3474 J. Agric. Food Chem.

1996, 44, 3474−3478

Edible Wheat Gluten Film: Influence of Water Content on Glass

Transition Temperature
N. Gontard*,† and S. Ring‡
ENSIA-SIARC/CIRAD-SAR, B.P. 5098, 34032 Montpellier Cedex, France, and IFR/BBSR 2, Colney Lane,
Norwich NR47 UA, United Kingdom

The depression of the glass transition temperature of a wheat gluten film by water was studied by
dynamic mechanical thermal analysis and differential scanning calorimetry. Wheat gluten film
behaved as a typical amorphous polymer, and the large plasticizing effect of water did not fit simply
on the prediction of the Couchman-Karasz equation. Temperature and water mass fraction, at
which large changes of film mechanical and barrier properties were previously observed, are well
correlated with glass transition.

Keywords: Edible film; wheat gluten; glass transition

INTRODUCTION 1972; Marshall and Petrie, 1980), collagen (Batzer and

Kreibich, 1981), or elastin (Kakivaya and Hoeve, 1975;
Functional properties of edible or biodegrable films Scandola et al., 1981), resulting in a drop of Tg. A
from food biopolymers are highly influenced by numer- variety of techniques including differential scanning
ous parameters, such as film-forming technology, sol- calorimetry (DSC), dynamical mechanical thermal analy-
vent characteristic, additives content, etc. (Guilbert, sis (DMTA), or pulsed nuclear magnetic resonance, have
1986; Kester and Fennema, 1986; Guilbert and Biquet, been used to show that wheat gluten is a highly
1989). Because of their hydrophilicity, film properties amorphous multipolymer system that is water platici-
are also highly dependent on usage conditions such as zable but not water soluble (Hoseney et al., 1986; Slade,
relative humidity and temperature (Kamper and Fen- 1984; Slade et al., 1989; Kalichevsky et al., 1992).
nema, 1984; Biquet and Labuza, 1988; Rico Pena and In previous investigations (Gontard et al., 1991, 1992,
Torres, 1991; Gontard et al., 1993). Water is the most 1993), an edible wheat gluten film was developed, and
ubiquitous and uncontrollable plasticizer. Until re- the effects of film-forming conditions, plasticizer content
cently, this temperature and water content dependence (glycerol), additives, relative humidity, and temperature
was only interpreted in terms of water activity or on various film properties (water vapor permeability,
disruptive water-polymer hydrogen bonding in a poly- mechanical, sorption properties) were studied. In the
mer hydrogen-bonded network. present study, the Tg of wheat gluten film is studied as
The structure-properties relationships of hydrated a function of water content by DSC and DMTA to gain
biopolymers could be better understood with the theo- a better understanding and control of the plasticizing
ries of glass transition used in polymer science; that is, effect of water on the film.
in terms of critical variables of time, temperature, and
diluent content (Slade, 1984; Levine and Slade, 1987, MATERIALS AND METHODS
1991; Slade et al., 1989). Glass transition of an amor-
phous or partially amorphous polymer is typically Wheat Gluten Film Preparation. A film-forming solu-
described as a transition from a brittle glass to a highly tion was prepared with gluten (Amylum Aquitaine, F 33000
viscous or a liquid-like rubber (Levine and Slade, 1991; Bordeaux), glycerol (95%, Merck, Darmstadt, Germany), acetic
Allen, 1993). The glass transition separates two do- acid, ethanol (Aldrich Chemie, Steinhem, Germany), and
water. The gluten concentration (7.5 g/100 mL solution),
mains according to clear structural differences, and
glycerol concentration (20 g/100 g of gluten), ethanol concen-
polymer properties are seriously modified when the tration (45 mL/100 mL solution), and pH of the solution (4.0
temperature rises above the glass transition tempera- adjusted with acetic acid) were chosen on the basis of results
ture (Tg). Theoretically, the addition of plasticizers such from previous investigations (Gontard et al., 1992, 1993). All
as water under isothermic conditions has the same effect components were mixed vigorously at 40 °C, and the film-
as increased temperature on molecular mobility. Water, forming solution was then immediately poured on a plexiglass-
which is a low molecular weight component, increases leveled surface and dispersed with a thin-layer chromatogra-
free volume and thereby allows increased backbone phy (TLC) spreader (Braive, 4000 Liège, Belgium) adjusted
chain segmental mobility. to 0.8 mm height. The film-forming solution was dried in a
ventilated oven at 30 °C to evaporate volatile solvents (ethanol,
In spite of their wide variety of structure, reflecting acetic acid, and water). This procedure resulted in the
the diversity of the aminoacids from which they are formation of a transparent film with a constant controlled
built, it is well established that most proteins undergo thickness (0.050 ( 0.003 mm) that was measured at several
a glass transition. Plasticization by water affects the positions with a micrometer (Roch).
Tg of amorphous or partially amorphous proteins such Disks (for DSC measurements) or rectangles (for DMTA
as caseine (Kalichevsky et al., 1993), gelatin (Yannas, measurements) of film were equilibrated for 5 days at 25 °C
in atmospheres with controlled relative humidities (using
saturated salt solutions of known water activity ranging from
* Author to whom correspondence should be ad- 0.06 to 0.97 at 30 °C (Spiess and Wolf, 1987; Multon, 1984;
dressed (fax 33 67 61 70 55; e-mail [email protected]). Stamp et al., 1984). The moisture content of each film was
† ENSIA-SARC/CIRAD-SAR.
evaluated with previously determined sorption isotherms
‡ IFR/BBSR 2. (Gontard et al., 1993).

