Home Search Collections Journals About Contact us My IOPscience

Optical system based on a CCD camera for ethanol detection

This article has been downloaded from IOPscience. Please scroll down to see the full text article.

2013 Meas. Sci. Technol. 24 105003

(http://iopscience.iop.org/0957-0233/24/10/105003)

View the table of contents for this issue, or go to the journal homepage for more

Download details:
IP Address: 189.129.167.191
The article was downloaded on 16/08/2013 at 01:35

Please note that terms and conditions apply.

IOP PUBLISHING MEASUREMENT SCIENCE AND TECHNOLOGY
Meas. Sci. Technol. 24 (2013) 105003 (6pp) doi:10.1088/0957-0233/24/10/105003

Optical system based on a CCD camera

for ethanol detection
C Martı́nez-Hipatl 1 , S Muñoz-Aguirre 2 , R Muñoz-Guerrero 1 ,
J Castillo-Mixcóatl 2 , G Beltrán-Pérez 2 and J M Gutiérrez-Salgado 1
1
Sección de Bioelectrónica, Departmento de Ingenierı́a Eléctrica, CINVESTAV-IPN. Av. Instituto
Politécnico Nacional No. 2508, Mexico City, DF, CP 07360, Mexico
2
Facultad de Ciencias Fı́sico-Matemáticas, Benemérita Universidad Autónoma de Puebla, Av. San
Claudio y 18 Sur, Col. San Manuel CU, Puebla, Pue., CP 72570, Mexico
E-mail: cmartinezh@cinvestav.mx and smunoz@fcfm.buap.mx

Received 7 March 2013, in final form 27 June 2013

Published 14 August 2013
Online at stacks.iop.org/MST/24/105003

Abstract
This work reports the optimization of an optical system used to detect and quantify volatile
organic compounds (VOC). The sensor consisted of a polydimethylsiloxane (PDMS) sensing
film deposited on a glass substrate by the spin-coating technique. The PDMS has the property
of swelling and/or changing its refractive index when it interacts with molecules of VOC in
vapor phase. In order to measure the PDMS swelling, a charge-coupled device (CCD) camera
was employed to evaluate the interference fringe shift in a Pohl interferometric arrangement.
With this approach, it is possible to use each pixel of the CCD camera as a single
photodetector in the arrangement. Similarly, different computer algorithms were developed in
order to acquire and process the obtained data. The improvements in the system allowed the
acquisition and plot of 1 datum per second. The steady-state responses of the PDMS sensors in
the presence of ethanol vapor were analyzed. The obtained results showed that noise level was
reduced approximately three times after performing data processing.

Keywords: CCD camera, ethanol vapor, optical sensor, PDMS sensing film

1. Introduction with the characteristics of interest which are present in the

Electronic noses have been proved advantageous in various
areas of food such as process monitoring, quality control,
freshness evaluation, shelf-life investigation and authenticity
assessment. Over the last few years, it became possible to find
applications related to meat [1], fish [2], eggs [3], grains [4],
cheese [5], chocolate [6], coffee [7], beer and other alcoholic
beverages [8] where the main objective was the evaluation of
the odor quality and even the food packaging materials. The
broad acceptance of these systems is mainly related to the use
of a simple methodology to obtain quantitative and significant
results within a short time. The main foundation of electronic
noses is the use of gas sensors whose response is based on the
absorption of molecules in gaseous fluids employing diverse
sensing materials, such as metal-oxide-semiconductor and
polymers. Generally, gas sensors are composed of a transducer
that converts the physical or chemical phenomena of the
sensing element into an electrical or optical signal. Such a
signal is conditioned and processed in order to be correlated
sample under analysis. The optical signal has some advantages
over the electrical one owing to immunity to electromagnetic
noise, the ability to perform remote detection without physical
contact with the sample, and its ability to be used in hostile
environments dangerous for a human user. For the detection
of light, there is a wide variety of sophisticated instruments
such as power meters, spectrometers, diode arrays and charge-
coupled devices (CCD). These instruments, together with
gas sensors, can be used in the design of analytical systems
focused on the detection and quantification of gases in many
applications.
In the literature there are reports of different types of
gas sensors that work with different operation principles,
such as quartz crystal microbalance (QCM) [9], conducting
[10] and non-conducting [11] polymers, optical fibers [12],
among others. In recent years, these types of sensors have
been incorporated in arrangements focused on the detection
of volatile organic compounds (VOC) vapors. One of the
reports on this topic was presented by Gauglitz et al, who

