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ABSTRA
CT
ers incr
eases the flexibility and wor
kability of films based on biopoly
ABSTRACT
CT:: The addition of plasticiz
plasticizers
increases
workability
biopoly-ation of these addiow ev
er
ers cause undesir
able rresults
esults
mers.. H
Ho
ever
er,, the use of some plasticiz
plasticizers
undesirable
esults,, such as the migr
migration
mers
tiv
es out the film or cr
ystallization dur
ing shelf life
aluate the effect of
tives
crystallization
during
life.. Thus
Thus,, the aim of this study was to ev
evaluate
blends with differ
ent rratios
atios of sorbitol and gly
cer
ol, at 2 plasticiz
er concentr
ations
different
glycer
cerol,
plasticizer
concentrations
ations,, on mechanical, viscoelastic, and water vvapor
apor barr
ier pr
oper
ties of films based on gelatin. The films w
er
e pr
epar
ed with 2 g gelatin/100
barrier
proper
operties
wer
ere
prepar
epared
mL of water and with 25 or 55 g plasticiz
er/100 g gelatin. The rratio
atio
cer
ol to sorbitol, was studied as 0:100,
plasticizer/100
atio,, gly
glycer
cerol
20:80, 40:60, 60:40, 80:20, and 100:0. The incr
ease of plasticiz
er concentr
ation fr
om 25 to 55 g plasticiz
er/100 g
increase
plasticizer
concentration
from
plasticizer/100
ease of flexibility and rreduction
eduction of rresistance
esistance and water vvapor
apor barr
ier as expected. IIn
n
increase
barrier
gelatin caused an incr
e, the incr
ease in the pr
opor
tion of gly
cer
ol caused a rreduction
eduction of the puncrelation to the effect of the mixtur
glycer
cerol
mixture
increase
propor
oportion
tur
e for
ce
ength, modulus of elasticity
ease of the punctur
e defor
mation, elongation at
ture
force
ce,, tensile str
strength,
elasticity,, and an incr
increase
puncture
deformation,
br
eak, and water vvapor
apor per
meability due to the higher plasticizing effect of gly
cer
ol. This behavior was exbreak,
permeability
glycer
cerol.
plained in ter
ms of molecular w
eight of the plasticiz
ers
ated that the studied pr
oper
ties
terms
weight
plasticizers
ers,, which demonstr
demonstrated
proper
operties
could be consider
ed as functions of the number of molecules of plasticiz
ers in the films
considered
plasticizers
films..
Keywor
ds: edible films
apor per
meability
oper
ties
oper
ties
er
eywords:
films,, water vvapor
permeability
meability,, mechanical pr
proper
operties
ties,, viscoelastic pr
proper
operties
ties,, plasticiz
plasticizer
Introduction
Film pr
oduction
production
The films were obtained by drying film-forming solutions (FFS)
with 2 g gelatin/100 mL water and 25 or 55 g plasticizers blends/
2005 Institute of Food Technologists
Further reproduction without permission is prohibited
Water vvapor
apor per
meability
permeability
Water vapor permeability was determined gravimetrically according to a method proposed by Gontard and others (1993), at
25 C, using silica gel and pure water in and out of the permeation
cells, respectively. These cells were weighed ( 0.01 g) daily for 7 d
to guarantee the steady state permeation, using a semi-analytical
balance (Marte, AS2000, Sao Paulo, Brazil). This property was always determined in triplicate.
V iscoelastic pr
oper
ties
proper
operties
The viscoelastic properties of the films were characterized by
dynamic mechanical analysis, always in triplicate, using the equipment DMA TA2980 controlled by a TA5000 module (TA Instruments,
New Castle, Del., U.S.A.), and with the film grips clamps that allowed
possible uniaxial traction tests. The analyses were carried out in the
frequency-scanning (0.01 to 100 Hz) mode, with a constant temperature at 30 C, an amplitude of deformation of 0.2%, and a flow of
N2 in the measure cell equal to 1180 mL/min).