S0021-8561(96)00230-0 CCC: $12.00 © 1996 American Chemical Society

Glass Transition of Gluten Film J. Agric. Food Chem., Vol. 44, No. 11, 1996 3475

Figure 2. Typical DMTA plot for a wheat gluten film stored

under 43% relative humidity (0.032 water mass fraction)
showing tensile modulus (E′) and tan δ as a function of
Figure 1. DSC thermogram of wheat gluten film stored at temperature.
0-90% relative humidity (water mass fraction, 0.008-0.224).

DSC Measurements. Ten milligrams of small film disks

of known dry matter were piled up in open stainless-steel pans,
which were designed to withstand high pressures and suppress
the volatilization of water, and equilibrated at the desired
relative humidity for 5 days. After equilibration, the pans
were immediately and hermetically sealed. Calorimetric
measurements were carried out with a Perkin Elmer DSC-4
calorimeter equipped with a thermal analysis data station. The
temperature was calibrated daily with the melting points of
Indium and cyclohexane II. An empty aluminium pan was
used as an inert reference.
The Tg was determined from the midpoint of the heat
capacity change observed at a heating rate of 10 °C‚min-1 on
at least triplicate samples, and verified from the second run
after cooling to eliminate the eventual effects of sample history.
Figure 3. DMTA tensile modulus (E′) as a function of
Dynamic Mechanical Thermal Analysis (DMTA) Mea- temperature for wheat gluten film with 0.08 (0), 0.032 (O),
surements. DMTA measurements were made with a Polymer 0.057 (4), 0.194 (2) and 0.292 (b) water mass fraction.
Laboratories PL-DMTA mark I apparatus (Loughborough,
U.K.). Sample rectangles of film (12.0 × 6 mm) of known dry
matter were previously equilibrated at the desired relative
Glass transition phenomenon in gluten film was
humidity for 5 days. After equilibration, they were im- confirmed by DMTA. A typical DMTA graph showing
mediately coated with silicon grease to avoid water evaporation E′ (elastic modulus) and tan δ as a function of temper-
and subjected to the tensile mode at a frequency of 1 Hz while ature is shown in Figure 2. Wheat gluten film clearly
the temperature was increased from -20 to 160 °C at 2 displays the behavior of an amorphous polymer: with
°C‚min-1. Sample displacement gave the storage modulus (E′), increasing temperature, this amorphous protein traverses
the loss modulus (E′′), and tan δ () E′′/E′). The storage the glassy region, the transition region (tan δ peak and
modulus is a measure of the stiffness or rigidity of the material modulus drop), and a rubbery plateau. The size of the
and is calculated as the ratio of the stress to the applied strain. tan δ peak that is thought to reflect the volume fraction
The loss modulus reflects the ability of a material to dissipate of the material undergoing the transition (Wetton, 1986)
mechanical energy by converting it to heat through molecular
motion. As the specific molecular groups undergo rotation at
is similar to the typical tan δ peak of other totally
a given temperature, a peak is observed in the loss modulus amorphous biopolymers such as elastin (Lillie and
data due to the absorption of the energy applied by the Gosline, 1993), amylopectin, gelatin, or native wheat
mechanical spectrometer. Tan δ is a useful index of material gluten (Kalichevsky et al., 1993).
viscoelasticity (Urzendowski and Pechak, 1992). In the glassy state, the storage modulus E′ displays
The Tg was defined as usual by the tan δ peak or the a value of ∼109 Pa and is insensitive to moisture content
inflexion point of the decrease in E′ on at least triplicate changes (Figure 3). At the glass-to-rubber transition,
samples. a characteristic decrease of 103 Pa is observed. These
results are consistent with those for native wheat gluten
RESULTS AND DISCUSSION or other biopolymers, such as casein (Kalichevsky et al.,
1993), starch, gelatin, or ovalbumin (Kalichevsky et al.,
The Tg of wheat gluten films was determined by DSC 1993; Yannas, 1972). The absence of a flow region
as well as by DMTA measurements. DSC measure- precludes the presence of intermolecular covalent cross-
ments (Figure 1) show only a change of the baseline bondings, such as disulfide bonds. Gluten has been
toward a higher value, indicating that gluten is a highly described as a thermosetting polymer (Slade et al., 1989)
amorphous polymer undergoing a glass transition phe- and glutenin subunits (the higher molecular weight
nomenon. But the heat capacity change is relatively component of gluten) are linked by interchain disulfide
small (∼5 cal/g) and induced a 10-20% experimental bonding of cysteine residues which maintains high
error (compared with a 5-8% error for DMTA measure- rubber-like modulus.
ments). The Tg, which was taken in the curves as the Glycerol, which was used as plasticizer, appears to
inflection point, decreases with increasing water con- be miscible with gluten at the composition used because
tent. only one transition is observed. However, the broaden-
3476 J. Agric. Food Chem., Vol. 44, No. 11, 1996 Gontard and Ring

