Bioresource Technology 100 (2009) 18281832

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Rheological behaviour and physical properties of controlled-release gluten-based

bioplastics
D. Gmez-Martnez, P. Partal *, I. Martnez, C. Gallegos
Departamento de Ingeniera Qumica, Facultad de Ciencias Experimentales, Campus el Carmen, Universidad de Huelva, 21071 Huelva, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Bioplastics based on glycerol, water and wheat gluten have been manufactured in order to determine the
Received 30 June 2008 effect that mechanical processing and further thermal treatments exert on different thermo-mechanical
Received in revised form 6 October 2008 properties of the biomaterials obtained. An active agent, KCl was incorporated in these matrices to
Accepted 12 October 2008
develop controlled-release formulations. Oscillatory shear, dynamic mechanical thermal analysis
Available online 20 November 2008
(DMTA), diffusion and water absorption tests were carried out in order to study the inuence of the
above-mentioned treatments on the physicochemical characteristics and rheological behaviour of these
Keywords:
bioplastic samples. Wheat gluten protein-based bioplastics studied in this work present a high ability for
Protein
Bioplastic
thermosetting modication, due to protein denaturation, which may favour the development of a wide
Viscoelasticity variety of biomaterials. Bioplastic hygroscopic properties depend on plasticizer nature and processing
Processing procedure, and may be a key factor for industrial applications where water absorption is required. On
Controlled-release the other hand, high water absorption and slow KCl release from bioplastic samples (both of them suit-
able properties in agricultural applications) may be obtained by adding citric acid to a given formulation,
at selected processing conditions.
2008 Elsevier Ltd. All rights reserved.

1. Introduction and increases the mobility of polymeric chains, thereby improving

Population and economy growth worldwide have caused an
enormous increase in waste production. To minimize this problem,
some alternatives are being studied, such as, for instance, recycling
of plastic materials and substitution of conventional plastics by
biodegradable polymers (Heller et al., 2003; Kim, 2008). Biopoly-
mer materials derived from renewable agricultural resources have
centred a great interest in the last few years. In this sense, many
different thermoplastic biopolymers have been developed and
commercially produced using current levels of technology (Lrck
et al., 2000). The main renewable sources of biopolymers are pro-
teins, polysaccharides and lipids. Proteins are thermoplastic het-
eropolymers of both polar and nonpolar amino acids that are
able to form numerous intermolecular linkages, and undergo dif-
ferent interactions, yielding a wide range of potential functional
properties. Moreover, plant proteins are inexpensive, renewable
and abundant raw materials (Irissin-Mangata et al., 2001; Song
and Zheng, 2008).
A way of processing protein-based biomaterials is the mechan-
ical method, or thermoplastic processing, which consists of mixing
proteins and plasticizer to obtain a dough-like material
(Attenburrow et al., 1999; Jerez et al., 2007; Song and Zheng,
2008). The use of plasticizers reduces the intermolecular forces
* Corresponding author. Tel.: +34 959 21 99 89; fax: +34 959 21 99 83.
E-mail address: partal@uhu.es (P. Partal).
the exibility and the extensibility of the lm (Gao et al., 2006).
Therefore, bioplastics can be processed using existing plastics pro-
cessing machinery, including thermoforming, various types of
injection moulding, compression-moulding, extrusion (lms and
bers), and extrusion coating and lamination (Kim, 2008; Kumar
and Singh, 2008; Kunanopparat et al., 2008; Kadokawa et al.,
2009).
Biopolymer applications include matrices for enzyme immobili-
zation, matrices for controlled-release devices, etc. (Chen and Tan,
2006; Suda et al., 2000). It is possible to use the advantage of their
low solubility in water, as well as their enormous water up-taking
(swelling), in order to develop further applications, such as water
absorbent materials. Thus, they are mainly used as absorbents in
healthcare, agriculture and horticulture applications. In such appli-
cations, water absorbency and water retention are essential (Li
et al., 2006). Moreover, a number of advanced technologies are
being applied to bioplastics to provide added value, including active
packaging technology, natural ber reinforcements, nanotechnol-
ogy, and innovative product design (Kumar and Singh, 2008;
Kunanopparat et al., 2008; Kadokawa et al., 2009).
Chemical fertilizers used in conventional agriculture are well
known for their ability to pollute the environment, particularly
ground water. Entrapping, encapsulating or dispersing the fertilizer
in polymeric matrices could be a good way to minimize these ef-
fects (Devassine et al., 2002; Montain et al., 2004). In addition, using
biodegradable polymers would imply fertilizer controlled-release

