Sie sind auf Seite 1von 8

The Effect of

Temperature Range of Potato Starch


By I.D. Evans and D.R. Haisman,
Sharnbrook, Bedford (England)
The gelatinizationbehaviour of potato starch in an excess ofwater or
solutions of sugars, other organic hydroxy compounds, or various
inorganic salts was studied. The distribution of water and solutes
between the external phase and the starch granules was measured by
refractometryand adye exclusion technique. When the limited water
uptakeofnative starchgranulesistakenintoaccount, thecooperative
nature of gelatinization and the effect of water content on
gelatinization behaviour can be explained solely on the basis of the
Flory theory of polymer melting. Following the same argument, the
effect of many solutescan be approximatelydescribed by the derived
relationshipbetween initial gelatinizationtemperature,water activity
of the system and volume fraction of water in the granules.

Die Wirkung geloster Stoffe auf den VerkleisterungstemperaturBereich von Kartoffelstarke. Das Verkleisterungsverhalten von

Kartoffelstarke in einem UberschuD von Wasser oder Losungen von


Zuckern, anderen organischenHydroxyverbindungenoder verschiedenen anorganischen Salzen wurde untersucht. Die Verteilung von
Wasser und gelostem Stoff zwischen der externen Phase und den
Starkekornernwurde durch Refraktometrieund ein FarbausschluRverfahren gemessen. Wenn die begrenzte Wasseraufnahme der
nativen Starkekorner mit in Betracht gezogen wird, kann die
mitwirkende Natur der Verkleisterung und die Wirkung des
Wassergehalts auf das Verkleisterungsverhalten ausschlieRlich auf
der Basis der Flory-Theorie des Polymerschmelzens erklart werden.
Den gleichen Argumenten folgend, kann die Wirkung vieler geloster
Stoffe annahernd durch die Beziehung zwischen Anfangs-Verkleisterungstemperatur,Wasseraktivitlt des Sysems und Volumenanteil des
Wassers in den Kornern beschrieben werden.

1 Introduction
The gelatinization of starch granules heated in water is a wellknown phenomenon, during which the granules lose their
semi-crystallinity and swell. As a result of this change, starch
pastes develop the viscosity which makes them technically
useful as ingredients in foods, and as adhesives and sizes, and
consequently the process of gelatinization has been a subject
for research for many years.
In water, gelatinization (as defined by loss of birefringence)
occurs over a range of temperatures characteristic of the type
of starch and usually of the order of 10C. Under the
microscope it can be seen that individual granules gelatinize
over a much shorter temperature range - of the order of 1C
- so that the broad range observed for total gelatinization of
the starch is due to differences in susceptibility amongst the
granules.
The gelatinization temperature range is influenced by changes
in the environment of the starch granules - for instance by
reducing the amount of water available t o the granules, or by
adding high levels of hydrophilic solutes such as sugars or
other polyhydroxy compounds, or even by the zddition of
simple salts. The most general effect is to raise the
gelatinization temperature compared to gelatinization in
excess ofpure water, but sometimes, particularly in the case of
salts, the gelatinization temperature is lowered. There is
however considerable confusion in the literature about the
actual nature of many of these effects, at least partly because
of the many different techniques which have been used to
examine the phenomenon.
Thus, although salts are generally thought to inhibit
gelatinization, G u m [l] observed that sodium chloride (at a
level of 2.5%) increased the peak viscosity of corn and wheat
starches (but not waxy maize) in the Brabender Viscoamylograph. The onset temperature for viscosity development was
not affected by this concentration of sodium chloride. Other
salts, however, can cause gelatinization at room temperature
[2], whilst saturated sodium sulphate inhibits gelatinization

224

even at the boiling point [3]. Oosten [4] observed that sodium
chloride generally elevated the gelatinization temperature of
corn starch except at high concentrations, when it fell again.
Sodium hydroxide (-0.5-M)
in the presence of high
concentrations of sodium chloride unexpectedly raised the
gelatinization temperature of corn and other starches by up to
25C - an effect which was much less marked at lower
sodium chloride concentrations or in the presence of sodium
sulphate. Gough and Pybus [5] also observed strange effects
when wheat starch was gelatinization in various metal
chloride solutions ;in general, an initial increase was followed
by a decrease in gelatinization temperature as the concentration was increased. With some salts, such as calcium chloride,
a further increase in concentration raised the gelatinization
temperature again.
There is a greater measure of agreement about the effect of
non-ionic solutes. Thus, saccharides and polyhydric alcohols
have been found to raise the gelatinized temperature of
starches by varying amounts [6, 7, 8, 9, lo]. Some of these
effects have been qualitatively explained in terms of the effect
of the solutes on water structure, or by specific ion effects [5,
61. It is however, difficult t o completely rationalise all the
results on this basis. In an alternative approach Lelieure [ll]
has used the theories of polymer chemistry [12], treating the
gelatinization of starch as the melting of a homogeneous
polymer.
Support for this model of gelatinization as a melting
phenomenon is provided both by X-ray diffraction studies
which show that there is a loss of semicrystalline order during
gelatinization and from calorimetric studies which show that
this is associated with a highly cooperative loss of structure.
Solvents such as water, or aqueous solutions, can be regarded
as diluents in the system and their effects explained in terms of
their volume fractions and the various interaction constants.
By this view, the presence of water and other additives would
be generally expected t o lower the melting point (gelatinization temperature) ofthe pure (i.e. dry)starch, and there are

