Bioscience, Biotechnology, and Biochemistry

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Sol—Gel Transition and Elasticity of Starch

Akiko Kawabata, Sayuri Akuzawa, Yasuko Ishii, Toshiaki Yazaki & Yasufumi
Otsubo

To cite this article: Akiko Kawabata, Sayuri Akuzawa, Yasuko Ishii, Toshiaki Yazaki & Yasufumi
Otsubo (1996) Sol—Gel Transition and Elasticity of Starch, Bioscience, Biotechnology, and
Biochemistry, 60:4, 567-570, DOI: 10.1271/bbb.60.567

To link to this article: https://doi.org/10.1271/bbb.60.567

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Biosci. Biotech. Biochem., 60 (4), 567 570, 1996

Sol-Gel Transition and Elasticity of Starch

Akiko KAWABATA, Sayuri AKUZAWA, Yasuko ISHII, Toshiaki YAZAKI,* and Yasufumi OTSUBO**
Department of Nutrition. Faculty of Agriculture, Tokyo University of Agriculture. 1-1-1 Sakuragaoka, Setagaya-ku. Tokyo
156, Japan
* Eiko Seiki Co .. 2-1--6 Sasa::.uka. Shihuya-ku. Tokyo 151. Japan
** Center of Cooperative Research. Chiba University. 1-33 Yayoi-cllO. Inage-kll. Chiha 263. Japan
Received May 16, 1995

The concentration dependence of the mechanical properties of starch pastes near the sol-gel transition
point was analyzed by the scaling law derived from percolation theory. Since the storage modulus curves
for a starch paste slowly decrease with decreasing frequency, the plateau region at a frequency of 10- 1 S - 1
is shown to represent the elastic modulus that characterizes the network structure. The percolation threshold
can be taken as 1.5 wt% for corn starch and as 1.0 wt% for cassava starch. The storage modulus was
scaled on C-Cc (concentration-critical concentration, the critical exponents being determined as 4.2 and
1.8 for corn starch and cassava starch, respectively. It is suggested from these results that the intermolecular
bonding of corn starch was rigid and that of cassava starch was flexible.

Key words: sol-gel transition; percolation theory; scaling law; dynamic viscoelasticity; critical exponent

Starch gelatinization is a typical example of sol-gel
transition, and appears commonly in our dialy life and in
many industrial processes. As a main food category, starch
is processed in various ways and aggregation often occurs
during processing, giving rise to the shape and texture which
mainly contribute to the sensory attributes of food products.
Mechanical properties such as the viscosity of the sol and
elasticity of the gel change dramatically near the sol-gel
transition point. However, the behavior of the viscosity
and elasticity near the sol-gel transition point has not been
well analyzed. De Gennes I, has suggested that sol-gel
transition could be a type of percolation transition, enabling
scaling concepts to be applied to the dramatic changes in
physical properties that occur with sol-gel transition. Since
then, experimental studies have been made on synthetic
polymers, and the critical exponents which appear in the
scaling law have been experimentally evaluated,2 - al- 4,
though not much work has been done on natural polymers
like food gels. In addition, a few studies have been conducted
on application of the theory to whey protein 5, and gelatin. 6)
There has been considerable research in recent years on
the fundamental mechanical properties of the sol and gel
of starches to find a relationship between the physical
properties and aggregation behavior of these materials. 7 )
Dynamic viscoelastic methods provide an excellent tool for
studying rheological changes near the sol-gel transition
point. Starch is composed of two polymers with different
structures, amylose and amylopectin, and consequently, the
mechanical properties of starch gels are different from those
of pure amylose and pure amylopectin gels. 8) Very few
dynamic rheological data are available for near the sol-gel
transition point of starch.
During the gelatinization process, a starch solution is
converted from a viscous liquid to an elastic gel. The process
and mechanical properties of a gel strongly depend on the
molecular structure of the starch. However, according to
the scaling rule, the physical properties near the sol-gel
transition point are independent of many details of the
molecular structure, and a scaling analysis enables us to
understand the characteristics of the starch gelatinization
process.
In this study, dynamic viscoelastic measurements were
performed to investigate the relationship between the
molecular structure and macroscopic properties of starch
pastes near the sol-gel transition point. The characteristic
behavior during the sol-gel transition of starch will be
discussed on a molecular basis.
Theoretical
A dilute aqueous solution of starch consists of a collection
of discrete chains. With increasing concentration, these
chains are crosslinked, forming finite randomly branched
chains. When the concentration is increased beyond a
critical value, an infinite network is formed that is composed
of three-dimensional elements and finite branched chains.
A collection of finite branched chains is called a sol, and a
system made up of an infinite three-dimensional network
is called a gel. The structural changes from discrete chains
to the infinite network in the course of increasing con-
centration can be analyzed as sol-gel transition or per-
colation transition.
The distribution of monomers in branched chains and
the network formation process are often described by the
percolation theory. Site percolation deals with the
distribution of cluster size for monomers distributed in an
infinite lattice composed of sites linked together by bonds.
When sites these occupied at random with probability pS
and adjacent occupied sites are inevitably connected, there
exists critical probability p~, above which an infinite
network is built up. The main task in the percolation
problem is to evaluate the physical properties of the
percolating network above critical probability p~. Once the
infinite network has been built up, the system elastically
responds to a small deformation. Although the elasticity
arises only from the deformation of each monomer, the
infinite three-dimensional network is essential for elastic
response as an overall effect of the system. Therefore, the