0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.10.016
 D. Gmez-Martnez et al. / Bioresource Technology 100 (2009) 18281832
without any additional residue in the soil. Moreover, protein-based
matrices may also play the role of water-reswelling materials (sav-
ing water), and as additional nitrogen source after its degradation,
at a reduced material cost, if compared with other polymers, such
as poly (e-caprolatone), chitosan, poly (acrylic acid-co-acrylamide),
etc. (Montain et al., 2004; Yuan et al., 2006; Zhang et al., 2006).
The aim of this work was to develop new controlled-release bio-
plastics based on glycerol, water, wheat gluten and an active
agent, KCl (source of potassium chloride in agriculture). In this
sense, important tasks were the characterisation of the effect that
formulation, processing, and further thermal treatments exert on
the thermo-mechanical properties, physicochemical characteris-
tics and rheological behaviour of the bioplastics obtained. KCl re-
lease from the bioplastic into water was modied by adding
citric acid to a specic formulation.
2. Experimental
Wheat gluten was provided by Riba S.A. (Spain). Protein content
was 83 wt.%, lipids 1.52 wt.%, and ashes 0.70.8 wt.%. Its moisture
content was 8 wt.% on dry basis. Water, glycerol (from Prolabo,
Spain), KCl, and citric acid (from Panreac Qumica, S.A., Spain) were
used as protein-plasticizer, active agent, and modifying agent,
respectively.
The bioplastic compounds were mixed in a torque-rheometer
(Polylab, Haake, Germany), which consists of two counter-rotating
rollers in a batch mixer (Rheomix 600p), turning with different
angular velocities (ratio 3:2). Both torque and temperature were
continuously recorded during the mixing process. The mixing
chamber can be considered adiabatic, as it was not cooled or
heated. The volume of the chamber (69 cm3) was lled with
approximately 56 g of sample, corresponding to 85% lling ratio.
The mixing process was always carried out at 50 rpm (Jerez
et al., 2005a). The systems selected in order to investigate the ef-
fect of the thermo-mechanical processing were gluten/glycerol
(WG/G), gluten/water (WG/Wt), gluten/glycerol/water (WG/G/
Wt), gluten/glycerol/water/KCl (WG/G/Wt/KCl), and gluten/glyc-
erol/water/KCl/Citric acid (WG/G/Wt/KCl/Citric) blends. Table 1
gathers the different blend compositions. Plasticizer, active agent,
and modifying agent /protein ratio was 0.5.
Biomaterials were moulded by compressing the dough-like
materials, obtained after the mixing process, at 100 bar gauge pres-
sure, in a 50  10  3 mm mould (Jerez et al., 2005b). The process
was carried out at three different temperatures 90, 120, and 140 C,
for 10 min.
Frequency sweep tests, from 100 to 0.05 rad/s, in oscillatory
shear, at a constant strain within the linear viscoelastic region,
and at temperatures between 25 and 120 C, were conducted in a
controlled strain rheometer ARES (Rheometric Scientic, USA.),
using a serrated parallel-plate geometry (25 mm diameter and
11.4 mm gap). Previously, strain sweep tests, at 6.28 rad/s, were
carried out in order to identify the linear viscoelastic region of
these materials.
Table 1
Formulation of the protein-based bioplastics.
Wheat gluten Glycerol H2O KCl
(%) (%) (%) (%)
WG/G 67 33.0
WG/Wt 67 33.0
WG/G/Wt 67 16.5 16.5
WG/G/Wt/KCl 67 16.5 13.0 3.5
WG/G/Wt/KCl/ 67 13.5 13.0 3.5
Citric
1829
Dynamic mechanical thermal analysis (DMTA) experiments
were done with a Seiko DMS 6100 (Seiko Instruments, Japan),
using 50  10  3 mm samples in double cantilever bending mode,
according to the ASTM standard method D502301 (ASTM, 2001a).
All the experiments were carried out at constant frequency (1 Hz)
and strain (within the linear viscoelastic region). The selected tem-
perature ramp was 2 C/min.
DSC experiments were performed with a Q100 (TA Instruments,
USA), using 1020 mg samples, in hermetic aluminium pans, at a
heating rate of 5 C/min. The sample was purged with a nitrogen
ow of 50 mL/min.
Water absorption measurements were based on ASTM standard
method D570-81 (ASTM, 2001b). The water absorption (Ab) was
calculated as follows:
W 1  W 0 W sol
Ab  100 1
W0
where W1, W0 and Wsol are the weights of the specimen containing
water, the dried specimen, and water-soluble residuals,
respectively.
The dynamic tests for the determination of the active compo-
nents releasing rate, from a bioplastic sample, were carried out
with a conductimeter (Inolab cond level 1, Germany). Each test
was performed during 4 days. A xed amount of the bioplastic
was placed in a container with 50 ml of a solution of sodium azide
(0.0776 M). The releasing rate was evaluated as the amount (wt. %)
of KCL released after an elapsed time with reference to the initial
concentration of this component.
3. Results and discussion
3.1. Thermoplastic processing
Manufacture of bioplastics needs a complete mixing of all the
components during the so-called thermoplastic processing. Fig. 1
shows the evolution of torque during the mixing process, at
50 rpm, for the different blends studied. It is apparent that the evo-
lution of torque with time depends on the system studied. Thus,
the gluten/glycerol (WG/G) blend torque evolution presents three
different regions. In the rst region, also known as induction re-
gion, which corresponds to low mixing times, there is not a signif-
icant increase in torque. In the second region, torque undergoes an
exponential increase with mixing time up to a maximum value. Fi-
nally, in the last region, apparent torque decay is observed (Jerez
et al., 2005a). On the contrary, samples containing water (Wt) in
their formulation (WG/Wt, WG/G/Wt, WG/G/Wt/KCl and WG/G/
Wt/KCl/acid blends) only present two regions, characterized by
50
WG/G
WG/Wt
40 WG/G/Wt
WG/G/Wt/KCl
WG/G/Wt/KCl/Citric
Torque (Nm)
30
20
Citric acid
(%) 10
0
0 5 10 15 20 25 30
3.0 Time (min)
Fig. 1. Evolution of torque during the mixing process of different bioplastics.
1830 D. Gmez-Martnez et al. / Bioresource Technology 100 (2009) 18281832