Rectangular samples of about 19 mm 5 mm were submitted to
the oscillatory traction (sinusoidal stress applied) analysis, obtaining
the storage modulus (E), the loss modulus (E) and the phase angle
(tan = E/E) as functions of the frequency. For the study of the plasticizing effect of blends on viscoelastic properties, E, E, and tan
were calculated from DMA results at 1 Hz frequency (Pasckoalick
and others 2003), with the software Universal Analysis V1.7F (TA
Instruments).
Mechanical pr
oper
ties
proper
operties
The mechanical properties of the films were determined by the
puncture and tensile tests, through a texturometer TA.XT2i (SMS,
Surrey, U.K.), using 10 replicates. For the determination of the
mechanical properties (puncture force and puncture deformation)
through the puncture tests, the films were fixed in cells with 52.6
mm of opening diameter and perforated by a probe with 3 mm
diameter, moving at 1 mm/s (Gontard and others 1993).
For the determination of the mechanical properties through
tensile tests (tensile strength, modulus of elasticity, and elongation
at break), the films were cut in rectangles with 15 mm width and
100 mm length and fixed on the grips of the device with a gap of 80
mm. The films were tractioned at a speed of 0.9 mm/s (Pasckoalick and others 2003).
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Table 1Water vapor permeability (WVP) and humidity of gelatin films plastificized with blend of Gly:Sora
Cpb
25
55
Gly:Sor
(%)
WVP
(g mm m2 d1 kPa1)
Humidity (g water/100
g moist solids)
0:100
20:80
40:60
60:40
80:20
100:0
0:100
20:80
40:60
60:40
80:20
100:0
12.92 1.36e
15.27 1.59c,d,e
14.18 1.37d,e
15.11 0.82c,d,e
16.68 1.43c,d
16.90 0.77c
15.90 2.58c,d
21.69 1.49a,b
19.81 0.86b
20.79 1.76a,b
22.97 0.65a
22.87 0.86a
13.45 0.75f
13.46 0.67f
13.81 0.51e,f
14.88 0.36d,e,f
14.78 0.23d,e,f
16.81 1.31b
13.86 0.51e,f
15.30 0.13c,d
15.09 0.59d,e
15.33 0.72c,d
16.56 0.64b,c
18.60 1.36a
difference (P < 0.05) between averages obtained through the Duncan test.
bCp, plasticizer concentration (g/100 g of gelatin).
Statistical analysis
Duncans multiple range test was applied to compare the means
of physical properties of the gelatin-based films with a level of significance = 0.05, using the SAS software (Version 6.8, SAS Inc, Cary,
N.C., U.S.A.).
Per
meability to water vvapor
apor
ermeability
Normally, an increase of plasticizer concentration causes an
increase in the water vapor permeability of hygroscopic films because of a reorganization of the proteinic network with a consequent increase of free volume (Cuq and others 1997). For this reason, in a general manner, it was observed that the films with 55 g
plasticizers/100 g gelatin were more permeable to water vapor
(P < 0.05) than films with 25 g plasticizers/100 g gelatin comparing
films with the same Gly:Sor ratio (Table 1).
On the other hand, for each concentration studied, it could be
observed that the films produced only with Gly were more permeable (P < 0.05) than the films produced only with Sor, and the films
with 25 g Gly/100 g gelatin and 55 g Sor/100 g gelatin showed similar
permeability. In addition, it could be considered that the increase of
the proportion of Gly in the mixture increased the permeability of
the films (Table 1). These results were the consequence of a higher
plasticizing effect of Gly in relation to Sor. This behavior was observed by Cuq and others (1997) with films of Sardine myofibrillar
protein and Gennadios and others (1996) with egg albumen films.
Tanaka and others (2001) and Parris and Coffin (1997) verified an
increase of the water vapor permeability caused by an increase of the
proportion of glycerol in the mixture of glycerol:polyethylene glycol
in soluble fish protein films and the mixture of glycerol:polypropylene glycol in zein films, respectively.