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568 A. KAWABATA I.'t al.

appearance of elasticity in a starch paste is closely related
to the structural change from discrete chains to an infinite
network.
Experimental
Materials. The two starches used were produced in 1993: corn (Zea
mays L.) starch was supplied by Sanwa Starch Industry Co., and cassava
(ManillOt esqulenta CRANTZ) starch was supplied by Thailand Ajinomoto
Co. The starch samples were purified by washing several times with
demineralized water.
Preparation of the starch pastes. Each starch suspension was weighed
in a beaker to give a OS-4.0% cent ration (w'w on the basis of the
anhydride), demineralized water being added to bring the total to 100 g.
The starch suspension was allowed to swell for 15 min, stirred by hand
with a glass rod at about 120 rpm while being heated in a thermostatic
tank held at 85C and then heated for 20 min at 100"C under saturated
steam conditions in a steam oven (RO-3700: Mitsubishi Denki Co.). The
concentration (w/w) was then adjusted with demineralized water, before
each sample was degassed and stored at 20C for 20 h. Since each starch
paste was heat-treated under a condition at which complete dispersion
took place, the stable state was attained at the temperatures for sample
storage and rheological measurements.
Measurement (~l (~vnamic viscoelasticity. Dynamic viscoelasticity G *
(=G'+iG") was measured in the frequency range of6x 1O- 2 6x lOS-I
by using a Rheo-Stress RS 100 rheometer (Haake Co.). The measurements
were carried out under conditions of constant stress and a temperature of
50 C. The diameter of the upper disk was 60 mm, and the gap between
the two plates (sample thickness) was I mm. When the bottom disk was
moved upward for thickness adjustment, a very small amount of the sample
was trimmed from the edges, although this procedure did not significantly
damage the sample structure. The evaporation of water would a cause
structural change around the edge of a disk, so each experiment was
completed within 15 min; no significant changes in rheological properties
were observed during the measurements.
was 0.03 Pa and the resultant strain was in the order of
I x 10'- 3. These are typical viscoelastic curves for a starch
solution in the gel state. The moduli are relatively constant
at low frequencies, indicating a network structure with a
very long or infinite relaxation time. In a gel, elastic response
is predominant, producing values for the storage modulus
more than 10 times those of the loss modulus.
Figure 2 shows the stress dependence of the storage and
loss moduli and of strain at a frequency of 0.62 s - I for the
2.5 wt% corn starch paste. For all the solutions studied,
both moduli were constant at low stress and began to
decrease above a critical value. The sharp drop in storage
modulus reflects a breakdown of the structure that has
developed. If the measurements are carried out under a
cycle of increasing and decreasing stress, the moduli at a
given stress would be different. Therefore, the data under
low stress, at which structural breakdown would not be
significantly induced, are required to assess the rheology
related to the structure. Since our research interest was
centered mainly on the elastic properties, only the results
for the storage modulus will be presented here.
Figure 3 shows the frequency dependence of the storage
modulus for corn starch pastes of different concentrations.
At 1.5-1.8 wt% concentrations, the storage modulus rapidly
and linearly decreases with decreasing frequency on the
log-log plot. More dilute pastes would show no elastic
response. When the concentration is increased beyond
2 wt%, the frequency-dependent curve shows a plateau. In
1
10