at low water content because no water loss occurred.

These two methods could thus be considered as comple-
mentary.
On increasing water content, the value of the Tg
drops, at first rapidly (5 °C/1% water for 0-0.1 water
mass fraction) and then more slowly (3.5 °C/1% water
for 0.1-0.3 water mass fraction), indicating a large
plasticizing effect of water on wheat gluten film. The
sensitivity of Tg to polar diluent such as water makes
it very likely that this transformation involves the
regions that contain large polar residues such as Glu,
Asp, Arg, and Lys. This lowering of Tg is similar to the
value observed for gelatin/glycerol system (5 °C/1%
water; Yannas, 1972), starch (∼5 °C/1% water; Orford
et al., 1989), elastin (15 °C/1% for low water content and
5 °C/1% water for 0.1-0.2 water mass fraction; Kakivaya
and Hoeve, 1975), and other biopolymers (generally ∼5-
10 °C/1% water; Slade and Levine, 1989).
The depression of Tg by the addition of a diluent or
plasticizer may be explained by a number of theoretical
approaches such as free volume theories or classical
thermodynamic theories proposed by Couchman and
Figure 4. Tg of wheat gluten film determined by DMTA E′
inflexion point (O) and tan δ peak (4), and by DSC (9) as a Karasz (1978). A thermodynamic consideration of the
function of water content. The solid and dashed lines are the entropies of the components at the Tg of the mixtures
eq 2 theoretical curve obtained for K1 ) 2.1 (- - -) and K1 ) 4.0 leads to the following equation for a three-component
(s). The crosses indicate water mass fraction and temperature mixture:
at which wheat gluten film changes of mechanical and barrier
properties occur, according to Gontard et al. (1994). Tg (mixture) )
W1∆Cp1Tg1 + W2∆Cp2Tg2 + W3∆Cp3Tg3
ing of the transition (a few tens of °C) could suggest a (1)
lack of miscibility or simply reflect the high heterogene- W1∆Cp1 + W2∆Cp2 + W3∆Cp3
ity of gluten proteins molecular weights ranging from
30 000 to millions (Graveland et al., 1985; Bietz and In eq 1, the subscript 1 refers to water, the subscript 2
Wall, 1972). refers to wheat gluten, and the subscript 3 refers to
The Tg decreased when the water content of the film glycerol, W is the weight fraction of each component,
increased (Figure 3). It is interesting to note that, as and ∆Cp is the change in heat capacity observed at Tg.
observed with wheat gluten (Kalichesky et al., 1992) or This equation requires values for the ∆Cp of water that
gelatin (Yannas, 1972), increasing the water content have been subject of considerable debate (Kalichevsky
decreases the rubbery modulus (high-temperature value et al., 1992). Because there is one less constant and no
of E′). It has been observed that E′ values above Tg are need for water ∆Cp, the Gordon-Taylor equation (Gor-
highly dependent on the crosslink density of a polymer; don and Taylor, 1952) has been more easily and suc-
thus, the reduction of the rubbery modulus in the cessfully used to fit Tg data of various biopolymers such
presence of a plasticizer implies reduced cross-linking. as starch (Roos and Karel, 1991). But, this latter
In this case, the reduction in E′ may be due to polymer- equation cannot be extented to more than bicomponent
polymer hydrogen bonds being replaced by labile poly- system. Thus, to obtain a better fit to the predicted Tg
mer-water hydrogen bonds (Kalichevsky et al., 1992). of mixture, the following equation, which is equivalent
The inflexion point in the drop in E′ and tan δ peak to eq 1 but avoids the use of water ∆Cp, was used:
are plotted again water content in Figure 4 and can be
compared with DSC results. A good correspondence is W1K1Tg1 + W2Tg2 + 0.2W2K2Tg3
Tg ) (2)
obtained when DSC results are compared with the E′ W1K1 + W2 + 0.2W2K2
inflexion point. As previously reported for wheat gluten
(Kalichesky et al., 1992) or other biopolymers such as In eq 2, 0.2 ) W3/W2 (equal to the constant weigth ratio
casein (Kalichesky et al., 1993), the tan δ peak falls of glycerol/gluten), K1 ) ∆Cp1/∆Cp2, and K2 ) ∆Cp3/∆Cp2.
above the E′ inflection point and the midpoint in the In addition, K is a constant that is proportional to the
change in heat capacity observed by DSC. A simple plasticizing effect of diluent (water for subscript 1 or
comparison between mechanical and calorimetric de- glycerol for subscript 3) on the polymer (wheat gluten
terminations of Tg is not easy. Techniques are sensitive with the subscript 2).
to different degrees of molecular mobility. Glass transi- For dry film, W1 ) 0, and eq 2 becomes
tion is not observed at a unique temperature, but is
related to the frequency and nature of the measurement Tg(mixture) ) Tg2 + 0.2K2Tg3/1 + 0.2K2 (3)
technique. The Tg measured by DMTA is dependent on
frequency, and Tg measured by DSC depends on the Using Tg2 ) 435 K and Tg3 ) 180 K (from Kalichevsky
heating rate used because it is a kinetically determined et al., 1992), and Tg(mixture) ) 384 K (dry film Tg
transition. However, the DMTA method is a more determined in the present study), K2 was calculated
sensitive method and the glass transitions were easier from eq 3. The K2 value thus obtained was 1.28, which
to detect. Thus, DMTA results are very reproducible is a lower value than the one calculated (2.26) with dry
for high water contents (5% of experimental error), gluten and glycerol ∆Cp (respectively, ∆Cp2 ) 0.39 and
where glass transition occured at a low temperature ∆Cp3 ) 0.88 J‚g-1‚K-1) from Kalichevsky et al. (1992).
avoiding water loss. DSC results could be more reliable This result means that wheat gluten proteins were
Glass Transition of Gluten Film J. Agric. Food Chem., Vol. 44, No. 11, 1996 3477