starch/starke 34 (1982) Nr. 7, S. 224-231

0 Verlag Chemie GmbH, D-6940 Weinheim 1982


0038-9056/82/0707-0224$02.50/0

many indications in the literature of the corollary, that


reducing the water content of starches tends t o raise their
gelatinization temperature [13, 14, 151.
However, it was not until the use of Differential Scanning
Calorimetry (DSC) that it was discovered that the effect of
reducing water content on gelatinization temperature was
rather more complicated than would be expected from this
simple view. Donouan [16] showedthat when theratio ofwater
to starch was less than about 2 : l (g/g dry starch) the
gelatinization temperature range (as indicated by the DSC
endotherm) widened. As the water content was progressively
reduced, the endotherm split into two peaks, the upper end of
the range' moving t o higher and higher temperatures.
Eventually the lower peak disappeared, while the upper peak
continued to move upwards. These results could be fitted to
the standard equations for the melting ofpolymers in adiluent
system, assuming that the upper limit of the high temperature
endotherm represented the true melting point of the system.
Donovan suggested that thesplittingof theendotherm wasdue
to the swelling ofthe amorphous regions ofthe starch granule
"stripping" starch polymer chains from the crystallites and
effectively tearing them apart. Under limited water conditions
this process can only go so far and is then superseded by
conventional "melting" (the high temperature endotherm).
In a further elegant experiment Donovan [I71 showed that
when the amorphous parts of the granules were eroded by
treatment with acid, as in the so-called Niigeli amylodextrins,
the gelatinization temperature was moved to the higher
temperature range. This demonstrated that the amorphous
regions in the granule play an essential part in determining
both the gelatinization temperature and the temperature
range. In his deductions from the experiment, Donovan
postulated that the crystallites are coupled t o the amorphous
regions so that the swelling of the amorphous region exerts a
force on the crystallites which destabilizes them, and directly
determines the sharpness of the gelatinization transition and
the temperature at which it occurs. Biliaderis et al. [I81
reached a similar conclusion, describing the gelatinization of
starches as a solution-assisted melting of the starch crystallites, a process facilitated by the swelling of the amorphous
parts of the granule.
The Lelieure model for gelatinization uses the Flory-Huggins
equation for the melting of a polymer in the presence of a
diluent (1) :

where TO,is the melting point ofpure polymer, AH, is the heat
of fusion of the polymer repeat unit, V , and V1 are the molar
volumes of repeat unit and diluent respectively, v1 is the
volume fraction of diluent and $1 is the polymer-diluent
interaction constant. In the starch-water system it is assumed
that the starch-water interaction constant is small, so that the
second term in the bracket onther. h. s. oftheequationcan be
neglected in comparison to the first. With thisapproximation,
plots of the upper temperature limit of the DSC endotherms
(supposedly the melting point of the most perfect crystallites
in the starch polymer) against the volume fraction of water
(based on the water content ofthe whole starch-water system)
are found to be linear for volume fractions of water varying
from about 0.3 to 0.8.
As the Floryequation socloselydescribesat least oneaspect of
the gelatinization of starch granules in water, it should be
possible t o use the same approach to account for the effects of
different solutes, and, indeed, Lelievre [19] derived the
appropriate equation for the melting of a polymer in a 3starch/stBrke 34 (1982) Nr. 7 , S. 224-231

component system (solvent-polymer-solute) and applied it to


the gelatinization of wheat starch in the presence of either
maltose or glucose. Depending on the values assigned to the
different interaction constants, themselves not easily determined by experiment, the equation predicted the gelatinization
temperatures in these systems very well. However, it is more
difficult t o estimate the probable magnitude of the interaction
constants when the solute is not related t o the structural unit
of the polymer, and Lelieure stressed the complexities of
extending this approach.
So far, in applying the Flory theory to the phenomenon of
gelatinization it has been generally assumed that the relevant
volume fractions are those appertaining in the system as a
whole. This presupposes that the starch-water system is
homogeneous, whereas in fact, it consists of individual
granules suspended in a variable amount of liquid phase. The
granules are in osmotic equilibrium with this external phase,
and once they are fully swollen, further additions of the liquid
phase will not affect their composition. Thus it would be more
correct, in applying the Flory equation, to use volume
fractions based on granule composition rather than on the
composition of the complete system.
We have investigated the composition of potato starch
granules in equilibrium with external solutions of different
salts and polyhydroxy compounds. At the same time we have
determined the effects of these solutions on the gelatinization
temperature of potato starch, using DSC. These data have
been used to test and refine the model for gelatinization
outlined above, with the hope of rationalising the effects of
different solutes. In the event we have found that, when the
limited volume of the granule is taken into account, a large
part of the gelatinization phenomenon, including the effects
of many solutes, can be explained on thermodynamic
grounds.

