Determination of the Temperature
of Gelatinization and Energy of Transformation
of Starch by Dielectric Dissipation Induced Changes
In this work we present a new method which allows to determine the
structural changes of starches subjected to a thermal process. Using
that method, the initial and final gelatinization temperatures and the
amount of energy required to induce the thermal changes can be de-
duced. The method takes the advantage of the dielectric dissipation
of electrical energy in the system consisting of a mixture of starch
grains and water enclosed in a specially designed sealed cell. AC elec-
trical power at a fixed voltage and frequency is applied to the material
to be studied. The magnitude of the electric current is then moni-
1 Introduction
Gelatinization of starch is a phenomenon that manifest it-
self in the starch granule and reveals a disruption of molecu-
lar order of its main constitutive parts. The irreversible chan-
ges like water absorption, swelling granules, melting of the
crystals, lost of birefringence, increased viscosity and solubil-
ity of the granules [l], are some of the reported structural
changes induced by thermal treatments in various types of
starches. The techniques employed to evaluate the gelatiniza-
tion of starch are those based upon: optical microscopic tech-
niques to detect the swelling and lost of birefringence of
starch granules [2], viscosity changes measured by the Vis-
coamylographs [3]; lost of crystallinity evaluated by X-ray dif-
fraction [2,4,5]; heat absorption changes measured by differ-
ential scanning calorimetry (DSC), [6]; and electrical changes
measured by differential scanning calorimetry (DSC), [6]; and
electrical resistivity changes during thermal treatment of
starch [7]. In the review work of reference [ 8 ] , it is pointed out
that in the study of gelatinization of starch there are tech-
niques that depend on subjective evaluation of the data such
as the lost of birefringence of the granules during gelatiniza-
tion. Other techniques are very time consuming and usually
their results are not always consistent, this being the case of
those based on the resistivity changes of starch granules dur-
ing gelatinization. On the other hand, there are few other
methods that are more reliable and systematic in the interpre-
tation of the results employing sensitive but more expensive
equipment; examples of these are the differential scanning
calorimetry and X-ray dispersion at low and high angles. The
present work was aimed to develop a simple, economical, and
reproducible method to evaluate the important parameters
that characterize the gelatinization of starches such as: degree
of gelatinization, initial and final gelatinization temperatures
and energy required for the gelatinization of starches.
2 Experimental
Sample preparation:
The raw material used in this work were: corn, wheat, rice,
and potato. The corn we used commercial raw semi-crystal-
268 StarchlStXrke 49 (1997) Nr. 7/8. S. 268-272 0 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1997
E. Morales-Sanchez, C. Gdmez-Aldapa,
H. E. Martinez-Flores, J. Gonzdlez-
Hernandez, Y. Vorobiev, G. Martinez-
Montes and J. L. Martinez,
Queretaro (Mexico)
tored as the temperature is raised (by Joule effect) up to tempera-
tures of 120OC.The plots of the electric current Vs temperature in all
the samples studied yield two distinct extreme values: the onset and
the ending temperatures of the gelatinization of the processed sam-
ples. Analyzing the current Vs time plots during the gelatinization of
starch, we are able to determine the energy required for the transfor-
mation process. The method as such, demonstrates to be a useful
technique to determine the basic parameters during starch gelatiniza-
tion and it is much simpler then those known in the field.
line white corn grains (1995 crop, Notheast Mexico); the rice,
wheat and potato were uncooked commercial flours. Corn
grain samples passed through a 0.5cm wire mesh to remove
any undesirable particles. All starch flours were then milled in
a PULVEX" 200 knife mill with a 0.5mm mesh and a lOkg/h
capacity to obtain standard flours, each one having a char-
acteristic particle size distribution. The starting humidity con-
tents of the flours were in the range of 10-12% (w/w) as deter-
mined by weight loss. All mixtures of different starches and
distilled water (l:lw/w), were conditioned in lkg batches us-
ing a Kitchen Aid (2kg capacity) commercial mixer, before
measurement the mixtures were left in rest for 30min for ho-
mogenizing; the amount of mixture used in dielectric meas-
urements was log for each starch type. Samples of corn, rice,
wheat, and potato were prepared at room temperature by di-
