was spread all over
the dish stirring it slightly with a glass rod. In order to
obtain films of homogeneous thickness, these dishes were
placed on levelled surfaces. The quantity of solution added
onto each dish, regardless of film formulation, was 14 g.
The solutions were left to dry during approximately 18 h at
 ARTICLE IN PRESS
J. Osés et al. / Food Hydrocolloids 23 (2009) 125–131 127

room temperature and room RH. The films were then
completely detached from the surface.
2.3. Storage conditions
Once the films had been formed, they were cut in
rectangular strips of 25.4 mm in width and 75 mm length
and were stored inside cabins at 5075% or 7575% RH
and at room temperature during a week. The RH was kept
constant by means of saturated solutions of magnesium
nitrate (50%) and sodium chloride (75%) at the bottom of
the cabins. Preliminary experiments had shown that films
reached equilibrium with respect to moisture content
within a week of storage. Thus, after a week, mechanical
properties and moisture content of all films were deter-
mined. Films containing 50% Gly or 50% Sor were stored
during 6 months under the same conditions in order to
study the evolution of moisture content and mechanical
properties during storage. Samples were analysed at 5, 15
and 30 weeks of storage.
2.4. Films thickness measurement
Films thickness was determined using a micrometer
(Mitutoyo Corp., Code No. 543-551-1, Model ID-F125,
Japan) to the nearest 0.001 mm at 10 random positions
around the film, and average values were used in
calculations.
2.5. Moisture content
Moisture content was determined through the weight
loss undergone by the film after a 24 h stove drying at
70 1C. Preliminary experiments showed us that 24 h were
enough to fully dry up the samples. Ten repetitions were
made for each film type.
2.6. Mechanical properties
A texture analyser TA.XTZi (Surrey, United Kingdom)
was used to measure the tensile properties of the films
according to ASTM D882-00 (ASTM, 2000). Sample films
3. Results and discussion
3.1. Film appearance
All resulting films were transparent, flexible and homo-
geneous. Their surfaces were smooth without pores and
cracks. They had a thickness of about 130710 mm. The
films could be easily separated from the casting plates,
except for those with 60% plasticizer content, which
resulted very sticky. On the other hand, films with 30%
plasticizer content, especially those of Sor, were brittle and
broke easily. Films with a plasticizer content of 70% and of
20% were obtained but not analysed due to difficulty in
their handling owing to high adhesiveness in one case, and
excessive brittleness in the other.
3.2. Moisture content after equilibrium
As expected, films plasticized with both Gly or Sor
presented higher moisture content at 75% RH than at 50%
RH regardless of plasticizer content (Fig. 1). For equal
plasticizer content, films with Gly in their formulation
presented significantly higher moisture content as com-
pared with films containing Sor (Fig. 1). This fact is
probably due to the greater hygroscopic character of Gly,
which has a higher affinity for binding water than Sor
at equivalent RH and temperature (Shaw, Monahan,
O’riordan, & O’sullivan, 2002).
The higher the Gly content, the higher the moisture
content for both studied RH (Fig. 1). For example, at 50%
RH it can be observed an increase of humidity from 13.1%
for films with 30% Gly to 17.2% for films with 60% Gly.
The influence of Sor content on humidity was not as
important as that of Gly (Fig. 1). Thus, Sor content did not
affect significantly moisture content at 50% RH. For 75%
RH there was a significant but not important increase of
moisture content (from 12% for films with 30% Sor to
13.1% for films with 60% Sor). Similar results were found
by Shaw et al. (2002) who studied the variation of moisture
content in WPI films plasticized with different quantities of
35 50% RH Glycerol 75% RH g
30
Sorbitol
f
Moisture Content (%)

were cut into strips 25.4 mm wide and 75 mm long. Initial e

25
grip separation was set at 50 mm and crosshead speed at d
C
0.8 mm s 1. Force and distance were recorded during 20
b
c
B B BC
a a
extension of the strips and TS, percentage of elongation 15
A A A A
at break (EB) and elastic modulus (EM) were calculated as 10
outlined in ASTM D882-00 (ASTM, 2000). At least 10
5
samples of each film type were analysed.
0
30% 40% 50% 60% 30% 40% 50% 60%
2.7. Statistical analyses % Plasticizer