This higher efficiency of Gly was due to its lower molecular
weight than Sor (Cuq and others 1997), and also due to its higher
Vol. 70, Nr. 3, 2005JOURNAL OF FOOD SCIENCE
E173
Gly:Sor (%)
E (MPa)
E (MPa)
tan
25
0:100
20:80
40:60
60:40
80:20
100:0
0:100
20:80
40:60
60:40
80:20
100:0
1806.7 137.4a
1328.3 176.2b
1348.3 235.9b
1264.0 165.7b
845.8 104.0c
1179.0 125.9b
366.3 23.3d
272.8 24.9d,e
247.7 37.6d,e
183.7 16.4d,e
222.9 68.1d,e
119.4 25.6e
194.7 13.9a
170.7 20.5a,b
189.3 27.0a
182.1 2.1a
155.2 10.6b
183.8 15.4a
74.4 4.1c
62.0 3.9c,d
56.8 7.7c,d
45.6 5.4d,e
58.0 16.3c,d
32.7 7.1e
0.108 0.02g
0.129 0.03f,g
0.142 0.02e,f
0.146 0.02e,f
0.184 0.01d
0.157 0.02e
0.203 0.002d
0.228 0.01c
0.230 0.004c
0.248 0.01bc
0.261 0.01a,b
0.274 0.01a
55
aAverage standard deviation. Different letters (a to f) denote significant difference (P < 0.05) between averages obtained through the Duncan test.
bCp, plasticizer concentration (g/100 g of gelatin).
hygroscopicity. It was observed that the humidity of the films tended to increase with the increase of the proportion of Gly in the mixture (Table 1) and that the moisture of the films with 55 g plasticizer/100 g gelatin was in a general manner, higher than the films with
25 g plasticizer/100 g gelatin. This absorption of molecules of water
favored the increase of water vapor permeability in films based on
biopolymers (Gontard and others 1993; Cuq and others 1997).
Viscoelastic pr
oper
ties
proper
operties
The viscoelastic properties of the films of gelatin varied subtly
as a function of the oscillation frequency of the strain applied by
the dynamic-mechanical analyzer. Examples of responses obtained
during analyses of the films elaborated with blends of Gly and Sor
are presented in Figure 1, where it could be observed that E was
always greater than E in the entire frequency domain, which was
a characteristic of physical gels. Similar behaviors of E, between
0.1 and 100 Hz, could be observed in the work of Lazaridou and Biliaderis (2002), Paschoalick and others (2003), and Sobral and others
(2004).
The values of the viscoelastic properties calculated at the frequency of 1 Hz are shown in Table 2. It was verified that the increase
of the plasticizer concentration from 25 to 55 g of plasticizer/100
g of gelatin caused a reduction (P < 0.05) of both moduli. This behavior was caused by the increase of the plasticization of the polymeric matrix and was in accordance with the results observed in
films based on fish muscle proteins (Paschoalick and others 2003;
Sobral and others 2004). Paschoalick and others (2003) observed
this same behavior with films based on fish muscle proteins plasticized with different concentrations of glycerol and obtained values of the same order as those in this work.
In a general manner, it could be considered that the storage and
loss moduli were less sensitive to the type of plasticizer, with slight
tendency to reduction when the proportion of Gly in the mixture
increased. On the other hand, the phase angle (tan ) increased
(P < 0.05) with the increase of plasticizer concentration and the increase of glycerol in the mixture Gly:Sor caused an increase
(P < 0.05) of tan in both plasticizer concentrations (Table 2).
The increase of tan with the increase of Gly in the blend of plasticizers could be explained by the increase in the number of plasticizer molecules in films by virtue of the lower molecular weight of
Gly in relation with Sor. Representing the property tan as a function of the number of moles of both plasticizers present in the films,
it was observed (Figure 2) that this property could be considered as
a unique function of the number of molecules in the film. This
approach was proposed and verified by Cuq and others (1997) in
relation to other properties.
