Development of highly-transparent protein/starch-based bioplastics

J. Gonzalez-Gutierrez, P. Partal
*
, M. Garcia-Morales, 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
Article history:
Received 7 July 2009
Received in revised form 9 October 2009
Accepted 13 October 2009
Available online 8 November 2009
Keywords:
Albumen
Starch
Bioplastics
DMTA
Tensile
a b s t r a c t
Striving to achieve cost-competitive biomass-derived materials for the plastics industry, the incorpora-
tion of starch (corn and potato) to a base formulation of albumen and glycerol was considered. To study
the effects of formulation and processing, albumen/starch-based bioplastics containing 030 wt.% starch
were prepared by thermo-plastic and thermo-mechanical processing. Transmittance measurements, DSC,
DMTA and tensile tests were performed on the resulting bioplastics. Optical and tensile properties were
strongly affected by starch concentration. However, DMTA at low deformation proved to be insensitive to
starch addition. Thermo-mechanical processing led to transparent albumen/starch materials with values
of strength at low deformation comparable to commodity plastics. Consequently, albumen biopolymers
may become a biodegradable alternative to oil-derived plastics for manufacturing transparent packaging
and other plastic stuffs.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
In recent years, there has been a great interest to utilize renew-
able biomass in the manufacture of high-quality, cost-competitive
and biodegradable consumer goods, as a means to reduce the
dependence and consumption of petrochemical feedstock and to
diminish environmental pollution (Rosentrater and Otieno, 2006;
Tummala et al., 2006). Packaging lms and containers made of nat-
ural biopolymers are particularly interesting due to their biode-
gradability, since most of these products have a relative short
service life and end up in landlls. However, much work is still
needed to improve the mechanical and physical properties of these
bioplastics, and to reduce their production costs (Jerez et al.,
2007a).
Bioplastics have been manufactured from a variety of sources,
including proteins, lipids and polysaccharides (Avrous, 2004; Her-
nndez-Izquierdo and Krochta, 2008; Siracusa et al., 2008). Pro-
teins are renewable materials that are produced on an annual
kiloton scale. Recent studies have shown their suitability for the
manufacture of bioplastics. Examples of proteins, from a variety
of sources, include wheat gluten (Domenek et al., 2004; Gomez-
Martinez et al., 2009; Jerez et al., 2005; Song and Zheng, 2008;
Sun et al., 2008; Zuo et al., 2008), soy protein (Mohanty et al.,
2005; Tummala et al., 2006; Zheng et al., 2003), zein (Kim, 2008),
egg albumen and rice protein (Jerez et al., 2007a,b).
Proteins structure consists of very stable three-dimensional
networks maintained by interchain interactions which do not en-
dow the material with enough plasticity. For this reason a plasti-
cizer and, sometimes, a rupturing agent need to be added
(Sothornvit and Krochta, 2005; Pommet et al., 2005). Plasticizers
are molecules with low molecular weight and low volatility, which
reduce intermolecular forces and increase polymer chains mobil-
ity. The most common plasticizers include water, glycerol, propyl-
ene glycol and polyethylene glycol.
Three main steps must occur during the formation of protein-
based bioplastics: breaking of stabilizing intermolecular bonds,
orienting mobile polymer chains in the desired shape, and allowing
the formation of newintermolecular bonds that stabilize the three-
dimensional network. These three steps can be accomplished by
thermo-plastic or thermo-mechanical processing. During thermo-
plastic processing, proteins and plasticizers are mixed in a kneader
or extruder to obtain a dough-like material. In thermo-mechanical
processing the resulting material is further subjected to the appli-
cation of both heat and pressure (Jerez et al., 2007b). Each of these
processes yields bioplastics with very different properties. It
should be noticed that proteins like gluten display suitable
mechanical properties after thermo-plastic processing. On the
other hand, proteins like rice or albumen require thermo-mechan-
ical processing to achieve properties which suit current demands.