Fig. 1. Comparison of moisture content of WPI films plasticized with

SPSS version 12.0 was used for all statistical analyses. different contents of Gly or Sor after their equilibrium at 50% and 75%
Analyses of variance and Duncan’s means comparison test RH. For each type of plasticizer, values followed by different letters (a–g)
with a significance level of 0.05 were applied. and (A–C) present significant differences (Po0.05).
 ARTICLE IN PRESS
128 J. Osés et al. / Food Hydrocolloids 23 (2009) 125–131

Sor. They observed that when Sor content was increased The more plasticizing effect obtained with Gly could be
from 33% to 50%, no significant changes in moisture due to its higher hygroscopicity, which implies higher
content were produced. On the other hand, Mahmoud and moisture content (Fig. 1), and water is also an excellent
Savello (1992) observed that as the concentration of Gly in plasticizer. Our results were consistent with those observed
films of b-lactoglobulin increased so did its moisture content. by Shaw et al. (2002) who attributed the different effect of
plasticizers on WPI films to their different hygroscopicity.
The plasticizing effect of Gly and Sor could also be
3.3. Mechanical properties after equilibrium explained in terms of molecular weight. As Gly has lower
molecular weight than Sor, for the same plasticizer content,
Results of mechanical properties of the studied films the number of moles of Gly will be higher, and
after reaching moisture equilibrium (1 week of storage) are consequently their effect on the decrease of the number
shown in Table 1. It can be observed that, for the same of interactions between the protein polymeric chains will be
plasticizer content and RH, films with Gly showed more intense. This rationale had already been described by
significantly lower TS and EM and a higher EB compared Cuq et al. (1997) and Thomazine, Carvalho, and Sobral
with films with Sor. That is, Gly acted as a more effective (2005) for myofibril films of fish protein and gelatine films,
plasticizer, resulting in weaker and more flexible films. For respectively.
example, TS and EB values were of about 3.3 MPa and Some other authors have established a relationship
98% for films with 40% of Gly equilibrated at 50%, between the plasticizer effectiveness and the number of
whereas films with 40% Sor were of about 10 MPa and hydroxyl groups or oxygen atoms in its chemical structure
11%, respectively. (Siew, Heilmann, Easteal, & Cooney, 1999). Thus, Park,
Similar results were found for films based on WPI Weller, Vergano, and Testin (1993) concluded that the
(McHugh & Krochta, 1994; Shaw et al., 2002), number of hydroxyl groups contained in the plasticizer
b-lactoglobulin (Sothornvit & Krochta, 2001), egg albumin influenced the mechanical properties of cellulose films.
(Gennadios, Weller, Hanna, & Froning, 1996), fish protein From that point of view, since Sor has three more hydroxyl
myofibrils (Cuq, Gontard, Cuq, & Guilbert, 1997), casein groups than Gly, one would expect a higher plasticizing
(Chick & Ustunol, 1998), starch and gelatine mixtures effect on WPI film. However, Sothornvit and Krochta
(Arvanitoyannis, Psomiadou, Nakayama, Aiba, & Yama- (2001) proved that for b-lactoglobulin films plasticized with
moto, 1997), and sodium caseinate and starch mixtures Sor or Gly, the most influential factor in the film
(Arvanitoyannis & Biliaderis, 1998). plasticizing is the plasticizer molecular weight rather than
its number of hydroxyl groups.
An increase in plasticizer content resulted in weaker and
Table 1 more flexible films. This was reflected in a decrease in TS
Mechanical properties of WPI-based edible films after equilibrium at
and EM for films with either Gly or Sor. It was expected
different RHa
that an increase in the plasticizer content would increase
Plasticizer Plasticizer Tensile Elongation Elastic film elongation. However, this elongation increase only
type content strength at break (%) modulus took place up to a plasticizer content of 40% in the case of
(%) (MPa) (MPa)
films with Gly, and up to a plasticizer content of 50% in
50% RH the case of films with Sor (Table 1). Above these values, the
Glycerol 30 6.970.4 a 76.779.6 b 140.7710.6 a increase in plasticizer content did not result in an
40 3.370.1 b 98.2715.3 a 50.573.0 b elongation increase. This fact is likely due to film matrix
50 2.470.1 c 104.878.2 a 28.175.1 c saturation with plasticizers (including water). It is likely
60 0.970.1 d 103.877.6 a 6.270.6 d
that the mesoscopic structure of denaturated whey proteins
Sorbitol 30 12.171.3 A 4.470.5 C 421.3731.8 A (mainly b-lactoglobulin and a-lactalbumin) limited WPI
40 10.070.6 B 11.574.3 BC 207.4711.8 B film elongation up to a maximum of about 100%.
50 4.270.2 C 28.377.5 A 73.376.5 C
60 2.070.1 D 14.873.2 B 27.271.8 D
These results are consistent with Sothornvit and Krochta
(2001) who showed that an increase in Sor content in
75% RH b-lactoglobulin films had a more important impact on TS
Glycerol 30 4.670.5 a 107.978.3 b 58.275.4 a
40 2.370.1 b 118.576.5 a 19.772.7 b
and EM than on EB.
50 1.470.1 c 98.076.4 b 9.271.2 c In addition, the exposure of the films to a higher RH made
60 0.670.1 d 78.4715.6 c 2.070.2 d them less stiff due to the water’s plasticizing effect. As
Sorbitol 30 7.970.5 A 28.175.6 C 163.279.4 A
expected, water content was higher in films balanced at 75%
40 4.470.6 B 42.376.2 B 68.276.5 B RH with respect to those balanced at 50% RH (Fig. 1).
50 1.870.2 C 64.273.5 A 26.171.5 C
60 0.770.1 D 58.674.1 A 10.671.3 D 3.4. Evolution of film appearance
a
Two means followed by the same letter in the same column (different
analysis for different type of plasticizer and RH) are not significantly Films containing 50% Gly as plasticizer did not vary the
(P40.05) different through Duncan’s test. appearance after 30 weeks of storage either at 50% or 75%
 ARTICLE IN PRESS
J. Osés et al. / Food Hydrocolloids 23 (2009) 125–131 129