luting the starch in distilled water using the starch to water
weight ratio of 1:4. These samples were kept for 60min in the
conductive cell to allow the decantation of the excess water.
Additionally, samples for viscosity measurements were pre-
pared by a diluting 4g of starch flour (starting humidity of
9-1lo/o w/w, and particle size less than 0.5mm) in 25ml of dis-
tilled water.
Dielectric dissipation measurements:
The samples to be tested were placed in the conductive cell
which consisted of a PVC 3/4" outer diameter tube of 5cm in
length with threaded ends to allow two end caps to seal the
mixture against water or vapor leaks. Each end had a stainless
steel electrode attached to it, serving as the internal electrical
contact. The PVC tube had a lateral hole located at the middle
of its length to allow a thermocouple to be inserted in it until
a physical contact with the material was made. Electrical
power was applied to the cell by means of an in-house spe-
cially designed power generator. The experiments used a fixed
AC voltage power supply with amplitude between 60 to lOOv
in a frequency range from lOHz to 10kHz. Most of the electri-
cal power was dissipated in the samples by Joule effect. The
electrical load for the power generator had an equivalent elec-
trical circuit consisting of the sample cell connected in series
with a step down transformer. The step down transformer was
0038-9056/97/0707-0268$17.50+.50/0
used to detect the current through the samples by rectifying
the AC voltage present across its secondary windings. The rec-
tified voltage signal was the input to a specially designed auto-
matic data acquisition apparatus connected to a PC computer.
In the same way, a thermocouple sensor (J type) served as the
temperature indicator and connected to the same acquisition
system. A simple compiled BASIC program was used to con-
vert the current, temperature, and time data from the acquisi-
tion system to numeric format for latter manipulation and
plotting. All samples subjected to dielectric dissipation meas-
urements were at rest for a 90min interval in order to warrant
stabilization and reproducibility before dielectric dissipation
measurements.
Viscosity measurements:
The viscosity of the aqueous starch suspensions were deter-
mined as suggested in the application notes of a Rapid Visco
Analyzer (Newport Scientific PTY Ltd., Sidney, Australia).
The determination were done following the time-temperature
sequence; the suspension was heated from 50 to 92°C with a
heating rate of 5.6’C/min. (gelatinization), the temperature
was held at 92°C for 1.5min (pasting), and then cooled down
to 7OoC with a rate of 8.4’Clrnin (setback).
Energy of transformation determination. The shape of the
I-t curve during heating of the starch by dielectric dissipation
is governed by the behavior of the electric resistance of the
specimen which, in turn, is a function of a phase state (reflect-
ing the phase transition or gelatinization). For description of
the real situation from the energetic point of view we choose
the function C*=dQ/dT defining the effective thermal capac-
ity of a sample: in absence of a phase transition this is approx-
imately constant, whereas during the transition it varies great-
ly according to the amount of energy absorbed. In our case,
where heating is only produced by electrical current, the
amount of heat energy absorbed by the sample Q is given by:
To make a rough description of the process during the
phase transformation, we introduce the specific thermal ca-
pacities of the two coexisting phases c1 and c2 and the specific
transformation energy L, then for the time interval dt within
the transformation limits we have
dQ = c1 mdT + c2 (M-m)dT + Am (6)
and
dC*/dt = (CI-CZ)dm/dt + d/dt[d(Lm)/dT] (7)
where M is the mass of a sample and “m” is a mass which has
gone through the phase transformation before the time mo-
ment “t”.The first term in the last expression is not very sig-
nificant (if the thermal capacities of the two phases are not
much different, it is approximately zero); the second one
shows the speed of the energy absorption and is determined
by the value of L and by the dependence of m on both t and T
(i.e. by the speed of the phase transformation). The area un-
der the curve showing the dependence of the dC*/dt on time
(area under the “quasi-endotherm peak”) could be obtained
by integrating the last expression. It gives:
where AT is the temperature interval of the phase transforma-
tion. From this formula we can estimate the energy of the
transformation; so neglecting the first term, we get
AM = SAT. (9)
3 Results
Fig. 1 represents the electrical schematic arrangement of