Egg white protein (albumen) has been traditionally used as a
multifunctional ingredient in the food industry. Its main compo-
nent is ovalbumin (54 wt.%), which is a monomeric phosphogly-
co-protein with four free sulfhydril groups buried in the protein
core. Denaturation of albumen caused by heat results in the
exposure of these sulfhydril groups, accompanied by a decrease
0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.10.025
* Corresponding author. Tel.: +34 959 21 99 89; fax: +34 959 21 93 85.
E-mail address: partal@uhu.es (P. Partal).
Bioresource Technology 101 (2010) 20072013
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in its total content due to oxidation to disulde bonds (Van der
Placken et al., 2005). Proteins chains unfold and entangle with
other proteins, and new bonds arise, causing the texture to change.
As a novel alternative to the food industry, recent work on the
feasibility to produce bioplastics from egg white albumen has been
carried out (Jerez et al., 2007b). If compared to other common pro-
teins like gluten, egg white has proved to be an adequate raw
material for obtaining highly-transparent bioplastics, with suitable
mechanical properties for the manufacture of biodegradable food
packaging and other plastic stuffs. However, given the relative high
price of egg white and the need for cost-competitive materials
(Zheng et al., 2003), blends of this protein with other products
from agricultural sources are studied in the present paper. Natural
alternatives include polysaccharides such as cellulose and starch,
which are abundant (Kumar and Singh, 2008), biodegradable, and
of lower cost than protein and synthetic additives.
It has been proved that, with a combination of the appropriate
type and percentage of starch and plasticizer, and optimum pro-
cessing parameters, the resulting material can be lm blown in a
satisfactory manner by using the already existing converting tech-
nology (Thunwall et al., 2008; Altskr et al., 2008). On other hand,
proteins have been successfully formed into lms using thermo-
plastic processes such as compression moulding and, mainly,
extrusion, which can result in a highly efcient manufacturing
method with commercial potential for large-scale production of
edible lms and coatings (Hernndez-Izquierdo and Krochta,
2008). In that sense, these processes could be feasible alternatives
for the production of biodegradable food packaging from protein/
starch bioplastics.
The objective of this research was to investigate the effect of
processing and formulation on the thermo-mechanical and optical
properties of blends containing egg white protein and corn/potato
starch. The results obtained were compared with those obtained
for wheat gluten-based bioplastics, as well as other biodegradable
and synthetic plastics.
2. Methods
Wheat gluten (WG) provided by RIBA S.A. (Spain), spray-dried
egg white protein (EW) provided by OVOSEC S.A. (Spain), potato
starch (PS) supplied by Sudstrke GmbH (Germany) and corn
starch (CS) furnished by Cargill Espaa S.L. (Spain) were used as
base materials for bioplastics manufacture. Selected physico-
chemical characteristics of these materials are shown in Table 1.
Glycerol (G), from Panreac Qumica, S.A. (Spain), was used as plas-
ticizer. Additionally, and for the sake of comparison, PLA- (polilac-
tic acid) based commercial bioplastic BioFlex

467F (FKuR,
Germany) and LDPE 302R (Repsol, Spain) have been used.
Bioplastics were manufactured by a thermo-mechanical proce-
dure which includes two stages, mixing of raw materials to obtain
a dough-like mixture, and, then, moulding under pressure and
heat. Unless it is specically indicated in the text, all the bioplastics
tested have been manufactured according to the above-mentioned
protocol. Mixing of ingredients (protein, starch and glycerol) was
done in the kneading tool (Rheomex 600p) of a torque-rheometer
(Polylab, Thermo Haake GmbH, Germany). This device allowed for
the monitoring of both temperature and torque during the mixing
period. The mixing chamber can be considered as adiabatic, i.e. it
was not heated or cooled. Mixing was carried out at 50 rpm, using
two counter rotating rollers turning with different angular veloci-
ties (ratio 3:2, and lled 85% of its full capacity (69 cm
3
) (Jerez
et al., 2005). A constant 37.5 wt.% plasticizer concentration was
used, and four concentrations of starch (with respect to the total
mass of mixture) were studied: 5, 10, 20, and 30 wt.%. After the
mixing process, the dough-like material was stored at room tem-
perature for 5 days. Compression-moulded biomaterials were ob-
tained after the storage period, at a gauge pressure of 10 MPa
and a temperature of 120 C for 10 min in a hot plate press, as de-
scribed by Jerez et al. (2007b). Two types of moulds were used: one
to obtain rectangular beams (50 10 3 mm
3
) for DMTA experi-
ments and transparency measurements, and the second one to ob-
tain type IV dumbbell specimens (ASTM D638, 2003) for tensile
tests.