Table 2 7
107
10
Specic mechanical energy (SME), time for the torque maximum (tpeak) reached G' G" G' G"
during mixing process. 25C 100 C
50C 120 C
Bioplastics tpeak (min) SME (kJ/kg) 75C

WG/G 21.9 2647

WG/Wt 1.3 151 10
6
106

GG" (Pa)

GG" (Pa)
WG/G/Wt 1.6 289
WG/G/Wt /KCl 2.2 361
WG/G/Wt/KCl/Citric 2.2 467

10
5
105

an instantaneous increase in torque, up to a maximum value, and

then a continuous decay down to steady state values. Table 2 A B
shows that the maximum value of torque (torque overshoot) is 4
10 104
reached after 22 min mixing for the WG/G blend. On the contrary, 10
-1
10
0 1
10 10
2
10
-1
10
0
10
1
10
2

blends containing water as plasticizer reached the above-men- rad/s

tioned maximum much faster, being these values signicantly low-
Fig. 2. Frequency dependence of the storage and loss moduli, as a function of
er (i.e. between 2 and 3 min). In the same way, the plasticizer also temperature, for a 0.5 glycerol/wheat gluten blend (WG/G), after thermosetting at
affects the specic mechanical energy (SME) required to obtain a 120 C.
material with suitable mechanical properties. Thus, Table 2 also
gathers the SME values for the different bioplastic samples studied
calculated as follows (Redl et al., 1999): 0
10
Z tmix
X
SME Mtot 2
m 0

where X (rad/s) is the mixing speed, m (g) the sample mass, M(t)
(N  m) the torque and tmix (s) the mixing time.
Regarding mixing time, as was previously commented, the
Tan

