Modulated differential photoacoustic cell to study the gelatinization in a starch-water

suspension
J. A. Villada, W. Herrera, D. G. Espinosa-Arbelez, J. C. Mosquera, and M. E. Rodrguez-Garca
Citation: AIP Advances 4, 067136 (2014); doi: 10.1063/1.4885140
View online: http://dx.doi.org/10.1063/1.4885140
View Table of Contents: http://scitation.aip.org/content/aip/journal/adva/4/6?ver=pdfcov
Published by the AIP Publishing
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AIP ADVANCES 4, 067136 (2014)

Modulated differential photoacoustic cell to study

the gelatinization in a starch-water suspension
J. A. Villada,1,a W. Herrera,2 D. G. Espinosa-Arbelaez,
3 J. C. Mosquera,2
4
and M. E. Rodrguez-Garca
1
Departamento de Ingeniera, Universidad del Valle de Mexico, Campus Queretaro,
Queretaro, Qro., Mexico
2
Departamento de Fsica, Universidad del Quindo, Armenia, Quindo, Colombia
3
Posgrado en Ciencia e Ingeniera de Materiales, Departamento de Nanotecnologa,
Centro de Fsica Aplicada y Tecnologa Avanzada, Universidad Nacional Autonoma de
Mexico, Queretaro, Qro., Mexico
4
Departamento de Nanotecnologa, Centro de Fsica Aplicada y Tecnologa Avanzada,
Universidad Nacional Autonoma de Mexico, Queretaro, Qro., Mexico

(Received 23 February 2014; accepted 11 June 2014; published online 24 June 2014)

In this paper the design and implementation of a novel Differential Photoacoustic

Cell (DPC) system is presented. The system was used to study the thermo optic
transition in water-starch suspension called gelatinization. The melting temperature
of Gallium was used to calibrate the temperature of the system. Both temperature values for starch gelatinization and gallium melting were agreed with those
obtained using differential scanning calorimetry (DSC). The results show that this
system is suitable to study other thermal processes in food or any thermal transition
C 2014 Author(s). All article content, except where otherwise
at low temperature. 
noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
[http://dx.doi.org/10.1063/1.4885140]

I. INTRODUCTION

The development of new systems to study thermal transition at low temperature is important in
the food industry, in especial all studies related to starch. The most important and studied thermal
transition in water-starch suspension is the gelatinization in which the internal order of the amylose
and amylopectin is disrupted.
Starch is a naturally abundant nutrient carbohydrate found chiefly in the seeds, fruits, tubers,
roots, and stem pith of plants, notably in corn, potatoes, wheat, and rice. Microscopically a starch is
a microparticle formed by long chains of sugar molecules of amylose and amylopectin in different
percentages depending on the type of starch,1, 2 those kinds of molecules are called polysaccharide.
As a starch-water suspension is heated to a particular temperature (between 62 C and 78 C for
most types of starch), it begins to undergo gelatinization.3 In this process the intermolecular bonds
of starch molecules break down and the crystalline structure of the starch is disrupted allowing the
water absorption. Gelatinization is important because it changes the texture and the taste of starch
and makes it easier to digest.4
Differential scanning calorimetry (DSC) is the usual technique to study the gelatinization
transition in different kind of starches.57 In this technique a few quantity of the sample under
study is placed inside a sample holder near to a reference sample. Both the sample and reference
are maintained at nearly the same temperature throughout the experiment. The temperature of the
sample holder increases linearly as a function of time. In this technique the time to reach the thermal
equilibrium depends on the relation between sample and thermocouple size. Therefore, if the sample

a Author to whom correspondence should be addressed. Electronic mail: jhon.villadavi@uvmnet.edu