0957-0233/13/105003+06$33.00 1 © 2013 IOP Publishing Ltd Printed in the UK & the USA
Meas. Sci. Technol. 24 (2013) 105003
Figure 1. Operation principle of the sensor.
studied a system based on spectral interferometry [13]. They
used a bifurcated optical fiber that was excited by white
light from one end in order to illuminate a glass substrate
with a polydimethylsiloxane (PDMS) polymeric sensing
film deposited on one of its surfaces. The corresponding
interference spectrum was analyzed at the other end of the
fiber with a diode array and subsequently, they performed a
measurement of sensor responses to various types of VOC.
However, the experimental setup and data analysis were quite
complicated since the results were not obtained directly and
it was necessary to perform information extraction. In recent
years, similar works have been reported. De Girolamo et al
[14] described a method to characterize scattering materials
such as polymer/carbon black nanocomposites using swelling
evaluation of a thin film by interferometry with a similar
experimental setup proposed by Gauglitz. In this work, they
covered a silicon substrate with a thin sensing film of poly(2-
hydroxyethyl methacrylate) (PHEMA), and the response of
this material was analyzed under ethanol vapor exposure. In
this case, the response analysis was performed indirectly as
was done in the Gauglitz method.
Even though the current diode arrays and spectrometers
allow evaluating spectral interferometry of gas sensors
in interferometric arrangements covering a wide range of
wavelengths (190–900 nm), it is possible to simplify and lower
the total cost of the detection system employing a source of
monochromatic light, and measuring the response using a CCD
camera. With the CCD camera, the sensor response can be
monitored from the shift of the fringe pattern measuring the
intensity changes of a single pixel. In this respect, there have
been reports where a CCD camera has been used to detect gases
in systems that operate under different principles [15–17].
For instance, Malins et al [18] characterized the response of
fluorescent dyes immobilized in sol–gel thin films by imaging
of fluorescence from the oxygen and carbon dioxide using
a CCD. Moreover, Gibson et al [19] employed a CCD in a
system for acquisition and processing of images for detection
and visualization of a methane leakage. In another work, Lim
et al [20] examined the response of a cantilever array for
toluene and water vapors using alkane thiol thin sensing films.
The sensor response was obtained reflecting a laser spot on the
cantilevers and measuring its shift on a CCD.
In this work the optimization of an optical system that
uses a CCD camera to detect and quantify VOC is presented.
In a previous work, our research group reported a system
to measure the shift of a fringe pattern produced by the
2
C Martı́nez-Hipatl et al
interaction of a PDMS sensing film with VOC vapors. The
system comprised a Pohl interferometer arrangement, and
a conventional photodetector was used for the response
measurement [21]. In the present work, it has been possible
to improve the detection stage, which previously depended
on the user who would set manually an optimal point on the
fringe pattern to perform the measurement that was quite a
time-consuming process. The performed improvements were
the substitution of the photodetector by a CCD camera and
the development of a computer program to perform data
acquisition and processing. With the new system, the response
measurements were performed semi-automatically; the speed
and reliability of each measurement was increased; and the
total cost of the system was lowered. In this system, each
pixel of the CCD camera can be used as a single photodetector
which allows performing multiple measurements with a single
image. This approach allows calculating an average to improve
the signal to noise ratio.
2. Optical sensor theory
The sensor principle is shown in figure 1. It consists of a glass
substrate with a deposited polymer such as PDMS, which has
the property of swelling when it interacts with organic vapor
molecules [22]. In a previous work [21], it was found that from
the three reflected beams (see figure 1), I2 was negligible and
only I1 and I3 contributed to the interference fringe pattern
described by the following equation:

I = I1 + I3 + 2 I1 I3 cos(δ), (1)
where
δ = 2yk sin θ − . (2)
In the above equation, y is the position of the fringe on a screen,
k is the wave number of the light, θ is the interference angle
between light beams I1 and I3, and  is their phase difference
given by the following equation:
4π  2 1/2 4π  2 1/2
 = d n2 − n21 sin2 θi + d1 n3 − n21 sin2 θi ,
λ0 λ0
(3)
where d and d1 are the thickness of the glass substrate and the
sensing film, respectively; n1, n2 and n3 are the refractive index
for air, glass and PDMS film, respectively; θ i is the incident
angle of the light beam (I0) and λ0 is the wavelength.
In equation (3), if the thickness of the polymer sensing
film changes, it will produce variations in the phase of the
Meas. Sci. Technol. 24 (2013) 105003
Figure 2. Experimental setup of the optoelectronic sensor.
cosine argument, which is observed physically as a shift of the
fringe pattern. The response of the sensor was obtained with
the measurement of such shift.
3. Experimental setup
The experimental setup for the measurement of the steady-state
response of the gas sensor is shown in figure 2. An expanded
and collimated laser beam was reflected in the sensor, which
was located in a Teflon measurement chamber [21]. A CCD
camera (webcam) with a resolution of 640 × 480 pixels was
used to monitor the shift of the fringe pattern, and a computer
program was developed for data acquisition and processing.
The computer program starts with the statement of a video
input object that represents the connection between the PC
and the image acquisition device, and it enables knowing and
modifying the CCD camera parameters. The intensity of the
laser beam and the camera exposure time were modified to
avoid image saturation. A picture of the fringe pattern was
taken, a line perpendicular to the fringe pattern was drawn;
and the optical power in this direction was plotted. As is well
known, in the optical power profile of the fringes there is a
quasi-linear region where the intensity variation is proportional
to a small phase difference (fringe shift). Therefore, a fringe
shift can be detected simply by a measurement of the optical
power variation. Then, a pixel on this quasi-linear region was
selected to monitor such fringe shift. Since the noise was quite
large, the average of the selected pixel with its neighbors
was calculated in order to attenuate such signal noise. The
averaging filter used is described
 by the following equation:
imagei, j
averagem,n = k2
, (4)
where the sum is computed in a k × k window centered at
the pixel (m, n) and m(i), n( j) are the rows and columns,
respectively. Figure 3 shows a schematic of the average
calculation for a 3 × 3 window. However, the computer
program allows the user to select any size of window.
After this, the system starts the measurement, taking
pictures at a rate of 1 fps. The average intensity of the selected
pixel is calculated according to the size of the previously
chosen window and the result is plotted in the computer
screen. The program also stores the complete picture, which
enables performing a post analysis of the sensor response if it
is necessary.
3
C Martı́nez-Hipatl et al
Figure 3. Schematic of data averaging of a pixel m,n with its
neighbors (k = 3).
Figure 4. Optical power profile of the interference pattern for a laser
with a Gaussian beam (the inset shows the fringe pattern).
4. Results and discussion
The inset in figure 4 shows a fringe pattern picture obtained
from a glass substrate without sensing film. This image shows
that the fringe pattern has a high contrast and quality and does
not present distortion since the fringes are quite parallel. On
this pattern image a line was drawn and the optical power in
arbitrary units (au) in such direction was plotted. The curve
is shown in figure 4. The graph shows that the power of the
fringes at the ends has an amplitude less than those at the
center. This is due to the fact that the employed laser has a
Gaussian power profile.
A sensor with an estimated sensing film thickness of
9.5 μm of PDMS was fabricated. The steady-state response of
this sensor measured for 14 500 ppm of ethanol vapor is shown
in figure 5. The pixel (390, 226) of the CCD that was located
in the adequate position on the fringe was selected to monitor
the shift of the fringe pattern. Figure 5(a) shows the raw data
(k = 1), while figures 5(b)–(d) show the response processed
using different window sizes (k = 5, 9 and 15, respectively). At
the beginning of the response measurement only the baseline
was measured. After that, the ethanol sample was injected into
the measurement chamber. It was observed that the optical
power increases, which means the occurrence of the fringe
pattern shift, until the sensor response reaches a steady-state
level. Moreover, it can be said that the response was reversible,
since the optical power recovered its initial baseline after
the measurement chamber was purged. Furthermore, there is
a drift of the baseline caused probably by the temperature
change. Moreover, the level of noise of the sensor response was
on average 5.44 optical-power units, which means a standard
Meas. Sci. Technol. 24 (2013) 105003 C Martı́nez-Hipatl et al

(a) (b)

(c) (d)

Figure 5. Steady-state response of the sensor to 14 500 ppm of ethanol vapor for different window sizes. (a) k = 1 (raw data), (b) k = 5,
(c) k = 9 and (d) k = 15.