Tensile testing at room temperature was performed in a Shima-
dzu AG-IS 10kN Universal Testing Machine (Shimadzu Co., Japan).
All tensile tests were stroke controlled with a constant cross head
speed of 20 mm/min. According to the standard ASTM D638
(2003), ve tests were carried out for each sample.
Dynamic Mechanical Thermal Analysis (DMTA) experiments
were performed with a Seiko DMS 6100 (Seiko Instruments Inc.,
Chiba, Japan) in double cantilever bending mode. Temperature
sweeps were performed at a constant frequency (1 Hz) and strain
within the linear viscoelastic region. The selected temperature
ramp was 2 C/min with a temperature range from 30 to 140 C.
Frequency sweeps from 0.01 to 100 Hz were carried out, in the lin-
ear viscoelastic region, at four different temperatures (30, 70, 90,
and 110 C). All tests were done in triplicate.
Transparency measurements were done using a Photometer S-
2000 spectrophotometer (J.P. Selecta, S.A., Barcelona, Spain). Trans-
mittance (%) of rectangular specimens, 3 mm thick, was measured
using a wavelength of 600 nm. Air was used as blank (100% trans-
mittance). Low density polyethylene (LDPE), polypropylene (PP)
and polymethyl methacrylate (PMMA) were used to compare
transparencies of albumen bioplastics.
Differential Scanning Calorimetry (DSC) experiments on glyc-
erol/starch samples were performed with a Q100 (TA Instruments,
USA), using 10 to 20 mg samples, in hermetic aluminium pans. A
heating rate of 10 C/min was selected. The sample was purged
with a nitrogen ow of 50 ml/min.
3. Results and discussion
3.1. Bioplastic thermo-mechanical behaviour
Aiming to assess the mechanical response of commercial syn-
thetic and biodegradable plastics, as well as other protein-based
materials previously proposed, tensile and DMTA tests were per-
formed. The results here obtained will allow for the characteriza-
tion of a benchmark for novel albumen/starch-based bioplastics.
Table 2 shows the results from tensile tests performed on albumen
and gluten-based bioplastics. In addition, results for a PLA-based
commercial bioplastic and a commercial LPDE were included in
this Table. It can be observed that the gluten-based bioplastic sam-
ple has a large elongation at break (235.1 14.1%) but its tensile
strength is quite low (0.52 0.12 MPa). Starch addition does not
increase this value further. On the contrary, starch decreases bio-
plastic elongation at break. This fact evidences a certain starch
protein incompatibility, which is more pronounced for corn starch.
Table 1
Selected physico-chemical characteristics of the raw materials used.
WG EW PS CS
Protein (wt.%) 83 73 0.1 0.32
Lipid (wt.%) 2 Trace
Ashes (wt.%) 0.8 6 0.5
Moisture (wt.%) 8 8 20 11.8
pH 6.88
a
7.10
a
4.6
b
a
10 wt.% solution.
b
Suspension 20 g/100 ml.
2008 J. Gonzalez-Gutierrez et al. / Bioresource Technology 101 (2010) 20072013
The egg white bioplastic shows a much higher tensile strength
(7.1 0.8 MPa) than the gluten-based one. However, its elongation
at break decreases (130.4 7.8%). Compared to the commercial
PLA-based bioplastic, albumen bioplastic has a similar tensile
strength but higher elongation at break. Finally, the commercial
LDPE presented a much larger tensile strength (10.3 1.8 MPa)
and elongation at break (540.8 25.2%) than any of the bioplastics
tested in this study.