1
t the experimental set up. The figure includes an expanded
Q = I(t)Vdt view of the cell. The letter A denotes the position of the ther-
0 mocouple, B and C represent the stainless steel electrodes,

so that

I I -
U U i
W(t) = VI(t), (3) r I
00 VARIABLE
from (2) we have SAMPLE FREQUENO
Wdt = C*dT (4) CELL %Lym% X O Z E O T

and if dT/dt = /? = const, we obtain

 TIME (sec) ses with the increase of time, resembling the behavior of a
0 100 200 300 400 semiconductor where the electric conductivity is thermally ac-

1
tivated. In those experiments an increase in time corresponds
to an increase in temperature of the sample due to dielectric
Corn starch heating. However, for values of the temperature between 65
and 8OoC, there is an important decrease of the current by
0.13 a) Raw about 30% of its maximum value of the sample. Finally, for
n
cn b) Cooked temperatures greater than 8OoC, the electrical conduction
0.10 c 4 starts to increase again an its behavior resembles another ther-
mally activated process.

0.08 L
I f b /
L i I
To obtain more information from this “joule heating” pro-
cess, we let the electrically heated samples to cool down to
room temperature and started another heating process (sec-
ond temperature cycle), up to the same temperature value as
in the first cycle. A typical result of such procedure is shown
in curve b of the same Fig. 2. This curve shows monotonic in-
crease in the current as the sample gains temperature during
tI 1
0.03
0.001
n’ I

30
I I
40
’ I
50 60
’ ’
70
I I
80
I
the “joule heating” process, and does not show the extreme
values of electrical current in the temperature range chosen.
We attribute this behavior (curve b) to the complete disrup-
tion of the starch granules during the first heating cycle, and
the conduction mechanism to a yet unknown thermally acti-
vated process. All CG’s of several starches taken during di-
TEMPERATURE (“C) electric heating in presence of water, always show the same
two local extremes of current located in the temperature
Figure 2. Conductigrams of raw corn starch with water (l:l), during
heating, from room temperature to 98OC (curve a, cycle l), and heat- range of 5O-8O0C, but only during the first heating cycle.
ing from room temperature, after cycle 1, up to 98’C (curve b, cycle From here, we assume that the extreme values of the current
2). in a typical CG correspond to the temperature interval in
which the main disruption of the starch granules takes place
during heating in presence of water.
the enclosed material is placed between them. All dielectric To prove the above assumption, we made several conducti-
dissipation experiments were carried out with a fixed AC am- grams on various starches. The results are shown in Figure 3,
plitude voltage, and therefore the current versus temperature the CG’s curves from a to d correspond to corn, wheat, rice
curve corresponds to the admittance values of the sample be- and potato, respectively. Each starch shows a distinct behav-
ing under test. ior, and each curve displays its own characteristic onset (see
A typical result of the gelatinization process of corn starch arrow for each CG) and ending gelatinization temperature.
by dielectric dissipation is shown in Fig. 2, curve a; see also From these data, we constructed a comparisons table of the
Fig. 3. This type of plot will be called a “conductigram” (CG). characteristic temperature values determined from Figure 3
The CG curve for a mixture of corn grits and water shows sev- with the reported values for different starches as determined
eral features. For temperatures below 6OoC the current increa- from DSC measurements (see Table 1). We observed that
most of the onset and ending temperatures determined by
CGs are in close agreement with the values reported. The dis-
crepancies between the values found in our work and those
the literature, we attribute to the difference of preparation
conditions and the humidity content of the samples; the
importance of these factors has been recognized by several au-
h
cn 0.10 thors [9].
P b) Wheat flour We have also made a comparison of the CG for each starch
grain with its own Rapid Viscoamylogram. A representative
c) Rice flour /
s
z
W
t
Y
0.08 c w
J
d) Potato flour
result of such comparison is shown in Figure 4. This figure dis-