RH. On the other hand, films with 50% Sor turned the other hand, TS of Sor films stored at 75% RH
partially dull, whitish and more brittle as the storage time increased significantly from 1.7 MPa after 1 week to
lengthened. This was particularly intense in the case of 4.2 MPa after 30 weeks. In addition, EB of these films
storage at 50% RH. The brittleness of the films with Sor decreased from 64% after 1 week to 46% after 30 weeks.
became so high after 5 weeks at 50% RH that it was not
possible to analyse the mechanical properties. This
phenomenon could be due to Sor migration and its 5
subsequent crystallization on the surface of the WPI films. 30 w
That crystallization could be observed visually since white 4
15 w

Tension (MPa)
spots were becoming visible on the surface of the films, 5w
3 1w
which meant an undesirable appearance. Sakanaka, 50% RH
Sobral, and Menegalli (2001) also observed crystallization 2
of Sor films based on gelatine stored at 50% RH after 75% RH
30 days. 1 1 w 15 w
5 w 30 w
3.5. Evolution of moisture content 0
0 25 50 75 100 125 150
Elongation (%)
The effect of aging on moisture content is shown in
Table 2. Aging did not affect significantly moisture content Fig. 2. Graphic representation of the tensile tests of WPI films with 50%
of films regardless of plasticizer type or environmental RH. Gly stored at 50% or 75% RH during 1, 5, 15 or 30 weeks.

3.6. Evolution of mechanical properties

5
The effect of storage time on mechanical properties is 30 w
4
shown in Figs. 2 and 3. It can be observed that the 15 w
Tension (MPa)

mechanical properties of Gly-plasticized films remained

3
basically constant during the 30 weeks at both 50% and 5w
75% RH. On the contrary, Sor films become harder and 2 1w
less flexible as the storage time lengthens at 75% RH
(as stated, it was not possible to study the evolution of Sor 1
films at 50% RH). These effects can be appreciated more
clearly in Table 2 where the results of the tensile tests are 0
quantified. 0 25 50 75 100 125 150
TS and EB values were of about 2.4 MPa and 105% and Elongation (%)
of about 1.5 MPa and 96% for Gly films stored at 50% and Fig. 3. Graphic representation of the tensile tests of WPI films with 50%
75% RH, respectively, during the whole study (Fig. 2). On Sor stored at 75% RH during 1, 5, 15 or 30 weeks.