2 Materials and Methods


The potato starch used in this investigation was a commercial
sample (Perfectamyl D , supplied by Tunnel AVEBE Starches
Ltd.,Rainham, Kent, England). Other chemicals used were of
analytical grade.
For DSC investigations a Perkin Elmer DSC 2 was used with
liquid paraffin as the thermal reference, samples being
scanned at 10C per min (usually from 7"C-l47"C;
280K -420K). Areas of peaks (which are proportional t o
the enthalpy changes involved) were determined by cutting
out and weighing - two or more determinations were made
and are expressed relative to the dry weight of the starch.
Three temperature parameters were measured - the onset
temperature, the termination temperature, and the temperature of maximum differential heat flow (peak temperature).
The last of these is easily estimated, but onset and termination
temperatures are generally not very sharply defined. The
commonly used technique for these temperatures [I 6,181 is to
take the intersections between straight lines drawn through
the baselineandthesidesoftheDSCpeak. In practicethiscan
be a very arbitrary procedure, and difficult to apply when the
base lines are curved and peaks are broad or split. The
alternative, used here, is t o draw a smooth curve through the
base line and determine the intercepts with the peak. Unless
otherwise stated the DSC data refer to 10/1 (w/w) ratios of
medium t o starch.
The water activities of the solutions and starch-solution
mixtures were determined using a Sina Equihygroscope
(Nova-Sina, Zurich).
Solute and water distribution in starch-solution systems was
estimated from Blue Dextran exclusion [20,21] and refractive
225

index changes. Potato starch (of known moisture content, of


the order of 16%)was weighed (3 - 4 g) into a centrifuge tube
followed by 6 - 7 g of solution,containing solute and 1'YOBlue
Dextran. The tube was sealed and the contents thoroughly
mixed. Stainless steel ball bearings were added to the tube t o
facilitate mixing. The mixture was left overnight and then
centrifuged. A weighed quantity of supernatant was removed
and diluted for optical absorbance measurement. It was
replaced by an equivalent weight of the initial solution
without Blue Dextran, and the mixing and centrifuging
procedure repeated. A second sample of supernatant was
removed, diluted and measured in the spectrophotometer.
From the initial absorbance and the two supernatant
measurements, two estimates of the amount of water
absorbed by the starch were obtained. Agreement was
generally within 2% for these estimates and duplicate
determinations agreed within 3% of the average value.
Changes in solute concentration were followed by running
duplicate experiments without Blue Dextran and measuring
the refractive index of the solution before and after
equilibration with starch.

gelatinization temperatures. Curves showing how the onset


temperature of gelatinization varied with concentration of
glucose, sucrose, maltose, ribose, glycerol and ethanol are
given in Figure 2. The results are in good agreement with those
of previous workers [6, 191.

- 3 89 0

:I
u

370

rn

3 Results

10

20

30
LO
50
60
70
Concentration 1% w / w 1

80

90

Figure 2. The effect of hydroxy compounds on the initial gelatinization temperature of potato starch; * water, A ethanol, V glucose,
0 sucrose, 0 ribose, 0 maltose, o glycerol.

3.1 Gelatinization Temperatures


In general in the presence of a low ratio of starch to medium a
single endotherm corresponding t o gelatinization was observed, the position, shape and enthalpy of this endotherm being
independent ofthe starch t o medium ratio until this reached a
value near t o unity. If the samples were reheated immediately
no endotherms were seen - as expected from the irreversible
nature ofgelatinization ;if however, the samples were kept for
hours or days before reheating, an endotherm did appear
corresponding to retrogradation of the gelatinized starch.
In the presence of sugars and other hydroxylated compounds
the gelatinization temperature range increased monotonically with concentration, AH and the shape of the endotherms
being substantially unchanged, within experimental error as indicated by the parallelism of the curves in Figure 1 which
shows the effect of increasing concentrations of both glycerol
and idium chloride on t h e onset, peak and terminal

Salts had more complex effects on gelatinization, illustrated


here with five examples - sodium chloride, sodium acetate
(buffered to p H 7.0with acetic acid), sodium sulphate, sodium
hydrogen phosphate (pH 6.7) and calcium chloride. The
effects of increasing concentrations of these salts on the onset
gelatinization temperature are shown in Figure 3.

- 360

390

i!310t
+

380

'0
/

300)

370

rn

"360
P350

? 3LO
330
'.

320

10

20

30
LO
50
60
Concentration I%w / w )

70

80

90

Figure 1. The effect of glycerol and sodium chloride on the


onset, peak and
gelatinization endotherm ; o - 0,A - A, 0-0,
termination temperatures for various concentrations of glycerol ;
0 - 0 , A-A, - m, for sodium chloride.
226

Molarity

Figure 3. The effect of salts on the initial gelatinizationtemperature


of potato starch; * water, o sodium chloride, A sodium acetate,
0 sodium sulphate, 0 calcium chloride, sodium hydrogen
phosphate (pH 7.0).