Table 1. Comparisons for Onset and Ending GelatinizationTempera-

tures for Various Starches as Determined from Conductigrams with
those Correspondingly Reported in the Literature [l l-131.
w
3
0 0.06 Starch Onset temperature (“C) Ending temperature (“C)
58.0 (CG) 67.6 (CG)
Potato 58.6 ref. [ll] 72.2 ref. [ll]
62.0 (CG) 75.6 (CG)
Rice 61.0 ref. [9] 76.0 ref. [9]
0.04
40 50 60 70 80 90
59.5 (CG) 73.0 (CG9
TEMPERATURE (“C) Wheat 55.4 ref. [12] 68.0 ref. [I21
Figure 3. Conductigrams of various starches: curve a, corn; curve b, 64.5 (CG) 81.5 (CG)
wheat; curve c, rice; curve d, potato. The arrows indicate the tem- Corn 61.4 ref. [13] 75.0 ref. [13]
perature at which each starch starts the gelatinization process.

270 StarchlStiirke 49 (1997)Nr.718, S. 268-212

 Table 2. Speed of Heating, Area Under the Curve (current Vs time),
Temperature Range of Transformation, and Specific Energy of Trans-
formation for Several Starches, as Determined from Dielectric Dissi-
pation.

Starch dT/dt <v> S AT 1

('Clsec) (volts) (W sec/"C) ("C) (J/gr.)
Potato 0.2440 119.40 -8.799 16.00 14.10
Rice 0.2523 100.79 -5.257 52.00 27.33
Wheat 0.1952 101.51 -3.047 15.33 4.67
Corn 0.4827 100.10 -7.112 27.33 19.44

starch: 80ml of distilled water) was prepared in a glass baker

of 100ml; we let the starch sediment for 12h and then de-
/ canted the excess water into our test cell. Latter, we applied
the same electrical power conditions to this excess water and
monitored its CG. The CG evidences an almost linear growth
0'07 52 56 60 64 68 72 76 80 84 88
of current Vs temperature. We conclude from this experiment
TEMPERATURE ("C) that the AC conduction in the cell occurred throughout the
Figure 4. Comparison of current dissipation (curve a), and viscosity
solution due to a conduction property of the solvated ions
(curve b), of corn starch as temperature rises in the samples. and/or organic molecules present in the liquid. These solvat-
ed ions and/or organic molecules when in a starch mixture,
permeate through it and thereby transfer efficiently the Joule
plays a CG of a sample of corn grits with water showing its heating to the mixture. This means that the dielectric dissipa-
two main characteristic extremes (curve a), and in the same tion is a local heating process.
figure a Rapid Viscoamylogram of a sample belonging to the To verify the latter hypothesis, we proceeded t o perform
same lot (curve b). In the CG the temperature at which the several CG's on various samples of corn starch, using differ-
dissipation current attains its maximum is 69.88OC; in the ent heating rates (1.250, 0.987 and 0.597'C/s), using several
RVA curve, the departure of the viscosity from the baseline voltage amplitudes (80,70 and 60V) in the power generator.
correspond to the beginning of gelatinization of corn starch The corresponding CG's are shown in Figure 5 . Each current
[3], and is located at 70.5'C, On the other hand, the value of Vs temperature curve represents different heating rates for
the temperature at which the current attains the minimum samples having the same mixture conditions. It can be seeing
value (curve a of Fig. 4) is 85.22OC; the temperature at which from the figure that each curve displays the two extreme val-
the RVA attains its maximum is 86.2'C. Both values approx- ues in current; and that they are located at the same tempera-
imately correspond to the values at which corn starch ends the ture (onset: 66.82'C, ending: 79.94OC).
gelatinization process [3]. A similar behavior was observed for To evaluate the amount of energy required for transform-
all starch granules employed in this work. ing of raw starch into a gelatinization state, we determined I
In order to elucidate the conduction mechanism of mix- from equation (9) for various starches employing the data
tures of water and corn starch, we proceeded to carry out the from Figure 3. The results are displayed in Table 2. At the
following experiment. A diluted solution of starch (20g same time, this table includes the values of speed of heating,
amplitude of the applied voltage, area under the curve dl/dt,
and the transition temperature range AT (maximum and
75 c
I
I
,
a) 80 volts 1 250 "Clsec
I I
I l
minimum value of current) of starch during the gelatinization
process. The values for the energy of transformation 1 given in
Table 2 for corn, wheat, rice, and potato starches are in the
range of the values of energy of transformation reported in
n
cn the literature [lo].
2 60
a,
e
s. 4 Conclusions
5 45 In this work we have developed a new method for measur-
ing the temperature range in which a mixture of starch (corn,
W
nf wheat, rice and potato) with water develops its process of ge-
a latinization. The method consists of heating homogeneously
of a humid starch sample with AC current in a specially de-
signed cell. The curves of the dissipation current Vs tempera-
ture always display two characteristic extremes. The maxi-
mum value of a "conductigram" (current Vs temperature;
CG), is at the temperature for which starch is reported to start
I I I I I I
absorbing water and disruption of its the morphology in an ir-
40 60 80 100 reversible way. This fact is assessed, first, when we cycle two
TEMPERATURE ("C) times the dielectric dissipation heating process and compare
Figure 5. Conductigrams of a mixture of corn starch and water for the two corresponding CGs. The first cycle shows extreme val-
several different heating rates (amplitude voltages). ues in the current Vs time or temperature; the second cycle