Table 2
Humidity content and mechanical properties of WPI-based films with 50% Gly or Sor as affected by storage time and RHa

Plasticizer type Time (Days) Humidity content (%) Tensile strength (MPa) Elongation at break (%) Elastic modulus (MPa)

50% RH
Glycerol 7 14.770.7 a 2.470.1 a 104.878.2 a 28.175.1 a
30 14.970.6 a 2.370.1 a 105.6710.5 a 26.973.6 a
90 14.270.7 a 2.370.1 a 102.877.4 a 26.374.6 a
180 14.370.6 a 2.470.2 a 106.077.1 a 30.470.9 a

75% RH
Glycerol 7 27.170.8 a 1.470.1 a 98.076.4 a 9.271.3 a
30 27.870.5 a 1.570.1 a 97.174.0 a 9.071.4 a
90 27.670.4 a 1.570.1 a 94.775.3 a 9.470.8 a
180 27.370.7 a 1.670.2 a 95.674.8 a 9.771.3 a

Sorbitol 7 16.270.6 A 1.870.2 A 64.276.5 A 26.171.5 A

30 16.070.5 A 2.470.1 B 55.478.9 B 34.273.6 B
90 16.470.4 A 3.470.2 C 52.478.6 C 53.975.3 C
180 16.570.6 A 4.270.2 D 46.678.7 D 67.276.8 D
a
Two means followed by the same letter in the same column (different analysis for different type of plasticizer and RH) are not significantly (P40.05)
different through the Duncan test.
 ARTICLE IN PRESS
130 J. Osés et al. / Food Hydrocolloids 23 (2009) 125–131
EM evolution showed behaviour similar to TS evolution
for all film types studied.
The evolution of the mechanical properties (becoming
stronger and less flexible) of films plasticized with Sor
stored at 75% RH was likely due to Sor crystallization.
This crystallization decreased the amount of plasticizing
Sor and allowed increased molecular interactions in the
protein network and thus changes in the mechanical
properties of the films. This phenomenon was more intense
in films stored at 50% RH due to the lower availability of
water to dissolve Sor, and as a consequence the crystal-
lization rate was higher.
Krogars et al. (2003) described the crystallization of Sor
on the surface of films based on amylose-rich maize starch.
They observed this crystallization for films with Sor
content of 50% and 100% with respect to polymer content.
Talja, Helén, Roos, and Jouppila (2007) explained the
effect of various polyols types and contents on the
mechanical properties of potato starch-based films at
different RH after 1 week. They could observe Sor
crystallization at a content of 60% and at an RH of 33%
and 54%, but not at 76% RH. These results confirm our
own observations.
Gly as water is liquid at room temperature. Once Gly
content reaches a certain level, it saturates the film matrix
and is exudated during drying, which implies a sticky film
surface. This saturation level depends on the presence of
other plasticizer such as water. This exudation has been
described in the past (Anker et al., 2001; Krogars et al.,
2003; Talja et al., 2007) and it was observed in the present
research above certain Gly content (60% for WPI films).
In addition, due to its high mobility, Gly can migrate out
of the film matrix into a high porous material in contact
with the film surface due to molecular diffusion. This could
be the case of the results described by Anker et al. (2001)
who stored WPI-based films with Gly in paper envelopes,
and observed that the films became more fragile with time.
If the saturation level is not reached and if the films are
not in contact with a porous material, properties of films
plasticized with Gly are quite stable. This was our case as
well as other research such as the one reported by Butler
et al. (1996) who did not find any significant differences in
the mechanical properties of chitosan films plasticized with
Gly during 12-weeks storage at 23 1C and 50% RH.
4. Conclusions
After equilibrium, Gly was found to be a much better
plasticizer than Sor, since for the same content, films with
Gly were much more flexible and less brittle. Lower
molecular weight and higher hydrophilicity could be the
reason of such behaviour. There was a saturation value for
plasticizer content, above which films became weaker, but
not more flexible.
Our study clearly showed that Gly is a much more stable