2158-3226/2014/4(6)/067136/9

4, 067136-1


C Author(s) 2014

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dimensions are smaller than the thermocouple size it means that the phase transition can occurs
before it can be detected.
Another possible technique to study the gelatinization process is photoacoustic (PA). Fundamentals of PA involve the excitation of the sample due to interaction with electromagnetic radiation.
According to PA effect, the absorption process creates pressure changes that can be detected by a
microphone.8 PA signal have two contributions: the first one is the response characteristic, or transfer
function of the system and it depends on the configuration, system components and environmental
conditions; the second contribution is the sample response due to the excitation. A drawback of PA
spectroscopy is that variations in the room temperature or any other environmental noise can affect
the PA measurement and, in the interpretation of the signal, this noise can be related to non-existent
phase transitions or other misinterpreted results. In order to avoid all the problems involved in the
instrumentation and environmental conditions a reference sample is used to calibrate the system but
this calibration is done before measuring the studied sample, therefore the environmental conditions
can change.
In a recently variation of the PA technique this calibration can be done in situ using a differential
photoacoustic cell (DPC).9 For this system, two samples were used simultaneously: a reference
sample that is only affected by environment changes and the studied sampled that is affected in
addition by some physical process. The difference between the signal from the studied sample and
the reference sample is analyzed, allowing obtaining a very clean signal. When the sample undergoes
a physical transformation such as a phase transition, it absorbs or emits heat, depending on whether
the process is endothermic or exothermic. As a result, the waves (signal), generated in the sample,
decrease or increase its amplitude and phase. Therefore DPC can be used to observe phenomena
such as crystallization and melting. DPC was used before for the study of zinc deposition on steel
substrate and calcium ion diffusion into organic layers.9, 10
In this work a DPC was developed in order to study the gelatinization transition in corn starch.
This paper shows the design, implementation, and calibration of a new differential photoacoustic
cell used as DSC system in order to determine the phase transition in starch. The ability of this
technique is its capacity to measure only signals originated in the changes of physical properties of
the sample.

II. DIFFERENTIAL PHOTOACOUSTIC CELL DESIGN

In order to study a thermal transition in starch it was necessary to design and build a new cell
adapted to the experiment. Figure 1 shows the DCP designed for this purpose. It is an aluminum
solid cylinder (diameter: 2 in. length: 2.75 in.) containing different cavities. In the center of the
bottom face there is a cavity of 0.269 in. in diameter and 2.72 in in length to host the heat source:
a 150W electric cartridge heater from Maxiwatt. Two photoacoustic cells are located in the upper
face. The cells are symmetrically distributed in order to guarantee the same temperature in both
of them and to prevent the formation of temperature gradients. For each cell there is a cavity of
1 mm in diameter to connect it with the microphone housing cavity located in the lateral face of the
cylinder.

III. EXPERIMENTAL SETUP

A. Photoacoustic signal (PAS)

The PAS is generated by the generation of sound waves after the absorption of electromagnetic
radiation in any material. In order to obtain this signal, a periodic variation of the intensity of incident
light is needed. A 532 nm laser, with power of 200 mW was used as the electromagnetic radiation
source to excite the sample. The laser beam was modulated with the internal signal of a Lock-in
amplifier (Stanford Research System SR830) at different frequencies. Microphone (electrets) was
used in each cell and it was polarized with 9V DC battery, and connected to the same Lock-in
amplifier.

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FIG. 1. Differential photoacoustic cell designed to study gelatinization in starch.

B. DPC technique

Figure 2 shows the experimental setup of the DPC technique. The sample under study is located
inside one of the cells. Into the other cell a reference sample is placed. A window of quartz was
used to hermetically seal both of the cells with vacuum grace. The temperature in the DPC was
sense with a type J thermocouple connected to a temperature controller (Watlow 96). The system
was thermally isolated with a glass fiber skin. The signal from the microphones was detected using
a LM35 transistor connected to a digital multimeter (Kethley 2700). A beam splitter 60/40 and a
mirror are used to divide the light and direct it toward each cell.

C. Cell Calibration

In order to calibrate the DPC to obtain signals at low temperature (T < 100 C) it was used a
Gallium metal 99.9999% (Alfa Aesar USA) with a well know melting temperature (29.76 C).11
Figure 3 shows the temperature as a function of the time for the cell 1 (Figure 3(a)) and cell 2
(Figure 3(b)) using Ga in both cells as reference. The growth rate in the temperature was 3 C/min.
Black points correspond to the experimental data while the solid lines correspond to the best linear
fitting. The values obtained from the linear fitting are presented in each figure. From this figure it
is possible to establish that there are not considerable differences in the temperature of the cells.

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FIG. 2. DPC system.