Dynamic mechanical thermal analyses were also carried out on
those systems and the results (complex modulus and loss tangent)
are shown in Fig. 1. It can be seen that wheat gluten-based bioplas-
tics present the lowest values of the complex modulus in the tem-
perature range tested. Furthermore, wheat gluten-based
bioplastics show a rapid decay in |E
*
| until approximately 110 C,
temperature at which an apparent recovery in the complex modu-
lus values due to a further thermal protein denaturation arises (Jer-
ez et al., 2007b). Likewise, the egg white-based bioplastic also
shows a continuous decay in |E
*
| with a change in the decay rate
at the temperature of 60 C, coinciding with a maximum in the loss
tangent, which could be related to a gel-glasslike transition tem-
perature of the plasticized egg white proteins (Nakamura et al.,
1999; Sepe, 1997; Takushi, 1998). Both albumen and gluten-based
bioplastics did not show any melting processes during material
heating. On the contrary, LDPE shows the greatest decay in |E
*
|
as temperature increases, with values of the complex modulus rap-
idly going down when temperature approaches polymer melting
point (around 120 C). More complex viscoelastic behaviour,
suggesting the existence of a mixture of compounds with different
thermo-mechanical responses, was found for the PLA-based bio-
plastic. A sharp decrease at about 70 C (glass transition tempera-
ture of the polylactic matrix), causing a rubbery plateau until 90 C,
can be observed. At this point, cold crystallization occurred, yield-
ing a rapid increase in the complex modulus afterward, which was
followed by a nal decay starting at 110 C, corresponding to the
onset of melting (Ke and Sun, 2003; Oksman et al., 2003; Tokoro
et al., 2008).
Furthermore, Fig. 1 shows that the albumen-based bioplastic,
between 30 and 60 C, presents similar |E
*
| values to the PLA-based
bioplastic, and slightly lower values than LDPE. Similar results
were also reported by Jerez et al. (2007b), with a maximum in
tan d occurring at around 80 C (instead of 60 C, herein observed)
due most probably to the lower plasticizer content used. In addi-
tion, the loss tangent curve for the commercial bioplastic studied
shows a well-marked peak at approximately 70 C, which has pre-
viously been observed in other bioplastics and composites contain-
ing PLA in their formulations (Ke and Sun, 2003; Oksman et al.,
2003; Tokoro et al., 2008). Likewise LDPE shows a maximum in
the loss tangent at about 95 C. This transition was rst related
to a-relaxation due to vibrational and reorientational motion with-
in the crystals. Later, it was interpreted as relaxation of the con-
strained molecules with reduced mobility close to crystallites
(Bikiaris et al., 1999; Pedroso and Rosa, 2005).
Regarding wheat gluten bioplastics, the addition of potato
starch did not cause any major change, although a clear drop in
the values of |E
*
| after blending with corn starch was observed.
However, the behaviour seen was never signicantly altered by
starch addition, which may suggest that, at the starch concentra-
tion used, the thermo-mechanical properties at low deformations
are ultimately controlled by the properties of the protein matrix.
3.2. Processing of albumen/starch-based bioplastics
Previous results suggest that the albumen-based bioplastic
could be considered as a material able to be used in some of those
applications where PLA/starch-based materials are being em-
ployed. Aiming to investigate bioplastic processability and the ef-
fect of processing variables on the materials properties, DMTA
Table 2
Comparison of tensile elongations at break and strengths of egg white (EW), wheat
gluten (WG), WG with 20 wt.% corn starch (CS) or potato starch (PS) bioplastics,
starchPLA-based commercial bioplastic, and commercial LDPE.
Plastic type Elongation at break (%) Strength (MPa)
Commercial LPDE 540.8 25.2 10.3 1.8
Commercial starchPLA
bioplastic
17.9 2.4 7.7 1.0
EW + G 130.4 7.8 7.1 0.8
WG + G 235.1 14.1 0.52 0.12
WG + G + CS 20 wt.% 70.8 4.8 0.13 0.02
WG + G + PS 20 wt.% 163.5 12.9 0.32 0.05
Fig. 1. Comparison of DMTA spectra in bending mode of egg white (EW), wheat gluten (WG), WG with 20 wt.% corn starch (CS) or potato starch (PS) bioplastics, PLA-based
commercial bioplastic, and commercial LDPE.