occurrence of a torque overshoot suggests a dramatic evolution

of gluten structure upon mixing. The nal torque decay is associ-
ated with a change in consistency from powder/plasticizer disper-
sion to a cohesive and elastic material (Redl et al., 1999). Thus, the 10
-1
Thermosetting
time needed to reach an equilibrium torque depends on the ability 25C 50C 75C 100C 120C Temperature
T= 90C
of the constituents to interact together and, therefore, on the se- T =140C
lected plasticizer (Pommet et al., 2003). Consequently, for sake of 5 6
10 10
comparison, tmix was always estimated as 1.5 tpeak.
As may be seen in Table 2, water addition leads to a dramatic G* (Pa)
decrease in SME. Moreover, citric acid and KCl additions only lead Fig. 3. Black diagram of a 0.5 glycerol/wheat gluten blend (WG/G), after thermo-
to slight increases in torque (Fig. 1 and Table 2), related to a lower setting at 90 and 120 C.
water content in this samples.

3.2. Viscoelastic behaviour of gluten-based bioplastics
Fig. 2 shows the frequency dependence of the linear viscoelas-
ticity functions for a 0.5 glycerol/wheat gluten blend (sample
WG/G), after sample compression-moulding at 120 C, in a range
of temperature comprised between 25 and 120 C. A gel-like visco-
elastic behaviour, characteristic of a highly structured material, is
noticed (i.e. the storage modulus is always higher than the loss
modulus in the whole temperature range studied). Nevertheless,
the polymer network formed by proteins chains is affected by tem-
perature leading to a decrease in both moduli with temperature.
However, the rheological response of this material and, there-
fore, its mechanical and physicochemical properties may be mod-
ied by a further thermo-mechanical treatment, such as thermo-
moulding. Aiming to demonstrate this statement, some results
from frequency sweep tests carried out, at different temperatures
(25120 C), on WG/G blends submitted to compression-moulding,
at two different temperatures (90 and 140 C, respectively), are
summarised in the Black diagrams presented in Fig. 3. The Black
diagram is a plot of the phase angle vs the complex modulus, G*,
and provides time-independent curves very sensitive to changes
in microstructure. As may be observed, an increase in compres-
sion-moulding temperature leads to a more elastic material with
improved viscoelastic complex modulus values. Moreover, if the
compression-moulding temperature is low (i.e. 90 C), the samples
show a remaining thermosetting potential, related to further pro-
tein denaturation. As a result, the values of the linear viscoelastic-
ity functions, from frequency sweep tests carried out at 120 C, for
this sample are similar to those found for the sample submitted to
higher compression-moulding temperature. In addition, it is worth
mentioning that a more complex thermo-rheological behaviour is
found as compression-moulding temperature increases.
3.3. Thermo-mechanical behaviour of controlled-release matrices
Typical DMTA scans (from 30 to 160 C) for WG/G/Wt/KCl and
WG/G/Wt/ KCl/acid blends submitted to different thermosetting
temperatures (between 60 and 140 C) are shown in Fig. 4A. The
results obtained for WG/G/Wt/KCl blends demonstrate that an in-
crease in thermosetting temperature generally leads to an increase
in the complex modulus; more important as thermosetting tem-
perature is raised from 90 to 120 C. This is also conrmed by
observing the DMTA results obtained with samples submitted at
low temperatures (6090 C) during compression-moulding. Thus,
they show a remaining thermosetting potential above 100 C, lead-
ing to a remarkable increase in E* with temperature (Fig. 4A). This
fact may be related to incomplete protein denaturation during its
previous thermo-mechanical processing. On the contrary, E* values
do not signicantly increase for WG/G/Wt/KCl blends submitted to
thermo-mechanical processing above 120 C. These results are also
 D. Gmez-Martnez et al. / Bioresource Technology 100 (2009) 18281832 1831

9
10 120 120
E* Thermosetting Bioplastic Thermosetting A WG/G/Wt/KCl T=120C B
WG/G/Wt/KCl T= 60C (1) WG/G/Wt/KCl T=120C WG/G/Wt/KCl/Citric T=120C
WG/G/Wt/KCl T= 90C (2) WG/G/Wt/KCl/Acid T =120C WG/G/Wt/KCl
WG/G/Wt/KCl T= 120C 100 Citric acid solution 100
WG/G/Wt/KCl T= 140C (3) T=120C
WG/G/Wt/KCl/Citric T= 120C (1)

KCl Release (%)

80

KCl Release (%)

(2) 80

Heat Flow (W/g )

8
10
60 60
E* (Pa)