3
c

rn

Sodium sulphate and sodium hydrogen phosphate both


progressively increased the gelatinization temperature in the
same way as the saccharides previously discussed, AH also
being invariant within experimental error.
Sodium chloride and sodium acetate had a different effect. At
low concentration these salts slightly increased the gelatinization temperature, but when the salt concentration was
increased further the gelatinization temperature fell.
A similar trend was found in calcium chloride solutions, but
then, at higher concentrations still, a further change took
starch/starke 34 (1982)Nr. 7, S. 224-231

place. Thus at intermediate concentrations (2.5 and ~ . O - M )


gelatinization occurred during preparation of the starch/calcium chloride mixtures, but at higher concentrations (4.0 and
~ . O - M ) this did not occur. The latter two samples showed
single peaks with DSC, but these peaks were now exothermic
and considerably broader than the usual gelatinization peaks,
with A H values of about - 17.5 cal/g compared to + 4 cal/g
for starch in 1-M calcium chloride. The samples were fully
gelatinized after this treatment. These effects can be explained
if it is postulated that the starch becomes osmotically
dehydrated in the presence of high concentrations of calcium
chloride (a, in 5-M calcium chloride is 0.41). Then when the
sample is heated for DSC, the starch will rehydrate - an
exothermic process which overlaps and obscures the endothermic gelatinization peak. The estimated enthalpy for the
hydration of starch is about -25 cal/g [22], which, added to
the normal enthalpy of gelatinization of about f 4 cal/g,
corresponds fairly closely to the observed change.

In the presence of solutes the absorption of water was reduced,


roughly in proportion to the volume ofsolute absorbed. Thus,
at solute concentrations up to about 40% the amount of
solution absorbed was still between 0.5 and 0.55 ml/g starch.
At higher concentrations however, for most of the solutes
examined, the volume absorbed was reduced. In all cases the
solute concentration (based on the solute and total water
content of the granule) inside the granule was lower than the
external concentration. This probably indicates that some of
the water in the starch granule is very tightly bound to the
starch (hydration water) and cannot be regarded as in the
same phase as the absorbed solution. Calorimetric measurements [24] have shown that about 20% of the total absorbed
water is very much more strongly bound than the remainder,
and if the internal concentrations are corrected by this
amount they do approximate to theexternal soluteconcentration.

4 Discussion
3.2 Absorption Results
Potato starch granules in equilibrium with excess water were
found to have a water content of 0.538 g water/g dry starch
(standard error of the mean, 0.004) as measured by the
exclusion of Blue Dextran. This is in good agreement with
estimates in the literature of 0.509 [23] and 0.567 [24] and with
the extrapolation of water vapour adsorption results [22,24,
251. Our results were obtained at temperatures of 20 - 25 "C ;
no significant change in the total absorption was observed on
raising the temperature to 50C.
Curves for the absorption of water and water solute in the
presence of different solutes are shown in Figure 4.

0.t

4.1 Variation of Gelatinization Temperature with


Water Content

Many workers have now shown that under conditions of


limited availability of water, i.e. for potato starch at moisture
levels of less than about 67% of the total wet weight, the
gelatinization temperature of starches is raised above the
normal level when water is in excess. The effect is however
different according to whether one considers the temperature
at which gelatinization begins (the onset temperature) or at
which it ends (final temperature). A typical set of results for
potato starch (taken from our own and Donovan's data [16])
plotting gelatinization temperatures (initial and final) against
watercontent ofstarchisshownin Figure 5.Ascan be seen the
final gelatinization temperature starts to increase when the
water content of the starch falls below 2 g water/g starch. The
initial gelatinization temperature, on the other hand is
constant until the water content of the starch falls to 0.6 g
water/g starch. Below this water level the initial temperature
rises steeply.

z 0.:
L

c
rn

Ill

x
L

m
\

E, 0.1

-0
W

n
L

Q
W

-> 0 :.3
0

\
\

0.;

\
0

10

20
30
40
50
60
Concentration o f Solute (%w/wl

l i n t 0 Separate Peak

70

80

m
Figure 4. The absorption of water (solids symbols) and water
solute (open symbols) in presence of different solutes; water,
0 glycerol, A maltose, v ribose, 0 glucose, 0sucrose,
sodium
chloride, m calcium chloride, 1sodium sulphate.

starch/stiirke 34 (1982) Nr. 7, S. 224-231

Single Peak

320

0 3

10
20
Water Content ( g / g Dry Starch1

30

Figure 5 . The initial ( 0 )and final ( 0 )gelatinization temperatures


of potato starch as a function of water content (incorporating data
from Donovan [16]).