Mechanical pr
oper
ties
proper
operties
Figure 1Examples of spectra of the loss modulus (E), storage modulus (E), and angle phase (tan ) as a function of the
frequency of films plasticized with blends of glycerol:sorbitol
(60:40) at concentrations of 25 g plasticizers/100 g gelatin
() and 55 g plasticizers/100 g de gelatin (- - - - ).
E174
Gly:Sor (%)
PF (N)
25
0:100
20:80
40:60
60:40
80:20
100:0
0:100
20:80
40:60
60:40
80:20
100:0
26.57 2.77a
24.81 3.12b
22.61 1.94c
22.09 1.84c
17.23 2.03d
16.39 1.83d
21.19 2.11c
16.30 2.39d
16.03 1.93d
13.15 1.14e
10.19 1.44f
8.31 1.24g
55
PD (%)
2.53 0.52g
2.96 0.88f,g
2.43 0.45g
2.77 0.20f,g
3.13 0.37f,g
3.48 1.00f
6.96 0.64e
9.67 1.45d
9.45 1.17d
12.05 1.26c
15.18 1.79b
17.61 1.76a
TS (MPa)
EB (%)
47.81 6.38a
46.07 8.64a
41.18 4.43b
35.13 5.93c
26.18 2.59d
21.14 3.10e
23.83 3.12d,e
16.98 3.12f
12.11 2.22g
11.54 1.08g
9.39 1.16g,h
7.21 0.79h
5.89 1.00g
20.08 3.24f
15.47 3.91f
20.70 5.28f
39.05 5.41e
37.45 7.35e
74.20 10.58d
77.96 14.40d
73.56 12.90d
91.23 9.71c
110.09 19.17b
127.61 17.32a
ME (MPa)
15.96 2.03a
14.15 2.15b
11.24 2.17c
11.04 1.21c
6.24 0.99d
5.45 1.28d
3.25 0.23e
2.27 0.37f
1.67 0.35f,g
1.26 0.17g,h
0.78 0.23g,h
0.41 0.11h
into proteinic network and establish hydrogen bondings with reactive groups of amino acid residues reducing the protein-protein
interactions. The difference of size of these molecules (Gly and Sor)
did not justify the difference in the plasticizing effects observed in
this study. In addition, the higher plasticizing effect of Gly on Sor
could not be explained in terms of molecular structures (Sothornvit
and Krochta 2001), because both the compounds had similar structures like straight-chain molecules. Furthermore, the reasons could
not be explained in terms of the number of oxygen atoms in the
molecule, because sorbitol had more oxygen atoms (6) than glycerol (3), and therefore, should have better plasticizing effect, which
was different from that observed in this work.
However, the plasticizing effect of the components studied in
this work could be explained in terms of molecular weight. For example, representing the resistance properties as puncture force and
tensile strength as functions of the molar concentration of the plasticizers added, it could be observed that the reduction of these
properties occurred as functions of the increase in the number of
plasticizer molecules in the films (Figure 3). This same behavior was
observed in relation with the puncture deformation, elongation at
break, and modulus of elasticity. This behavior was verified by Cuq
and others (1997) working with films based on myofibrillar fish
proteins, but was not observed by Snchez and others (1998) and
E175
a Average standard deviation. Different letters (a to h) denote significant difference (P < 0.05) between averages obtained through the Duncan test.
b Cp, plasticizer concentration (g/100 g of gelatin).
Conclusions
he blends of plasticizers could be used in the production of edible films avoiding some problems with the use of a unique
plasticizer. The films plasticized by mixtures of glycerol and sorbitol showed water vapor permeability, mechanical and viscoelastic
properties intermediate to the films plasticized only with glycerol
or sorbitol. These results were related to the molecular weight of the
plasticizers, that is, the properties of the films were functions of the
total number of plasticizer molecules present in the films.
Acknowledgments
To CNPq for the research fellowship of PJAS, and to FAPESP. Work
of project XI.20 of CYTED.
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