plasticizer for WPI-based films than Sor at both studied
RH. We found that aging affected mechanical properties of
the films plasticized with Sor due to Sor crystallization on
the surface of films, making films harder and less flexible.
Mechanical properties and appearance of films plasticized
with Gly did not vary with time.
Selection of an appropriate plasticizer has to be done in
terms of conferring enough flexibility to the film and
keeping its functional properties stable for a desirable
period of time. This selection has to take into account
potential plasticizer crystallization, migration from the
surface to the food as well as saturation of the polymer
matrix.
References
Anker, M., Stading, M., & Hermansson, A. M. (2001). Aging of whey
protein properties films and the effect on mechanical and barriers
properties. Journal of Agricultural and Food Chemistry, 49, 989–995.
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.
Arvanitoyannis, I., Psomiadou, E., Nakayama, A., Aiba, S., &
Yamamoto, N. (1997). Edible films made from gelatine, soluble starch
and polyols, part 3. Food Chemistry, 60(4), 593–604.
Ashley, R. J. (1985). Permeability and plastic packaging. In J. Comyn
(Ed.), Polymer permeability (pp. 269–308). London: Elsevier Applied
Science Publishers.
ASTM (2000). Standard test method for tensile properties of thin plastic
sheeting. Designation: D882-00. In: Annual book of ASTM standards
(pp. 160–168). Philadelphia, PA: ASTM.
Butler, B. L., Vergano, P. J., Testin, R. F., Bunn, J. M., & Wiles, J. L.
(1996). Mechanical and barrier properties of edible chitosan films as
affected by composition and storage. Journal of Food Science, 61(5),
953–955.
Caner, C., Vergano, P. J., & Wiles, J. L. (1998). Chitosan film mechanical
and permeation properties as affected by acid, plasticizer, and storage.
Journal of Food Science, 63(6), 1049–1053.
Chick, J., & Ustunol, Z. (1998). Mechanical and barrier properties of
lactic acid and rennet precipitated casein-based edible films. Journal of
Food Science, 63(6), 1024–1027.
Cuq, B., Gontard, N., Cuq, J. L., & Guilbert, S. (1996). Stability of
myofibrillar protein-based biopackagings during storage. Lebensmittel-
Wissenschaft und-Technologie, 29, 344–348.
Cuq, B., Gontard, N., Cuq, J. L., & Guilbert, S. (1997). Selected
functional properties of fish myofibrillar protein-based films as affected
by hydrophilic plasticizers. Journal of Agricultural and Food Chemistry,
45(3), 622–626.
Gennadios, A., Weller, C. L., Hanna, M. A., & Froning, G. W. (1996).
Mechanical and barrier properties of egg albumen films. Cereal
Chemistry, 70(4), 426–429.
Gueguen, J., Viroben, J., Barbot, J., & Subirade, M. (1998). Comparative
properties of pea protein and wheat gluten films: Influence of various
plasticizers and aging. In J. Guéguen, & Y. Popineau (Eds.),
Plant proteins from European crops: food and non-food applications
(pp. 319–323). Berlin: Springer.
Guilbert, S. (1986). Technology and application of edible protective films.
In M. Mathlouthi (Ed.), Food packaging and preservation: Theory and
practice (pp. 371–394). London: Elsevier Applied Science Publishers.
Hernández, P., Rubio, A., Del Valle, V., Almenar, E., & Gavara, R.
(2004). Mechanical and water barrier properties of glutenin films
influenced by storage time. Journal of Agricultural and Food Chemistry,
52, 79–83.
Krogars, K., Heinämäki, J., Karjalainen, M., Niskanen, A., Leskelä, M.,
& Yliruusi, J. (2003). Enhanced stability of rubbery amylose-rich maize
starch films plasticized with a combination of sorbitol and glycerol.
International Journal of Pharmaceutics, 251, 205–2008.
 ARTICLE IN PRESS
J. Osés et al. / Food Hydrocolloids 23 (2009) 125–131
Lieberman, E. R., & Guilbert, S. G. (1973). Gas permeation of collagen
films as affected by cross-linkage, moisture, and plasticizer content.
Journal of Polymer Science Part C-Polymer Symposium(41), 33–43.
Mahmoud, R., & Savello, P. (1992). Mechanical properties and water