227

Semicrystalline polymer systems always melt over a range of


temperature. As equation (1) assumes that the system is at
equilibrium, Flory reasoned that, strictly, T , should be taken
as the temperature of completion of melting under very slow
heating conditions, as this should lie close to the equilibrium
melting point for the hypothetical macroscopic perfect
crystal. However there seems no reason why a similar
equation should not apply t o the melting of less perfect
crystallites. Certainly, from the practical viewpoint, data for
the initial gelatinization temperatures, corresponding to the
melting of the least perfect crystallites, also fit equation 1 over
a large part of the melting point range.
As already noted it has generally been assumed that the
relevant volume fractions to use in the Flory equation are
those for the total system. This is clearly inappropriate for
starches since, once the swelling capacity of the ungelatinized
granules has beenreached, changes in the quantity ofexternal
medium will not affect granule composition. Hence, the
volume fractions for the Flory equations should be based on
granule, composition rather than the composition of the whole
system, particularly when considering initial gelatinization
temperatures.
Our estimate ofthe water content of potato starch at a , = 1 is
0.54 g aater/g dry starch, corresponding to a volume fraction
of 0.45. It is significant (Fig. 6) that when the water content of
the starch is less than this amount ( i . e . at a , < l ) ,both initial
and final gelatinization temperatures are increased. Above
this water content the initial gelatinization temperature is
constant, and we suggest that this is related t o the fact that the
water content of the granules cannot increase, further added
water remaining extra-granular. The final gelatinization
temperature, however,continues to fall as the water content is
increased up to a level of about 2 g/g dry starch, when the final
temperature also becomes constant.

8E3 6 0 1

b
\

p,P

0.6 0.7 0.8


0.5
Water Activity (a,)

0.9

1.0

Figure 6. Initial gelatinization temperature us. water activity ;


* water, 0 maltose, 0 glycerol, 0sucrose, A glucose, 0 ribose,
v ethanol, @ sodium chloride, calcium chloride, x sodium
acetate. A sodium hydrogen phosphate (pH 7.0),
sodium
sulphate.

At this point the granules are effectively suspended in an


excess ofwater, and the gelatinization endotherm consists of a
single peak spanning, in the case of potato starch, a range of
about 16C. It isgenerally accepted that thisendothermis the
result of the melting of the starch crystallites in the
granules. It is to be expected that these crystallites will vary
quite widely from perfect or nearly perfect to imperfect or
rudimentary. If we extend the Flory theory t o cover imperfect
as wellas perfectcrystallites, then at constant volume fraction

228

of water, the melting points of individual crystallites will vary


according to their degree of perfection, or stability. Thus it is
reasonable that the gelatinization endotherm should cover a
broad range of temperatures. The surprising circumstance is
that, as microscopic observation shows, individual granules
gelatinize over a very narrow temperature range - generally
less than 1 C. Considering the stochastic processes in plant
cells which control the synthesis of the starch granules, it
seems very unlikely that this is because the crystallites in
individual granules all have the same stability - it is more to
be expected that each granule has its own population of
crystallites covering a broad range of stabilities.
If we examine the range of gelatinization ofthe granules rather
than the range of melting of the crystallites, it may be assumed
that thegranule whichcontains the least stablecrystallites will
be the first to start to change on heating. Initially, this granule,
like all the other granules in the system, contains 0.54 g
water/g starch. When the least stable crystallites in this
granule melt, some of the constraints restricting the swelling
of the granule are removed, and it can absorb some of the
external water. The water content of the granule is now
greater than 0.54, and hence the melting point of the
remaining crystallites will be lowered, possibly below the
immanent temperature of the granule. These crystallites will
therefore melt quickly, releasing further constraints and
allowing more water absorption (so long as water is available)
which will reduce the melting point of the remaining
crystallites still further. The process is thus highly cooperative
and all thecrystallites in the granule would beexpected t o melt
- as is indeed observed - over quite a narrow temperature
range, irrespective ofthe range oftheir stabilitiesat aconstant
water content. As the temperature is raised still further, other
granules will start to melt and, as long as free water is available
outside the granules, each granule would be expected to
gelatinize over a narrow temperature range, with the onset of
gelatinization being determined by the melting point of the
least stable crystallite in equilibrium with the initial water/
amorphous starch ratio of about 0.54/1. The gelatinization
temperature range of a population of granules would then be
determined by the distribution of the least stable crystallites
within the granules.
I f one now turns to consider lower water contents, between
about 0.6 and 2.0 g water/g dry starch, the final gelatinization
temperature rises above that observed in a free excess of
water, and we would suggest that there is now no longer
sufficient water that all the granules can absorb the water
necessary for the cooperative melting process to occur.
During gelatinization under these conditions there will come
a point when all the free water has been absorbed, but a
proportion ofthe granules have still not gelatinized. Once this
point has been reached there will be no more cooperativity
between the melting of different crystallites within the
ungelatinized granules, and one might expect the temperature
range of gelatinization of these granules to reflect the true
distribution of melting points of the crystallites they contain.
However, a further contingency can now come into effect.
Those granules that are in the process of melting when the last
of the free water has been absorbed will actually have a water
activity of less than 1 (since they would absorb more water if
this was available), and so they will abstract water from the
ungelatinized granules (whose water activity is still = 1 at this
point). Consequently the water content of the ungelatinized
granules will be reduced and the melting temperatures of the
crystallites in these granules will be increased. As a result, one
would expect t o observe endotherms corresponding to two
types of melting - a relatively low temperature cooperative
starchlstarke 34 (1982) N r . 7, S. 224-231