plasticized by glycerol but not as much as predicted. properties of the same wheat gluten film were studied.
Similarly, but to a greater extent, observations have During the hydration of the film, a dramatic decrease
been made on the plasticizing effects of fructose on in puncture strength and elasticity, and an increase of
sodium caseinate (Kalichevsky et al., 1993), or of extensibility and water vapor transmission rate were
fructose, sucrose, and glucose on wheat gluten (Kali- observed at 5, 30, and 50 °C for water mass fractions of
chevsky et al., 1992). It seems that the incomplete ∼0.25, ∼0.15, and ∼0.07, respectively. These results
compatibility of sugar and proteins was responsible for were discussed in terms of disruptive water-polymer
this phenomenon. Glycerol appears to be more miscible hydrogen bonding, but the highly discontinuous behav-
with gluten than sugars, because of its lower molecular ior could not be explained.
weight, but the compatibility is not complete and could The values in Figure 4 are well correlated with glass
explain the deviation from the Couchman-Karasz transition, especially with DSC measurements and E′
theory. inflection points for DMTA measurements. This cor-
The DSC and DMTA data were fitted with eq 2, with relation suggests that the important change of film
K1 as a variable. As shown in Figure 4, eq 2 could not functional properties could be attributed to a change
be easily correlated with the experimental curve with from the glassy to the rubbery state. The anomalous
a unique K1 that represents the ratio of water ∆Cp to diffusion behavior of glassy polymers may be directly
wheat gluten ∆Cp. With K1 ) 4.0, a very good correla- related to the influence of the changing polymer struc-
tion was obtained for water mass fraction of <0.1. This ture on the solubility of the penetrant and its diffusional
relatively high K1 value required for eq 2 to fit for low mobility (Crank, 1975), and the dependence of the
water content is consistent with results obtained by ultimate mechanical properties (rupture stress and
Kalichevsky et al. (1992) who found a ratio equal to 5 strain) on temperature and rate of deformation is
for wheat gluten. This value is comparable with the similar to that of viscoelastic properties and therefore
ratio of (4.55 for amylopectin (Orford et al., 1989), reflects the configurational rearrangement rates (Ferry,
indicating that the wheat gluten film is highly water 1980).
plasticizable. A glass transition could thus explain the discontinu-
ous behavior of the gluten film properties in response
The model seriously overestimates the plasticizing to changes in moisture content and/or temperature.
effect of water for higher water fraction. Use of K1 ) Below the glass transition, wheat gluten films retain
2.1 provided a better fit to the data for water mass relatively good mechanical and barrier properties and
fraction between 0.15 and 0.3 (Figure 4). This value is should thus be used under these conditions of temper-
equivalent to the results obtained by Kalichevsky et al. ature and water content.
(1993) for slightly water plasticizable proteins such as
casein (2.3) or sodium caseinate (1.3).
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