40 40
141C
Thermosetting
7 20 WG/G/Wt/KCl T=90C
20
10 124 C
WG/G/Wt/KCl T=120C
(3) WG/G/Wt/KCl/Acid WG/G/Wt/KCl T=140C
Without Thermosetting 0 Release model 0
A B 129 C
10 100 1000 10000 10 100 1000 10000
30 60 90 120 150 180 0 30 60 90 120 150 Time (min)
Temperature (C)
Fig. 5. KCl release behaviour of WG/G/Wt/KCl and WG/G/Wt/KCl/citric blends
processed at different temperatures.
Fig. 4. Dynamic mechanical thermal analysis results, complex modulus for selected
blends, after different thermosetting temperatures (A) and DSC thermograms for
WG/G/Wt/KCl and WG/G/Wt/KCl/citric blends, after thermosetting at 120 C and
without thermal treatment (B). Table 3
Effect of thermosetting temperature and citric acid content on the release parameters
from Eq. (3) and water absorption values for the different blends studied.

in good agreement with those obtained from DSC measurements Conditions Water Parameter Water absorption
(see Fig. 4B). Thus, WG/G/Wt/KCl sample shows an endothermic temperature (C) pH
Mo M1 t1/2 p Ab (%)
peak located at 141 C, which has been related to thermal denatur-
90 7.455.88 2.45 99.60 55.40 0.90 96
ation of gluten protein (Jerez et al., 2005a). As a consequence, bio- 120 7.455.88 7.00 92.53 95.00 0.85 84
plastics moulded at temperatures close to this value (i.e. 120 and 140 7.455.88 13.92 90.00 100.00 0.98 75
140 C) do not show remaining thermosetting potentials (see 120 7.115.90 0 98.90 149.73 1.16 164
120 5.755.62 0 100.00 69.52 1.26
Fig. 4). Indeed, a higher protein thermal denaturation is expected
in bioplastics thermoset at 120 and 140 C, leading to more struc-
tured systems with higher values of the linear viscoelasticity
functions. t1/2 is the time for 50% KCl release, and P is a parameter related to
However, when citric acid is added to the blend, an important the rate of release. Table 3 shows the values of the above-men-
decrease in the complex modulus values is observed (see tioned parameters.
Fig. 4A). Furthermore, DSC measurements performed on the sam- The effect of thermosetting temperature on KCl release can be
ple just after mixing show a thermal denaturation peak at 129 C, deduced from Fig. 5A and Table 3. Thus, it can be observed that
signicantly lower than that found for WG/G/Wt/KCl samples WG/G/Wt/KCl samples show an increase in t1/2 as thermosetting
(Fig. 4B). Moreover, the endothermic event decreases down to temperature increases. Furthermore, a higher thermosetting tem-
124 C after previous sample thermosetting at 120 C. As a result, perature leads to a higher instantaneous release concentration
no remaining thermosetting potential in samples thermo-moulded (M0), and to a lower nal concentration in water (M1).
at 120 C (Fig. 4A) should be expected. The lower values of E* might Table 3 also gathers water absorption values, after 24 h, for
be explained by a reduced cross-linking density. Thus, the acidic samples submitted to different thermo-mechanical treatments.
environment provided by this plasticizer might prevent aggrega- As can be observed, water absorption percentages decrease as ther-
tion of gluten protein (Pommet et al., 2005). mosetting temperature increases. This fact may be explained tak-
ing into account that the swelling ratio of a polymeric matrix
3.4. KCl controlled-release and bioplastic water absorption decreases as cross-linking degree increases (Zheng et al., 2002;
Buonocore et al., 2003). As described above, bioplastic severe ther-
The controlled-release of active agent and water absorption in mo-mechanical treatment leads to protein denaturation and,
biopolymer systems have received considerable attention in recent therefore, to an increase in the degree of cross-linking between
years, because of their important applications in the elds of bio- molecules (Fig. 4). Moreover, it is known that, as polymer cross-
medical, pharmaceutical, environmental and agricultural engineer- linking degree decreases, the available free space for active agent
ing (Castro et al., 2008; Buchholz and Graham, 1998). Previous diffusion increases, and the rate of active agent release also in-
results have pointed out that both processing conditions and bio- creases (Buonocore et al., 2003). On the contrary, an increase in
plastic formulation may lead to materials with a wide range of the degree of polymer cross-linking, due to material thermosetting,
mechanical responses and, therefore, microstructures (Rouilly decreases the available free space for active agent diffusion, which