In addition, the increase rate of the temperature in each cell is according to the growth set in the
heater.
Other important problem associated with the development of a modulated system is the frequency used to carry out the experiments. Figure 4 shows the amplitude of the PAS obtained for Ga
at three different frequencies: 20, 50, and 76 Hz taking into account the increase of the radiation to
heat conversion. From this figure it is clear that the best response is obtained at 20 Hz. The solid
vertical line in Fig. 4 corresponds to the melting temperature for Gallium.
The Photoacoustic Signal obtained from the cell consists of two signals, one belonging to the
reference sample and other signal belonging to the studied sample. In this configuration, both of
them are metallic gallium. These measurements are obtained simultaneously. The simultaneous
measurement of both signals eliminates the instrumental function, and the presence of noise, due to
any deviation originated by electrical, optical, and environmental factors.9
The photoacoustic amplitude and phase signals for Ga as a function of the temperature are shown
in Figures 5(a) and 5(b) respectively. The peak position for both amplitude and phase is 28.9 C.
According to Strouse,11 the temperature for the melting point in Ga is 29.76 C (indicated in Figure 5
with a long solid vertical line). By detail inspection of Figure 1, it is clear that the thermocouple
is not in direct contact with the samples, and then there exists a difference of temperature (T).
This difference in temperature corresponds to the recalibration temperature for any experiment. In
Fig. 5 T was -0.86 C. It means that after any experiment the temperature has to be calibrated. In
our case a new sample of Ga is used for each experiment in order to avoid problems related to the
Ga recrystallization. In Figure 5(c) it is presented the melting point of Ga obtained by DSC. In this

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FIG. 3. Temperature measures as a function of the time in cell 1 (a) and 2 (b).

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FIG. 4. Amplitude of the photoacoustic signal of Ga at three different modulation frequencies.

case it is possible to see that the T value from the DPC system is near to the T value obtained
from DSC (0.95 C).

IV. THERMAL STUDIES OF STARCH GELATINIZATION USING DPC

To perform the thermal analysis, it was prepared a sample whit 20% starch and 80% water
(2 milligrams of corn starch and 8 milligrams of water), and disposed in a steel tray in the DPC
isolated with a quartz window and vacuum grease. The temperature was changing from 23 to 85 C
in 20 minutes (steps 3.1 C/min). The reference was 5 milligrams of metallic gallium disposed in
the other sample holder and isolated alike.

V. RESULTS

In order to analyze the PAS, is used the thermal diffusion model designed for Rosencwaig
and Gersho (RG),12 this model involves a gas chamber in which a sample absorbs radiation that is
periodically modulated, this generates pressure fluctuations in the sample.
Figures 6(a) and 6(b) shows the amplitude and phase of the water-starch suspension respectively
and Figure 6(c) shows the DSC thermogram for the sample starch with the same experimental
conditions.
According to this figure, it is clear that both amplitude and phase signals from the starch-water
suspension are sensitive to the thermal transition (gelatinization) that take place when water and
starch are heating together. From a physics point of view the changes in the amplitude and phase
are as result of the thermal transition that produces a disruption in the amylose and amylopectin
order. These structural changes in turn cause changes in the absorption coefficient of the system as
a function of the temperature and time.

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FIG. 5. Comparison between the photoacoustic (amplitude (a) and phase (b)) and DSC signals obtained for Ga.

The temperature axis in Figures 6(a) and 6(b) was adjusted in -0.86 C. This value was obtained
from the calibration in Figure 5(a). Similarly, for the DSC signal shows in Figure 6(c) the temperature
axis was calibrated in 0.95 C, as it was obtained in Figure 5(c).
By observation of Figures 6(a) and 6(b), it is clear that for the gelatinization process, the phase
signal is more sensitive than the amplitude.

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FIG. 6. Comparison between the DPC (amplitude (a) and phase (b)) and DSC signals obtained for a starch-water suspension.

VI. DISCUSSION

A technique was developed to study the gelatinization process in starch. The differential photoacoustic cell in the present configuration can be an excellent tool to study not only gelatinization
phenomena but also other thermal transitions in food at low temperatures with an in situ auto calibration. This system is also suitable to study any other thermal transitions in organic or inorganic
materials. The modulated signal improves the noise to signal ration and eliminate data misinterpretation.
In addition, the system developed can be used as a complementary technique to
DSC.

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ACKNOWLEDGMENTS

This work was supported by project PAPPIT in115113, Universidad National Autonoma De
Mexico. J.A. Villada wants to thank the National Science and Technology Council of Mexico,
CONACYT for the financial support to develop this research, through the SNI program. Authors
want to thank to Rosa Maria Jimenez Aguilar, from the language department of the Universidad Del
Valle de Mexico, campus Queretaro, for the English review of this paper.
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