Table 1. Results of sensor 1 for different window sizes. Table 2. Results of sensor 2 for two window sizes.
Response Standard deviation Response Standard deviation
K (optical-power units) (optical-power units) LOD (ppm) k (optical-power units) (optical-power units) LOD (ppm)

1 57.21 2.72 1378 1 70.92 2.19 1791

5 56.61 1.89 968
9 58.1 1.32 658
15 58.1 0.99 494
deviation of 2.72 units (inset in figure 5(a)). Under these
conditions, a PDMS sensing film with the above-mentioned
thickness when applied to an ethanol sample produced a
sensitivity of 0.0039 optical-power units/ppm, which means
a limit of detection (LOD) of 1378 ppm. In figures 5(b)–
(d) we can see that the level of noise of the curves was
progressively attenuated when the size of k was increased
(inset in the figures), the curves were smoothed and the
main profile was preserved. For the case of figure 5(d), the
level of noise was 1.98 optical-power units, which means a
LOD of 494 ppm. Such value represents an improvement of
approximately 2.8 times in the resolution. These results are
summarized in table 1. It is important to mention that k must not
be increased arbitrarily, since for larger k values it is possible to
count pixels outside the linear region, which would degrade the
measured signal average. Furthermore, the signal processing
time would be increased. For this specific case, the length of
the linear region was 15 pixels. Such length can be changed
15 69.52 0.66 550
depending on the interference angle (θ in equation (2)), which
in turn, depends on the incident angle (θ i in equation (3)).
In order to corroborate the previously mentioned analysis,
the response to 29 000 ppm of ethanol vapor of another sensor
with a 12 μm thickness sensing film, was measured. Two
windows with k = 1 and 15, respectively, were used to perform
the data averaging to attenuate noise. The pixel (228, 264) was
selected to monitor the fringe shift. The ethanol sample was
injected in two concentration steps of 14 500 ppm. Figure 6(a)
shows the raw data (k = 1); in this curve the level of noise was
4.39 optical-power units, which means a standard deviation of
2.19 units. In this case, the sensitivity was 0.0024 optical-
power units/ppm, which means a LOD of 1791 ppm. On
the other hand, for the case of k = 15 (figure 6(b)), the
level of noise was 1.32 optical-power units, which means a
LOD of 550 ppm. Such value represents an improvement of
approximately 3.3 times in the LOD. The results for this case
are summarized in table 2.
These results are in agreement with those found for the
first sensor. Therefore, it can be said that the use of the CCD
camera not only allows easy and simple measurement of the