et al., 2006). As a result, different swelling and release capabilities results in a decrease in active agent release rates (Fig. 5A).
should be expected. Fig. 5 shows, KCl controlled-release kinetics However, this microstructural interpretation cannot explain the
for samples submitted to a range of thermo-mechanical treatments results found with the bioplastic sample containing citric acid
or differing in their formulations. A sigmoidal model ts fairly well (Fig. 5B and Table 3). Thus, citric addition leads to a remarkable
the KCl controlled-release results obtained decrease in active agent release rate (Fig. 5B). In this sense, t1/2 in-
M  M1 1 creases from 95 to 150 min (Table 3). This is an unexpected result,
3 taking into account the dramatic increase in swelling ratio result-
M 0  M1 1 t=t 1=2 P
ing after citric addition, from 84 to 164% (Table 3). This modied
where M0, M and M1 denote the concentration (wt. %) of KCl ini- bioplastic microstructure does not permit any instantaneous re-
tially diffused, after a time t, and for very long time, respectively; lease of KCl (M0), but it is able to allow diffusion of up to 99% of
1832 D. Gmez-Martnez et al. / Bioresource Technology 100 (2009) 18281832
KCl at long elapsed time. In addition, these results are not related
to water pH, as previously pointed out by other authors (Jiugao
et al., 2005; Vallejo et al., 2005). Thus, the release test was also car-
ried out in a citric acid solution of pH 5.6, for a WG/G/Wt/KCl sam-
ple thermoset at 120 C (Table 3 and Fig. 5B). As can be seen in
Table 3, the release test performed at pH 5.6 shows a t1/2 value
even lower than that found at pH 7.7 (70 and 95 min, respectively),
and, consequently, much lower than that found in protein matrices
containing citric acid (Table 3). As a result, both the decrease in re-
lease rate and the increase in swelling ratio may be related to some
bioplastic microstructural changes resulting after citric acid
addition.
Rheological and thermal results reported in Fig. 4A and B demon-
strate that citric acid addition leads to an important decrease in the
cross-linking degree of the protein network, which may explain the
dramatic increase in swelling ratio with larger available free spaces
within the protein matrices. However, the observed slow release of
KCl seems to be related to the increase in the number of hydrophilic
bonds, probably due to a disaggregation of the protein network by an
acidic plasticizer (Pommet et al., 2005). Thus, the presence of a polar
plasticizer may affect hydrogen bonds, increasing the compatibility
between protein molecules and the saline solution (i.e. glycerol,
water, citric acid and KCl). As a result, the relative afnity of the plas-
ticizer to the polymer matrices is improved, affecting the release pat-
terns in both the slope and the shape of KCl release curves (Siepmann
et al., 2008). A low protein-plasticizer afnity (sample WG/G/Wt/KCl
at 120 C) leads to a fast leaching out of the plasticizer from poly-
meric matrices, yielding high instantaneous release concentration,
M0, and high concentration of water-soluble residuals (Wsol/Wo,
see Eq. (1)), close to 25%. On the contrary, a high protein-plasticizer
afnity (sample WG/G/Wt/KCl/Citric) leads to M0 values close to
zero and lower concentration of water-soluble residuals (Wsol/Wo ,
see Eq. (1)), close to 20%. A fact that points out that the plasticizer
would act as a carrier of the active agent during its leaching out
the matrices.
4. Conclusions
Processing conditions give raise to bioplastic materials with dif-
ferent characteristics, depending on the selected formulation. An
increase in compression-moulding temperature leads to a more
elastic material, with improved viscoelastic modulus values. Lower
water absorption and KCl release rates are obtained as more severe
thermo-mechanical treatments are applied on the sample. On the
contrary, citric acid addition to bioplastic formulations leads to a
remarkable decrease in the cross-linking degree of the protein net-
work. As a result, signicantly higher water absorption and slower
KCl release rate (both of them suitable properties for agricultural
applications) have been found by adding citric acid.
Acknowledgements
This work is part of a research project sponsored by the Junta de
Andaluca Programme (P06TEP02126). The authors gratefully
acknowledge its nancial support.
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