melting peak, and a higher temperature true melting


process (which also reflects the progressively lower water
content of the ungelatinized granules as repartitioning of the
water takes place). The latter process would be expected t o be
manifest as a hump in the first peak moving to higher
temperatures as the water content is decreased. As the amount
of free water initially present is reduced, so one would expect
the first cooperative melting peak t o become progressively
smaller and at the point when there is just no free water (i.e.
the water level to which starch granules equilibrate at a, = 1
or about 0.54 g water/g starch) one would expect this first
peak to completely disappear. Thereafter, as the water
content is further reduced, one would expect the remaining
(second) peak to move to higher and higher temperatures. In
practice these predictions are just what is observed (Fig. 5).
The model proposed by Donovan [I71 attributing the
endotherm shift to stresses induced by the swelling of the
amorphous regions of the starch granules also accounts for
these observations, but postulates an extra unmeasureable
and, it would seem, unnecessary factor - the effect of
imposed stress on the melting point of the crystallites.
Furthermore, it does not in itself fully explain the very narrow
temperature range of gelatinization of single granules, unless
one assumes the stress rises rapidly as crystallites melt.
4.2 Variation of Gelatinization Temperature with
Added Solute

We have shown that the effect of varying water content on the


gelatinization behaviour of potato starch can be adequately
explained on purely thermodynamic grounds. The presence
of a solute in the water inevitably influences the volume
fraction of the water in the system and hence also influences
the gelatinization temperature. Lelievre [I91 examined the
effect of simple sugars on the gelatinization temperature of
wheat starch, and found that the effects could be predicted on
the basis of an extension of equation (1) t o embrace a third
component, making certain assumptions about the interaction constants, now increased to three in number. As in the 2
component system, he also assumed that the system was
homogeneous at all the starch-solution ratios he examined.
Our absorption studies show that, for native potato starch
granules, the maximum volume fraction of water (i.e. at a,
= 1) is 0.45. The calculated volume fractions of water or sugar
solutions in Lelieures work (with wheat starch) range from
0.6 upwards, indicating that his systems probably contained
extra-granular solvent or solution. Although this extra liquid
phase would be rapidly absorbed once gelatinization of the
sample had started, the exact volume fractions relating to his
systems when the last starch crystallites were melting are
indeterminate.
The alternative procedure, which we have adopted, is t o carry
out the gelatinization in the presence of an excess of solvent or
solution ( i . e .starch/liquid ratio O.l), when the distribution of
solute and solvent can be determined and is constant in the
ungelatinized granules throughout the gelatinization process.
Under these conditions the DSC peaks d o not vary in width,
so similar relationships appertain for both initial and final
gelatinization temperatures. We have used the initial gelatinization temperatures.
Flory [I21 showed that equation (1) can be derived by
considering the equilibrium between the crystalline and
amorphous phases of the starch at the melting point of the
crystallite. The condition for equilibrium is equation (2) :

starch/starke 34 (1982) Nr. 7, S. 224-231

where pLis the chemical potential ofthe liquid polymer repeat


unit, pcand po the chemical potentials in the crystalline form
and in the standard reference state. The 1.h.s. of equation (2)
can be expressed as equation (3) :
(3)

where AH,, is the heat of fusion of the polymer repeat unit, T,,,
is the melting point of the system under consideration and T:
is the melting point of the pure crystalline polymer.
In ther. h.s. ofequation (2) wecanallow for thelowering ofthe
chemical potential of the polymer unit in the liquid phase by
the presence of diluent. For a tertiary system this is given by
the general formula (4):
l n v 2 + ( 1 -v2)-v1

where p2 and p; are the chemical potentials of liquid polymer


and polymer in the standard state, R is the gas constant, vl, v2
and v3 are the volume fractions, x l , x2 and x3 the number of
segments per molecule, of solvent, polymer and solute
respectively, and $ij the interaction constants between each
species. A segment is defined as that portion of a molecule
requiring the same space as a solvent molecule, and hence the
xs correspond t o molar volume ratios and x1 = 1.
Lelievre [19] showed that equation (4) could be simplified by
a ) changing the expression from the chemical potential per
mole of polymer t o the chemical potential per mole of
repeat unit, by dividing by the number of repeat units per
X2V where V and V,, are the molar
polymer molecule ( = --,
V,.
volumes of segment and repeat unit respectively) ;
b) assuming x2 is very large and v2 comparatively large;
c) substituting $12x2 for t,hz1.
By these means he obtained an equation (5) relating the
melting temperature t o the composition in terms of volume
fractions of solvent and solute:

To apply this equation we need t o know not only the volume


fractions of solute and solvent, but also the appropriate
interaction constants, and as Lelievre pointed out this largely
restricts its use t o cases where simplifying assumptions can be
made (such as when the solute is chemically similar to the
polymer repeat unit and $13 can be taken t o equal t j l 2 , and
$32 can be assumed negligible). For other solutes none of the
terms in equation (5) can be taken as zero and accurate
estimates of the interaction constants are not easily derived.

Referring t o Figures 2 and 3 it can be seen that the effect of


solutes on gelatinization temperature increases as the
concentration is increased, and is in fact only marked at high
solute concentrations, when the water activity starts to fall. If
the data of Figure 2 and 3 are replotted as a function of water
activity instead of concentration (Fig. 6), it is evident that
there is no universal relationship with gelatinization temperature - each solute follows its own curve. However, it is
interesting that for glycerol, where we able to span a very wide
range of concentrations, the gelatinization temperature
varied virtually linearly with water activity.