J. Gonzalez-Gutierrez et al. / Bioresource Technology 101 (2010) 20072013 2009
specimens of albumen with 20 wt.% potato starch were prepared
by following two different procedures: (a) die-cutting from a sheet
formed with the just prepared dough-like material, and (b) mould-
ing of the dough-like material, at 120 C, with a gauge pressure of
10 MPa for 10 min. Thus, dynamic mechanical thermal analysis
was carried out on samples of the materials prepared by both
methods detailed above. On the one hand, the die-cut material
shows a steady decay in both moduli (E
0
and E
00
) with increasing
temperature up to 60 C. At this point both E
0
and E
00
start increas-
ing as a consequence of protein/starch thermal denaturation, with
the storage modulus being larger than the loss modulus, which
indicates that the material is more elastic than viscous. Finally,
from around 100 C onwards the loss modulus slightly decreases
whereas the elastic one tends to a plateau. Interestingly, the ther-
mal behaviour exhibited by this material provides useful informa-
tion on the optimum temperature intervals to be used in the
different stages within the manufacturing process of albumen-
based bioplastics. Thus, temperatures close to 60 C, where the
material presents the lowest values of the elastic and viscous mod-
uli, may be very suitable for extrusion/mixing operations. More-
over, temperatures above 70 C, for which the material shows a
predominantly elastic behaviour (E
0
> E
00
) with the elastic modulus
reaching its highest values, would enhance the material mechani-
cal properties during moulding operations.
On the other hand, the moulded material shows much higher
values of the viscoelastic moduli than the die-cut material, with
a monotonous decay of both E
0
and E
00
with increasing temperature.
Also, a more signicant elastic behaviour can be observed within
the entire range of temperature tested. Moreover, the most rele-
vant difference between both samples (i.e. between both process-
ing procedures) is found in their optical properties. Hence, the
material obtained after processing in the kneading device is opa-
que after heating (inset in Fig. 2). Nevertheless, if the same mate-
rial is further subjected to a combined thermal and pressure
treatment, a transparent albumen/starch-based material is ob-
tained (inset Fig. 2). It is worth remarking that thermal denatur-
ation of egg white proteins has extensively been studied
(Damodaran and Paraf, 1997; Hegg, 1982; Mine, 1995). The mech-
anism by which gels are formed from globular proteins, like oval-
bumin, differs from that of other proteins. Egg white is a
transparent viscous liquid that changes into a turbid gel after ther-
mal treatment. In general, coagulum-type gels are characterized by
a three-dimensional network structure formed by protein aggre-
gates. Spectroscopic observations reveals that the conformation
of heat-denatured ovalbumin in the secondary structure level is
not very different from that of the native molecule, but some of
the hydrophobic areas that were buried in the native molecule be-
come exposed after heating. Thus, the aggregation of ovalbumin
during heating mainly results from hydrophobically driven pro-
teinprotein interactions. Under certain condition, those intermo-
lecular interactions between heat-denatured ovalbumin
molecules, which are still in globular shape, lead to the formation
of random aggregates, making the gel show an opaque appearance.
However, random aggregates can be dissociated by the application
of pressure (Smeller et al., 1999), a result later conrmed by Jerez
et al. (2007b) for albumen-based bioplastics using Atomic Force
Microscopy (AFM). Consequently, proteins order into a network
of linear aggregates and the resulting gel appears transparent. In
addition, heat-treatment is known to destroy starch granules,
resulting in improved transparency (Hayashi, 2004). As a result,
thermo-mechanical processing (application of the combined action
of heat and pressure to the dough-like material) becomes an effec-
tive way to obtain highly-transparent albumen/starch-based bio-
plastics. Moreover, the addition of starch in the formulation
seems to increase the compatibility between plasticizer and albu-
men, but it could be further increased by pre-gelatinization of
starch with glycerol. Finally, the combination of heat and pressure
led to an increase in the material strength at low deformations as
deduced from the DMTA results (higher values of E
0
and E
00
).