Scaling analysis. Scaling arguments show a power law dependence of >--

elastic modulus G' on the difference in concentration from critical value C c : 10°
G'=k(C-CY ro
a..
where C is the concentration, and n is the critical exponent. Many 10'1
authors'} - I,}) have analyzed the scaling behavior near the percolation ~
threshold by the use of storage modulus G' at low frequencies. In this
study, the value at a frequency of 10- I S - I was used as the elastic modulus 'c.9
to characterize the network structure. 10- 2
10,2 10,1
10 ° 10 1
Results 5t ress (Pa)
T
Figure I shows the frequency dependence of storage
Fig. 2. Stress Dependence of Storage Modulus G', Loss Modulus Gil,
modulus G', loss modulus Gil, and the absolute value for and Strain at a Frequency of 0.62 s - I for a 2.5 wt% Corn Starch Paste.
complex viscosity 11]*1 (= 1G* I/ev) for the corn starch paste
at a concentration of 3 wt% by weight. The applied stress 3
10
2 ro
\I) 10 a..
ro 2
a.. 10
'<-, ~-~
*.c:-- 10 1
G'I \I)
~

~
'0 10
1 3 1] 1
0
ro
a.. 10° ----- G" --- E
1 ~.., 4J
~ 17*1 :).,a 01 10°
<-'
~
0
~
10,1

Angular frequency w

Fig. l. Frequency Dependence of Storage Modulus G', Loss Modulus

An gular f requ ency w ( S'I )

Gil, and Absolute Value of Complex Viscosity 111* 1(= 1G* liw) for a Corn Fig. 3. Frequency Dependence of Storage Modulus G* for Corn Starch
Starch Paste at a Concentration of 3 wt %. Pastes at Different Concentrations.

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 Sol Gel Transition of Starch 569

2
-; 10
a..
,
(!)

11'1
10 1
:J
1
:J &. 10
'0
0
E 10°
CIJ
01
III 1.5
~
0
10- 1
Vi 10- 2 10- 1 10°
Angular frequency
Fig. 4. Frequency Dependence of Storage Modulus G' for Cassava
Starch Pastes at Ditferent Concentrations.

the time scale of experimentation, the concentrated pastes (wt%)

did not have a significant relaxation process. An important
Fig. 5. Critical Behavior of Storage Modulus G' near the Percolation
feature with regard to the concentration dependence of the Threshold for Corn (0) and Cassave (.) Starch Pastes.
storage modulus is the existence of a critical value for the C is the concentration and C, is the critical concentration for a 1.5 wt%, corn starch
appearance of this plateau region. and I wt%, cassava starch.
Figure 4 shows the frequency dependence of the storage
modulus for cassava starch pastes at different concentra- offrequency studied. Such pastes are regarded as percolating
tions. At low concentrations of 1.0-1.4wt%, the pastes do systems. On the other hand, dilute pastes did not respond
not show the plateau on the curve, the storage modulus elastically, even at high frequency, these pastes being
rapidly decreasing with decreasing frequency on the log-log classified as nonpercolating systems. At intermediate con-
plot. More dilute pastes would show no elastic response. centrations, the storage and loss moduli are comparable
Above 1.5 wt%, the cassava starch pastes can be regarded in the high frequency range, although they rapidly decrease
as percolating systems, because the storage modulus is with decreasing frequency. In this study, we have assumed
higher than the loss modulus over the entire range of that the concentration at which the storage modulus was
frequencies. detected in the frequency range of I 0 ~ 1_6 x lOs ~ 1
From the dynamic viscoelastic measurements, as the corresponds to the percolation threshold. By repeating the
concentration was increased, each starch paste changed experiments, the percolation threshold could be taken as
from a viscous fluid to a gel-like paste which showed an being 1.5wt% for corn starch and 1.0wt % for cassava
elastic response at very low frequencies. It is reasonably starch.
accepted that a starch paste at a particular concentration Figure 5 shows the critical behavior of the storage
may be in the critical state between a sol and gel. A sol can modulus near the percolation threshold for the corn starch
be defined as a substance that shows continuous flow with and cassava starch pastes, respectively. For each system,
the application of stress and that gives an infinite strain the plots are closely related by a straight line, the slope
after a long time_ A gel-like solid can be defined as a of which gives the critical exponent. The storage modulus
substance that has a certain shape, the deformation of which was scaled on C-Cc ' and the critical exponents were
reaches equilibrium after a long time under constant stress. determined to be 4.2 and 1.8 for corn starch and cassava,
In respect of the gelation process, a system consisting of respectively.
finite branched polymers is regarded as a sol, and one
conteining a infinite three-dimensional network with Discussion
unbounded polymers is regarded as a gel. As a result, the De Gennes 1) has pointed out that the elastic modulus of
elastic response is considered to be the manifestation of a a polymer gel is analogous to the electrical conductivity,
network structure. because the transmission of force in the network can be
For a polymer system whose molecular weight and modeled by an isotropic force constant. For an electrical
fraction of functional groups are controlled, the relationship network in which the conductor carries a scalar quanity,
of G' = G"( G"/G' = I) can be established irrespective of the the critical exponent is estimated to be 1.8. It has been
frequency at a point where an infinite three-dimensional reported 13) that the value for a polymer gel is 1.9, which is
network has been developed. 20 ) The gelation point can be close to that predicted from scalar elasticity percolation.
experimentally determined by this procedure. However, for The value for the critical exponent of gelatin 6 ) and
a starch paste, ratio G"/G' depends on the frequency, and polyacrylamide 19 ) is about 2, which is also similar to the
hence cross-over does not provide the gelation point. The value predicted by the scalar percolation theory. The elastic
percolation threshold was thus determined from the network for cassava starch can be modeled by an isotropic
frequency-dependent curve for the storage modulus. force constant. The isotropic elasticity may arise from the
When the concentration was increased to a point at which entropy effect of the chains. Since the polymer molecules
the storage modulus reached 10 ~ 1 Pa in the range of are considered to behave as freely jointed chains in solution,
6 x 10 ~ 2-10 s ~ 1, all the pastes studied showed a storage the conformation of a linear polymer can be described by
modulus higher than the loss modulus in the overall range the random walk model. Considering that the high internal