vapour transferability through whey protein films. Journal of Dairy
Science, 75(4), 942–946.
Maté, J. I., & Krochta, J. M. (1996). Comparison of oxygen and water
vapour permeabilities of whey protein isolate and beta-lactoglobulin
edible films. Journal of Agricultural and Food Chemistry, 44(10),
3001–3004.
Matveev, Y. I., Grinberg, V. Y., & Tolstoguzov, V. B. (2000). The
plasticizing effect of water on proteins, polysaccharides and their
mixtures: Glassy state of biopolymers, food and seeds. Food
Hydrocolloids, 14, 425–437.
McHugh, T. H., Aujard, J. F., & Krochta, J. M. (1994). Plasticized whey
protein edible films: Water vapour permeability properties. Journal of
Food Science, 59(2), 416–419 423.
McHugh, T. H., & Krochta, J. M. (1994). Sorbitol-versus glycerol-
plasticized whey protein edible films: Integrated oxygen permeability
and tensile property evaluation. Journal of Agricultural and Food
Chemistry, 42, 841–845.
Micard, V., Belamri, R., Morel, M. H., & Guilbert, S. (2000). Properties
of chemically and physically treated wheat gluten films. Journal of
Agricultural and Food Chemistry, 48, 2948–2953.
Miller, K. S., & Krochta, J. M. (1997). Oxygen and aroma barrier
properties of edible films: A review. Trends in Food Science &
Technology, 8(7), 228–237.
Park, H. J., Bunn, J. M., Weller, P. J., Vergano, P. J., & Testin, R. F.
(1994). Water vapour permeability and mechanical properties of grain
protein-based films as affected by mixtures of polyethylene glycol and
glycerin plasticizers. Transactions of the Asae, 37(4), 1281–1285.
Park, H. J., Weller, P. J., Vergano, P. J., & Testin, R. F. (1992). Factors
affecting barrier and mechanical properties of protein-based edible,
degradable films. Presented at 53rd Annual Meeting of the Institute of
Food Technologists, Paper 428, New Orleans, LA, June.
131
Park, H. J., Weller, P. J., Vergano, P. J., & Testin, R. F. (1993).
Permeability and mechanical properties of cellulose-based edible films.
Journal of Food Science, 58(6), 1361–1370.
Sakanaka, L. S., Sobral, P. J. A., & Menegalli, F. C. (2001). Proceeding of
a meeting on cross-linked gelation biofilms mechanical and permeability
properties as affected by storage conditions. III Congreso Ibero-
Americano de Ingenierı´a de Alimentos. Valencia, España: Press of the
Politechnique University pp. 197–202.
Shaw, N. B., Monahan, F. J., O’riordan, E. D., & O’sullivan, M. (2002).
Physical properties of wpi films plasticized with glycerol, xylitol or sor.
Journal of Food Science, 67(1), 164–167.
Siew, D. C. W., Heilmann, C., Easteal, A. J., & Cooney, R. P. (1999).
Solution and film properties of sodium caseinate/glycerol and sodium
caseinate/polyethylene glycol edible coating systems. Journal of
Agricultural and Food Chemistry, 47(8), 3432–3440.
Somanathan, N., Narres, M. D., Arumugan, V., Ranga-Nathan, T. S., &
Sanjeevi, R. (1992). Mechanical properties of alkali treated casein
films. Polymer Journal, 24(7), 603–611.
Sothornvit, R., & Krochta, J. M. (2001). Plasticizer effect on mechanical
properties of b-lactoglobulin films. Journal of Food Engineering, 50,
149–155.
Startin, J. R., Sharman, M., Rose, M. D., Parker, I., Mercer, A. J., Castle,
L., et al. (1987). Migration from plasticized films into foods. 1.
Migration of di- (2-ethylhexyl) adipate from pvc films during home-
use and microwave cooking Food Additives and Contaminants, 4,
385–398.
Talja, R., Helén, H., Roos, Y., & Jouppila, K. (2007). Effect of various
polyols and polyol contents on physical and mechanical properties of
potato starch-based films. Carbohydrate Polymers, 67, 288–295.
Thomazine, M., Carvalho, R. A., & Sobral, P. (2005). Physical properties
of gelatine films plasticized by blends of glycerol and sorbitol. Journal
of Food Science, 70(3), 172–176.
Viroben, J., Barbot, J., Mouloungui, Z., & Guéguen, J. (2000).
Preparation and characterization of film from pea protein. Journal of
Agricultural and Food Chemistry, 48, 1064–1069.