Starch/Stiirke 49 (1997) Nr. 718, S. 268-272 27 1

shows only a monotone increase of current Vs time or tem-
perature; the comparison is an indication that the sample has
suffered a physical transformation as far as the dielectric con-
duction properties are concerned. Second, when we com-
pared several C G of samples of corn starch mixed with water
with the corresponding Rapid Viscoamylograms (RVA), we
found a direct correlation in the temperatures for the begin-
ning and the end of the gelatinization process of starch. An-
other finding is that the heating process to induce gelatiniza-
tion of starch by dielectric dissipation is a local heating pro-
cess, this was demonstrated by the independence of the onset
and ending temperature values on the rate of the dielectric
dissipation. Finally, by determining the amount of electrical
energy supplied to the samples and taking the area under the
curve of the current Vs time, along the time (temperature)
transformation range, we were able to calculate the energy of
transformation of starch during the gelatinization process em-
ploying this dielectric dissipation method. The values thus ob-
tained are closely related to those reported in the literature.
Bibliography
[l] Atwell, A . W ,P. L . Hood, R. D . Lineback, E. Varriano-Martson, and
E H . Zobel: The terminology and methodology associated with
basic starch phenomena. Cereal Foods World 33 (1988), 306-
311.
[2] Liu.H., J. Lelizvre, and Ayoung-Chee: A study of starch gelatiniza-
tion using differential scanning calorimetry, X-ray, and birefrin-
gence measurements. Carbohydr. Res. 210 (1991), 79-97.
[3] Doublier, J. L., G . Llamas, and M . L e Meur: A rheological investi-
gation of cereal starch pastes and gels. Effect of pasting proce-
dures. Carbohyd. Polym. 7 (1987), 251-275.
[4] Zobel, l? H., N. S. Young, and A . L . Rocca: Starch gelatinization:
An X-ray diffraction study. Cereal Chem. 65 (1988), 443-446.
[5] Jenkins, P. J., R . E. Cameron, A . M . Donald, W Bras, G . E. Derby-
shire. G . Mant, and A . J. Ryan: In situ simultaneous small and
wide angle X-ray scattering: A new technique to study starch ge-
Effect of Moisture Level on the Crystallinity
of Wheat Starch Aged at Different Temperatures
Differential Scanning Calorimetry (DSC) was used to study retrogra-
dation of wheat starch. For storage at 4"C, enthalpy (AH) values of
retrogradation endotherm (recrystallization) of wheat starch contain-
ing various moisture levels (25-80%) slowly continued to increase ex-
cept in samples with moisture level of 50,60 and 70%. For storage at
26°C and 32OC, most recrystallization of wheat starch occurred with-
in one and two weeks of storage time, while recrystallization with a
moisture level of 50% at 26OC occured for 4 weeks. The peak tempera-
tures of retrogradation endotherm at various moisture levels (25-
1 Introduction
In starch gels or baked products after gelatinization, starch
retrogradation has been the subject of extensive investigation
[l-41. The physical changes accompanying the retrogradation