229

The water activity in the starch system can also be derived by


the principles ofpolymer thermodynamics. Thus the chemical
potential of the solvent, water (Component 1) in the three
component system is given by equation (6) :

_I
O390

Inv,

+ (1 - v l ) - v 2

i3801

where E is a term allowing for the expansion of the network


structure of the starch granules against an elastic restraint.
But x1 = 1, x2 can again be assumed to be very large, (v2 v3)
x2
= (1 - v l ) and tj23= tj32- so, simplifying gives (7):
x3

~ _ _ _-_
RT
- *32

"1

v3
-

~ - +13v1
~ v j -~

x3

The first term in brackets on the r.h.s. of equation (7) also


occurs in equation (5), so substituting and rearranging gives
(8) :

1
1
- - - - - - R - v u r l -Ina,+Invl
T,
T i AH,V,

+E++,,(v,-v,)

Estimates of the interaction constants such as tj12 are


generally of the order of 0.1 to 0.5, so in most cases the last 3
terms on the r.h.s. of equation (8) will be products of small
fractions and numerically small. In excess of solvent or
solution, we have shown that the starch granule is always
swollen to about the same extent, so we can also take the
elastic term E to be constant. Hence, assuming T, is of the
same order of magnitude as TL, we can write (9):
(9)

Equation (9) shows that, to a broad approximation, it should


be possible t o express the gelatinization temperature T , as a
logarithmic function of the activity of the water divided by its
volume fraction. The inclusion of the volume fraction of the
water (solvent), which varies in inverse fashion to the volume
fraction of solute, serves to unify the effects of different
solutes, all of which have different water activity concentration relationships.
Figure 7 shows the result of re-plotting the data of Figures 2
and 3 as initial gelatinization temperature against the natural
logarithm of the water activity divided by the volume fraction
ofthe water. Clearly therelationshipexpressedinequation (9)
holds well for a large number of different solutes. It accounts
not only for the raising of the gelatinization temperature by
sugars and other polyhydroxy compounds, but also for the
lowering of the gelatinization temperature by simple salts
such as sodium chloride and calcium chloride. This is because
the main variable affecting T,,, is the ratio a,/vl . For sugars a
large change in v1 corresponds to only a small change in a,,
whereas for salts it is the other way round. There are, of
course, still exceptions to this rule. Thus the salts sodium
sulphate and sodium hydrogen phosphate have greater effect,
and compounds such as ribose and ethanol less effect on
gelatinization temperature than would be expected from

230

05

10
Ln aw/"l

15

Figure 7. Initial gelatinization temperature us. the logarithm of


water activity divided by water volume fraction; * water, 0maltose,
0 glycerol, 0sucrose, A glucose. 0 ribose, v ethanol, %sodium
chloride,xcalcium chloride, x sodium acetate,A sodium hydrogen
phosphate (pH 7.0), sodium sulphate.
equation (9), which probably indicates some specific interactions.
However, in view of the many approximations involved, the
spread of the points about a common line is still small, and no
doubt reflects the contribution of the different interaction
constants where these d o not cancel each other out. This
apart, equation (9) on the whole predicts both the direction
and the relative magnitude of the effect of many different
solutes on the gelatinization temperature reasonably well.

Acknowledgement
Thanks are due to Dr. J . W . Donovan for helpful comments on our
hypotheses.

Bibliography
[I] Ganz, A . J . : Cereal Chem. 42 (1965),429.
[2]Lindqvist, I.: Starke 31 (1979),195.
[3] Banks, W.,and C. T. Greenwood: "Starch and itsComponents",
University Press, Edinburgh 1975.
[4]Oosten. B . J . : Starke 31 (1979),228.
[5] Gough, B. M., and J . N . Pybus: Starke 25 (1973),123.
[6]Gerlsma, S.Y.:Starke 22 (1970),3.
[7]Bean, M . L., and E. M . Osman: Food Res. 24 (1959),665.
[8]D'Appolonia, B. L. : Cereal Chem. 49 (1972),532.
[9]Freke, C.D.: J. Food Technol. 6 (1971),273.
[lo] Bean, M . M.,and W . T. Yamuzaki:CerealChem.55(1978),936.
[ll] Lelievre, J . : J. Applied Polymer Sci. 18 (1974),293.
[I 21 Flory, P.: "Principles of Polymer Chemistry", Cornell University Press, Ithaca 1953.
[I31 Hellman, N . N . , B. Fairchild and F. R. Senti: Cereal Chem. 31
(1954),495.
[14] Collison, R., and W.G. Chilton: J. Fd. Technol. 9 (1974),309.
[I51 Priestley, R. J . : Starke 27 (1975),416.
[I61 Donovan, J . W . : Biopolymers 18 (1979),263.
[I71 Donovan, J . W , and C. J . Mapes: Starke 32 (1980),190.
[18]Biliaderis, C.G., T.J. Muurice and J. R. Vose: J. Fd. Sci. 45
(1980),1669.
starch/starke 34 (1982)Nr. 7,S. 224-231

[19] Lelieore, J . : Polymer 17 (1976), 854.