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570 A. KAwARATA
degree of freedom achieved in deformable polymer coils starch gel was rigid and that of cassava starch gel was
leads to isotropic elasticity, the chains of cassava starch that flexible with isotropic elasticity.
make up the network may be highly flexible. On the other
hand, for many suspensions in which the particles are References
connected by rigid bonds, the critical exponent has been I)
found to be about 4. 21 . 22 )
This difference in critical exponents shows that the two 2)
lastic properties have different characteristics. In an elastic
3)
network, the bonds transmit central and transverse forces.
According to theoretical studies on the percolation of an 4)
elastic network, 1 0.11) the critical expponent depends on the
local elastic constant, which is given by a set of central and 5)
transverse (anisotropic) elastic constants. The critical
6)
exponent determined for corn starch suggests that the chains
between crosslinks were rigid, especially with respect to 7)
transverse bending forces. For corn starch pastes, the energy
effect may be responsible for elasticity. The factor
controlling the critical behavior of the elastic network in a 8)
starch paste is the vector nature of the chain between the 9)
crosslinking points. 10)
The amylose content of starch is 25.0% for corn, and for II)
cassava. 23 ) The weight average molecular weight (M~\.) of 12)
amylose measured by the light-scattering method is 0.5 x 10 6
13)
for corn, whereas it is 1.4 x 10 6 for cassava, 2.5 times 14)
larger. 24) The weight average molecular weight (Mw) of 15)
amylopectin is 6.2 x 10 7 for corn, whereas it is 40.1 x 10 7
for cassava, being about 6.5 times as large. 24 ) 16)
Starch is composed of two macromolecular components
17)
which differ in their chemical structures; namely, amylose 18)
is almost totally linear with few branches,25) whereas 19)
amylopectin is highly branched. During the gelation of a
starch paste, the first rheological change in the sol-gel 20)
21)
transition of the starch is induced by amylose matrix gela-
22)
tion due to amylose association. 26 ) An amylopectin gel is 23)
postulated to be the result of the formation of pairwise
intermolecular association, presumably due to the helix 24)
formation between the outer A chains of the amylopectin
molecule in the amylose matrix. 27 ) The dynamic visco-
25)
26)
elasticity of a starch system strongly depends upon the
amylose-amylopectin ratio and aggregated state. 28 ) On the 27)
basis of the percolation analysis, the difference in the
28)
network structure of different starch gels can be explained
by the scaling exponent obtained in this present work. The
critical exponents were determined to be 4.2 and 1.8 for
corn starch and cassava starch, respectively. It is suggested
from these results that the intermolecular bonding of corn
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