212 StarchlStirke 49 (1997) Nr. 7/8. S. 272-277 @ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1997 0038-9056/97/WW4272$17.50+.50/0
latinization. J. Polymer Science: Part B: Polymer Physics. 32
(1994), 1579-1583.
[6] Biliaderis, G . C., J. Z Maurice, and R. J. Vose: Starch gelatiniza-
tion phenomena studied by differential scanning calorimetry.
Journal of Food Sci. 45 (1980), 1669-1674.
[7] Leszczynski, W :New methods for determination of starch gelati-
nization temperatures. Starch/Starke 39 (1987), 375-378.
[8] Wroclaw, L. W ; New methods for determination of starch ge-
latinisation temperatures. Starch/Starke 39 (1987), 375-378.
[9] Biliaderis, G. C.: Thermal analysis of food carbohydrates; Ther-
mal Analysis of Foods, Eds. V. R. Harwalkar and C.Y. Ma, Else-,
vier Applied Science, London, N.Y., 1989, pp. 168-220.
[lo] Burros, B. C., L. A . Young, and P. A . Carried: Kinetics of corn
meal gelatinization at high temperature. J. of Food Science 52
(1987), 1372-76.
[ll] Jacobs, H., R. C . Eerlingen, W Clauwaert, and J. A . Delcour: Influ-
ence of annealing on the pasting properties of starches from
varying botanical sources. Cereal Chem. 72 (1995), 480-487.
[12] Ghiasi, K.,R. C. Hoseney, and Varriano-Marston: Gelatinization
of wheat starch. 111: comparison by differential scanning calori-
metry and light microscopy. Cereal Chem. 59 (1982), 258-262.
[13] Miller, L. A., J. Gordon, and E. A . Davis: Dielectric and thermal
transition properties of chemically modified starches during
heating. Cereal Chem. 68 (1991), 441-448.
Addresses of authors: E. Morales-Sanchez', C . Gornez-A1dapa2~',
H. E. Martinez-Flores', J. Gonzalez-Hernandez', !l Vorobiev', G. Marti-
nez-Montes',', and J. L. Martinez'.
') Laboratorio de Investigacih en Materiales del CINVESTAV,
QuerBtaro, Centro Universitario/Facultad de Quimica, Cerro de
las Campanas SIN, QuerBtaro, Qro. 76010, MCxico.
*) Posgrado en Alimentos, Fac. de Quimica, UAQ, Centro Universi-
tario, Cerro de las Campanas SIN, QuerBtaro, Qro, 76010, MBxico.
3, Becario CONACYT.
4, Depto. de Biotecnologia, CINVESTAV, Av. IPN 2508, Zacatenco,
C.P. 07300, D.F., MBxico.
') On sabbatical leave from Instituto de Fisica, UAP, Apdo. Postal
5-48, Puebla, MCxico.
(Received: January 17, 1997).
J.K. Jang and Y.R. Pyun, Seoul (Korea)
80%) after 4 weeks of storage time increased largely as the storage
temperatures increased from 4 to 32OC. The enthalpy values of retro-
gradation endotherm after 4 weeks of storage occurred to a greater
extent at a lower storage temperature. The glass transition tempera-
ture and starch recrystallization have a close relationship. In the re-
crystallization of wheat starch, the nucleation and propagation rate
after 4 weeks of storage can be converted into enthalpy and peak tem-
perature of retrogradation endotherm.
have been suggested as the main cause of baked items going
stale.
Calorimetry provides a means of monitoring the progres-
sive development of ordered structures and the staling endo-
therm in starch gels and baked products. This transition is at-