3.3. Formulation of albumen/starch-based bioplastics
As an attempt to reduce protein concentration, the most expen-
sive ingredient in the nal bioplastic, corn and potato starch at dif-
ferent concentrations were added to the base formulation of egg
white protein and glycerol. Fig. 3 shows frequency sweeps tests,
performed in bending mode, at several temperatures (between
30 and 110 C) for selected samples containing potato or corn
starch, at different concentrations. Both samples show a predomi-
nantly elastic response at every temperature tested, with dramat-
ically higher values of the storage modulus (E
0
) than the loss
modulus (E
00
) in the whole experimental frequency window. An in-
crease in temperature was seen both to decrease the values of both
moduli and cause notable changes in the shape of the mechanical
spectra obtained. Thus, at room temperature, samples show a vis-
coelastic behaviour typical of a transition from the glass to the rub-
bery region. This viscoelastic behaviour, characterized by both
moduli showing similar slopes, suggests a highly elastic material
and the development of a three-dimensional network structure
that involves a large amount of interactions among chain
segments.
In the high temperature region, albumen/starch-based bioplas-
tics show a plateau region in E
0
(and a minimum in E
00
). This plateau
region has been extensively described in polymer rheology in
terms of an entanglement network formed by the simple topolog-
ical interaction of polymer chains rather than by crosslinking. In
this case, they behave like pseudo-gels at frequencies higher (time-
scale shorter) than the lifetime of the topological entanglements
(Ferry, 1980). In a variety of biological systems (which include
globular proteins and polysaccharides) the plateau observed comes
from a situation that falls between a temporary entangled network
and covalent crosslinking (Ross-Murphy, 1995). The rheological
behaviour described above would be consistent with the molecular
structure of an albumen/starch mixture, where hydrophobic inter-
actions usually act not at a point on the chain as covalent crosslinks
do, but involve more extended junction zones.
Fig. 2. DMTA spectra, in bending mode, of two albumen/potato starch bioplastics
(EW + G + PS 20 wt.%) obtained by two different processing methods: thermo-
plastic (solid symbols) and thermo-mechanical (open symbols). Inset: Appearance
of the resulting die-cut and moulded albumen/potato starch bioplastics.
2010 J. Gonzalez-Gutierrez et al. / Bioresource Technology 101 (2010) 20072013
Further, a study focused on the effect of starch type and concen-
tration on bioplastic thermo-mechanical behaviour was carried
out. Thus, DMTA temperature sweeps, at 1 Hz, were performed
on different blends containing starch in concentrations ranging
from 0 to 30 wt.%, and the values of |E
*
| and tan d at 40 and
120 C shown in Fig. 4. It can be observed that the addition of
starch caused slight changes in the values of both parameters,
which varied showing no clear pattern with increasing starch
concentration. From these results, it can be concluded that the
addition of starch to albumen bioplastic, within the concentration
and temperature interval tested, has no major effects on its
thermo-mechanical behaviour at small deformations, which, as
previously mentioned, seems to be mainly controlled by the pro-
tein matrix.
Regarding the tensile properties of the albumen/starch-based
bioplastics, Fig. 5 shows a rapid and monotonous decrease in both
elongation at break and tensile strength with increasing concentra-
tion (from 0 to 30 wt.%). This effect was more pronounced when
potato starch was used. These results suggest that starch granules
create heterogeneities in the protein matrix that acted as stress
concentration points, inducing cracking and resulting in lower val-
ues of strength and elongation (Wang et al., 2001). If compared
Fig. 3. Frequency sweeps, in bending mode, at different temperatures for thermo-mechanically processed albumen-based bioplastics containing 5 wt.% potato starch (PS), or
30 wt.% corn starch (CS).