[20] Dengate, H. N . , D. W .Baruchand P. Meredith:Starke30 (1977),
80.
[21] Evans, I. D., and D. R . Haisman: J . Text. Studies 10 (1979), 347.
[22] Vanden Berg, C., F. S. Kapev, J . A. G. Weldvingand I. Wolters:J.
Fd. Technol. 10 (1975), 589.
[23] Hellman, N . N . , T. F. Boesch and E. H. Melvin: J . Amer. Chem.
SOC.74 (1952), 348.
[24] Leach, H. W .: In Starch, Chemistry and Technology, Vol. 1

(Eds. R. L. Whistler and E. F. Puschull), Academic Press, New


York 1965.
[25] Suir, L., and W . R . Fetzer: Ind. Eng. Chem. 36 (1944), 205.

I. D. Evuns, M.A., and D. R . Huisman, B. Sc.,


Ph. D., Unilever Research, Colworth Laboratory, Colworth House,
Sharnbrook, Bedford MK44 1LQ (England).

Address of authors:

(Received: December 17, 1981)

Effects of Storage on Dynamic Rheological


Properties of Wheat Starch Pastes
By R. B. K. Wong and J. Lelievre,
New Zealand
The variation of the dynamic rigidities of wheat starch pastes during
storage at various temperatures has been measured. The results
suggest that a crystallization process is responsible for the observed
increase in dynamic rigidity with time. The Aurami equation was used
to interpret the results in an attempt to establish the mechanism of
crystallization.

1 Introduction
Starch pastes are formed by heating an aqueous suspension of
starch granules above the gelatinization temperature [l], this
process has been described in detail elsewhere [2]. Recently, a
number of fundamental investigations of the rheological
properties ofsuch pastes have been made [3,4,5].A significant
feature of starch pastes is that their consistency changes on
storage. Although this phenomenon has been studied by
empirical methods [6], fundamental methods have not been
used. The present paper describes an investigation of the
changes in the dynamic mechanical behaviour of starch pastes
as a function of ageing temperature and ageing time. These
kinds of measurements have been used to study the ageing
process in other polymer systems [7], where the dynamic
rigidity has been shown to be a useful means of studying the
structural changes occurring with time.
It has been suggested that the crystallisation of starch
polymers accounts for the variation in the properties of pastes
during ageing [8]. In synthetic polymer-diluent systems, the
changes that occur during crystallisation have been evaluated
by the Aurami equation in an attempt to establish the
mechanism of crystallisation [9]. Starch gels have been
investigated in this manner [lo]. The possibility of using the
Aurami equation to interpret the rheological measurements
obtained during the ageing of wheat starch pastes was
therefore studied.

2 Materials and Methods


Starch was extracted according t o the method of Meredith et
al. [ll] from Gamenya and Aotea wheat varieties, air-dried at
starch/starke 34 (1982) Nr. 7, S. 231 -233

Die Wirkung der Lagerung auf die dynarnisch-rheologischen


Eigenschaften von Weizenstarkepasten. Die Verlnderung der

dynamischen Festigkeit von Weizenstiirkepasten wiihrend der


Lagerung bei verschiedenen Temperaturen wurde untersucht. Die
Ergebnisse lassen darauf schlieBen, daB der KristallisationsprozeR
fur die beobachtete Zunahine der dynaniischen Festigkeit init der Zeit
verantwortlich ist. In einem Versuch, den Mechanismus der
Kristallisation festzustellen, wurde zur Deutung der Ergebnisse die
Avrumi-Gleichung herangezogen.

ambient temperature to a moisture content of about 10% and


stored at 5C [32].Thestandardmethod ofmaking pastes was
by heating an aqueous suspension of starch granules at
95.0C for 1 h using the procedure specified elsewhere [4].
The behaviour of pastes during storage was monitored with a
top-drive oscillatory co-axial viscometer as described previously [4]. The variation of the dynamic rigidity during
ageing was measured using a single angular frequency (o
=0.02 rad s-), a range of ageing temperatures (10.0
- 30.0C)and ageing times of up to 150 h. During the course
of these experiments, the pastes were kept in the viscometer
and a very thin film of oil was placed on top of the pastes to
prevent evaporation [3].

3 Results and Discussion


Figure 1 demonstrates that the dynamic rigidity of Gamenya
starch pastes increases on storage, both varieties of starch
were found to give the same trend. The data indicates that as
temperature increases, the equilibrium values reached when
ageing is complete increase. Figure 1 also shows that the rate
of change of dynamic rigidity with respect to time decreases
with increasing temperature in a manner that is characteristic
of crystallization in polymer-diluent systems [7,9]. The above
results are similar to those obtained during the ageing of
polyvinyl chloride gels [7]. The corresponding dynamic
viscosity measurements were found to follow a similar pattern
except that the equilibrium values reached when ageing is
complete decrease with temperature.
The Aurami equation has been extensively applied to the
crystallisation of polymer systems. In order to interpret the
above results in terms of this equation, the assumption must

0 Verlag Chemie GmbH, D-6940 Weinheim 1982


0038-9056/82/0707-023 1S02.50/0

231