4
Meas. Sci. Technol. 24 (2013) 105003
(a)
Figure 6. Sensor responses for different concentration increments (14 500 and 29 000 ppm) of ethanol for two window sizes. (a) k = 1
(raw data), (b) k = 15.
sensor response, but also achieves an important improvement
in the LOD by processing the image of the fringe pattern.
5. Conclusion
An optoelectronic system to measure the steady-state response
to ethanol vapor of sensors that use a PDMS sensing film has
been optimized by the substitution of a photodetector by a CCD
camera. This has the advantage that each pixel can be used as
a single photodetector. A computer program was designed for
data acquisition and processing which allows obtaining and
displaying 1 datum per second. The processing consisted in
an averaging performed inside a window with k × k pixels.
It was found that, as k is increased, the noise level could be
reduced. However, k is limited by the linear region of the
sinusoidal fringe pattern and it cannot be increased arbitrarily.
In our case, it was found that a suitable limit value for k was
15 pixels.
On the other hand, the steady-state responses of sensors
fabricated with 9.5 and 12 μm thickness PDMS sensing films
were measured with the system. For the case of the first sensor,
the level of noise was 5.44 optical-power units in the raw data,
while after data processing using a window with k = 15, the
level of noise was reduced to 1.98. This means a reduction
of approximately 2.8 times, and in this case, the LOD was
improved from 1378 to 494 ppm. In the second sensor, the
level of noise was reduced from 4.39 to 1.32 optical-power
units (approximately 3.3 times) and the LOD was improved
from 1791 to 550 ppm. Therefore, we can say that the CCD
camera allows easy and simple measurement of the sensor
response and an important improvement in the LOD.
Currently, work is under progress to achieve an
improvement in the data acquisition and processing for better
automation.
Acknowledgments
This work was supported in part by the projects Conacyt
Jovenes Investigadores 61126 and Conacyt 154243.
5
C Martı́nez-Hipatl et al
(b)
References
[1] Musatov V Yu, Sysoev V V, Sommer M and Kiselev I 2010
Assessment of meat freshness with metal oxide sensor
microarray electronic nose: a practical approach Sensors
Actuators B 144 99–103
[2] Alimelli A, Pennazza G, Santonico M, Paolesse R, Filippini D,
D’Amico A, Lundström I and Di Natale C 2007 Fish
freshness detection by a computer screen photoassisted
based gas sensor array Anal. Chim. Acta 582 320–8
[3] Yongwei W, Wang J, Zhou B and Lu Q 2009 Monitoring
storage time and quality attribute of egg based on electronic
nose Anal. Chim. Acta 650 183–8
[4] Perkowski J, Buśko M, Chmielewski J, Góral T
and Tyrakowska B 2008 Content of trichodiene and analysis
of fungal volatiles (electronic nose) in wheat and triticale
grain naturally infected and inoculated with Fusarium
culmorum Int. J. Food Microbiol. 126 127–34
[5] Cevoli C, Cerretani L, Gori A, Caboni M F, Toschi T G
and Fabbri A 2011 Classification of Pecorino cheeses using
electronic nose combined with artificial neural network and
comparison with GC–MS analysis of volatile compounds
Food Chem. 129 1315–9
[6] Werlein H-D 2001 Discrimination of chocolates and
packaging materials by an electronic nose Eur. Food Res.
Technol. 212 529–33
[7] Suslick B A, Feng L and Suslick K S 2010 Discrimination of
complex mixtures by a colorimetric sensor array: coffee
aromas Anal. Chem. 82 2067–73
[8] Baldwin E A, Bai J, Plotto A and Dea S 2011 Electronic noses
and tongues: applications for the food and pharmaceutical
industries Sensors 11 4744–66
[9] Muñoz-Aguirre S, Yoshino A, Nakamoto T and Moriizumi T
2007 Odor approximation of fruit flavors using a QCM odor
sensing system Sensors Actuators B 123 1101–6
[10] Kukla A L, Pavluchenko A S, Shirshov Y M,
Konoshchuk N V and Posudievsky O Yu 2009 Application
of sensor arrays based on thin films of conducting polymers
for chemical recognition of volatile organic solvents
Sensors Actuators B 135 541–51
[11] Mönch W, Dehnert J, Prucker O, Rühe J and Zappe H 2006
Tunable Bragg filters based on polymer swelling Appl. Opt.
45 4284–90
[12] Brambilla G 2010 Optical fibre nanotaper sensors Opt. Fiber
Technol. 16 331–42
[13] Gauglitz G, Brecht A, Kraus G and Nahm W 1993 Chemical
and biochemical sensors based on interferometry at thin
(multi)layers Sensors Actuators B 11 21–7
[14] De Girolamo Del Mauro A, Immacolata Grimaldi A,
La Ferrara V, Massera E, Lucia Miglietta M, Polichetti T
Meas. Sci. Technol. 24 (2013) 105003
and Di Francia G 2009 A simple optical model for the
swelling evaluation in polymer nanocomposites J. Sensors
2009 703206
[15] El-Sherif M, Bansal L and Yuan J 2007 Fiber optic sensors
for detection of toxic and biological threats Sensors
7 3100–18
[16] Jorez S, Laconte J, Cornet A and Raskin J-P 2005 Low-cost
optical instrumentation for thermal characterization of
MEMS Meas. Sci. Technol. 16 1833–40
[17] Han F, Inoue T, Kurauchi Y and Ohga K 2007 Reichardt’s dye
as optochemical sensors materials detected polar gas ARPN
J. Eng. Appl. Sci. 2 9–15
[18] Malins C, Niggemann M and MacCraith B D 2000
Multi-analyte optical chemical sensor employing a plastic
substrate Meas. Sci. Technol. 11 1105–10
C Martı́nez-Hipatl et al
[19] Gibson G, Van Well B, Hodgkinson J, Pride R, Strzoda R,
Murray S, Bishton S and Padgett M 2006 Imaging of
methane gas using a scanning open-path laser system
New J. Phys. 8 26
[20] Lim S-H, Raorane D, Satyanarayana S and Majumdar A 2006
Nano-chemo-mechanical sensor array platform for
high-throughput chemical analysis Sensors Actuators B
119 466–74
[21] Martı́nez-Hipatl C, Muñoz-Aguirre S, Beltrán-Pérez G,
Castillo-Mixcóatl J and Rivera-De-la-Rosa J 2010
Detection of volatile organic compounds by an
interferometric sensor Sensors Actuators B 147 37–42
[22] Ng Lee J, Park C and Whitesides G M 2003 Solvent
compatibility of poly(dimethylsiloxane)-based microfluidic
devices Anal. Chem. 75 6544–54