Fig. 4. Evolution with the starch content of the complex modulus and loss tangent, at 1 Hz, at two different selected temperatures (40 and 120 C), for thermo-mechanically
processed albumen-based bioplastics containing either potato starch (PS), or corn starch (CS).
J. Gonzalez-Gutierrez et al. / Bioresource Technology 101 (2010) 20072013 2011
with the PLA/starch commercial sample, it should be noticed that
sample containing 10 wt.% corn starch shows similar values of
strength and much higher elongation at break.
Finally, the modication of albumen-based bioplastics formu-
lation with starch also affected their optical properties. As previ-
ously indicated, the transmittance of rectangular 3 mm thick
specimens was used as a measure for the transparency of the bio-
plastics studied, and the results for albumen/starch blends with a
starch concentration ranging from 0 to 30 wt.% are shown in
Fig. 6. Several commercially available synthetic polymers are in-
cluded for the sake of comparison. The upper photograph inset
in Fig. 6 shows that the albumen-based thermo-mechanically
processed bioplastic is a highly-transparent material with a value
of transmittance (38%) much higher than that of commodity poly-
mers like PP (6%) and LDPE (2%). Such a high value of transmit-
tance is lower than that for highly amorphous synthetic
polymers, such as PMMA (77%) though. In addition, it can clearly
be observed that the transmittance decreases as the content of
starch increases in the albumen bioplastics. After application of
heat and pressure, denatured starch granules structure seems to
produce a reduction in the material transparency, more important
than that corresponding to the linear aggregates structure of the
denatured globular albumen proteins. On the other hand, the
addition of corn starch had a higher effect on reducing the trans-
mittance than potato starch did. Thus, at 30 wt.% starch concen-
tration, the former presented a transmittance similar to that of
LDPE, whereas the latter still showed a transmittance higher than
PP. Differential scanning calorimetry (DSC) may shed light on this
issue. Endothermic events located at the gelation point of each
starch (corn and potato) were seen in the thermograms obtained.
Gelation is known to change the semi-crystalline structure of
starch into an amorphous one, which in turn produces a very
notable increase in transparency. Interestingly, potato starch pre-
sented its gelation peak at a temperature lower than corn starch
(115 and 120 C, respectively). Hence, corn starch gelation tem-
perature coincides with bioplastic moulding temperature. As a
consequence, structure transition would occur in a higher extent
for potato starch, which would satisfactorily explain the develop-
ment of a more transparent material. Despite the transparency
reduction after starch addition, the bioplastics studied allow light
to pass through. By looking at the pictures in Fig. 6, it can be seen
that even when 20 wt.% potato or corn starch was added, the
background is still visible.
4. Conclusions
This paper shows that albumen/starch-based bioplastics prop-
erties were greatly affected by the processing method. Thus, after
thermo-plastic processing, an opaque dough-like mixture with a
limited strength is obtained. However, when both heat and
Fig. 5. Evolution with starch concentration of the elongation at break and tensile strength for thermo-mechanically processed albumen-based bioplastics, containing either
potato starch (PS) or corn starch (CS).
Fig. 6. Evolution with starch concentration of the % transmittance (600 nm
wavelength light) for 3 mm thick specimens made of thermo-mechanically
processed albumen-based bioplastics, containing either potato starch (PS) or corn
starch (CS). Some common synthetic polymers results included for the sake of
comparison. Inset shows their macroscopic appearance.
2012 J. Gonzalez-Gutierrez et al. / Bioresource Technology 101 (2010) 20072013
pressure are further applied, it turns into a transparent material
with high elasticity.
No signicant changes in the DMTA spectra were detected by
starch addition, which would suggest that the viscoelastic behav-
iour at low deformation is ultimately controlled by the protein ma-
trix. On the contrary, blends showed a decrease in tensile
mechanical properties at high starch concentrations. Transparency
was also seen to decrease with increasing starch concentration.
Acknowledgements
This work is part of a research project sponsored by the Junta de
Andaluca, Spain (project P06TEP02126). The authors gratefully
acknowledge its nancial support.
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