International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN IN 0976 INTERNATIONAL JOURNAL OF ADVANCED RESEARCH 6480(Print),

, ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

ENGINEERING AND TECHNOLOGY (IJARET)

ISSN 0976 - 6480 (Print) ISSN 0976 - 6499 (Online) Volume 4, Issue 6, September October 2013, pp. 175-184 IAEME: www.iaeme.com/ijaret.asp Journal Impact Factor (2013): 5.8376 (Calculated by GISI) www.jifactor.com

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METAL OXIDE SEMICONDUCTOR BASED EXHALED BREATH PELLET SENSOR

Pauroosh Kaushal1, Tapan Dhalsamanta2, Rohini Prashant Mudhalwadkar3
1 2

(Instrumentation & Control, College of Engineering Pune, India) (Instrumentation & Control, College of Engineering Pune, India) 3 (Instrumentation & Control, College of Engineering Pune, India)

ABSTRACT The analysis of the exhaled breath components allows clinicians and researchers to assess different body functions in a convenient and flexible way. In this study, a proportion of zinc oxide and tin oxide nanopowder was used to fabricate gas sensor in the form of pellet. The effect of exhaled breath and exhaled breath components at room temperature on the electrical conductivity, sensitivity, response time and recovery time of pellet sensor has been studied. The study revealed that the electrical conductivity of pellet sensor decreases with exposure of exhaled breath. The electrical conductivity of the pellet sensor gives response differently for different exhaled breath components. Characterization of pellet sensor for response of exhaled breath is done and can be useful for disease detection or quantification of exhaled breath components. Keywords: exhaled breath, gas sensor, tin oxide, zinc oxide, sensitivity 1. INTRODUCTION In last few years, breath analysis is emerged as one of the most effective technique for exhaled breath analysis [1]. Comparing the traditional diagnosis tests for normal clinical practices, breath analysis is non-invasive, real-time, and least harmful to not only the subjects but also the personnel who collect the samples. Breath is a complex matrix where flow rate, temperature, humidity, and gas concentration are multifarious, time-dependent variables. Certain gases in the breath are known to be indicators of the presence of diseases and clinical conditions [2]. Furthermore, volatile organic compounds (VOCs) found in human breath have been linked to various physiological conditions. For example, nitric oxide is indicative of pulmonary dysfunction, acetone has been linked to diabetes, ammonia is an indicative of renal disease etc [3] [4]. Table 1 shows typical composition from the exhaled breath of the healthy persons. Hence, understanding the correlation between breath compounds and the condition of the human body has attracted increasing interest in clinical diagnostics.
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Table 1: Typical composition from the exhaled breath of the healthy persons Concentration (v/v) molecules Percentage Oxygen, water , carbon dioxide Parts-per-million Acetone, carbon monoxide Parts-per-billion Nitric oxide, ammonia In order to detect the breath compounds, many techniques have been proposed. There are analytical methods and non conventional methods to detect compounds of exhaled breath. Laser spectroscopy, conducting polymer nanojunction, Quantum Cascade Lasers are some of the techniques used for real time analysis of exhaled breath. These techniques are quite accurate but are expensive, time consuming, and non-portable [5][6][7]. One of the techniques for gas analysis is metal oxide semiconductor (MOS) gas sensors which respond to specific gases [1][8][9]. When metal oxide crystals like SnO2 are heated at certain high temperature, they exhibit sensitivity towards oxidizing and reducing gases by a variation of their electrical properties. Different composition of metal oxide gas sensors has sensitivity towards specific target gases [10]. This technique eliminates the disadvantages of other techniques by its low cost and easy operation features. These sensors are one of the efficient and cheapest ways to analyze gases and can be used for analysis of the exhaled breath components. Among many of the market available gas sensors for different gases, these pellet sensors are one of the cheapest and effective methods for analyzing the exhaled breath. The proposed system makes use of MOS sensor, made up of tin oxide doped with zinc oxide that at are sensitive to composition of exhaled breath components. Characterization of the sensor for response of exhaled breath and its components is done. The usefulness of the system for disease detection and quantification of breath components are discussed. 2. MATERIAL AND METHODS This section is focused on fabrication of sensor which are prepared in the laboratory in the form of pellets. Tin oxide nanopowder and zinc oxide nanopowder are selected for pellet preparation because of their availability, non-toxicity, suitability of doping and high chemical stability. The resistance of pellet changes when gases pass through it and adsorbed on the surface. The adsorption is maximum for the nanopowder as they have high surface to volume ratio which makes it very sensitive upon gas injection. The size of the particle used is less than 100 nm. Formations of Pellets involve the following steps: Weighting Weighting of the powder is done with micro balance machine available in the lab. The two powder ratio is pre decided and the weighing is done, deciding the percentage composition of mixture. The weight ratios decided for pellet design is a mixture of zinc oxide nanopowder (10%) and tin oxide nanopowder (90%). 2.2 Pulverizing Pulverizing is done to mix properly both the powders to obtain a properly mixed ratio. This process is carried out with isopropyl alcohol being added at each interval. 2.3 2.1

Pressing Before forming the pellets using any hydraulic press machine, the pulverized powder is mixed with a drop of Poly Vinyl alcohol (PVA) which acts as a binding agent. This process results in good formation of pellets and enhances the press effect carried out further. The formation of pellets is done using a hydraulic pellet press machine available in the laboratory. The pulverized powder is
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

taken in the required quantity, 0.3 grams, and put into the die set. Pellets are pressed for duration of 5 mins usually with a pressure range from 90- 100 Kg/cm2 resulting in pellets of size 8mm. Sintering Sintering is the process wherein the formed raw pellets undergo heat treatment under closed conditions. This hardens the raw pellet and makes it quiet sturdy. Sintering is carried out at a temperature from 800C for 6 hours of time. Contacts The contacts for pellets are made up of material having high conductivity. Silver paste is used as a contact material. They are placed on the pellet ends to reduce contact resistance and so to get better response of the pellet sensor. The sensor was fabricated on a small piece from general purpose board. The output resistance is measured from the two ends of silver wire. Since the output is of high resistance, it needs to be converted in voltage form to get processed and displayed. To achieve this conversion, output of pellet is fed to input of wheatstone bridge. Fig. 1 shows the pellet sensor with the contacts. 2.5 2.4

Figure 1: Pellet sensor with contacts attached 3. GAS SENSOR ASSEMBLY Composition of nanopowder tin oxide (90%) and nanopowder zinc oxide (10%) is used for pellet sensor fabrication. The pellet is placed in a small enclosure, where sample gas is injected. The sample gases are either exhaled breath or individual exhaled breath components. To collect exhaled breath sample, a mouthpiece is used for direct injection of sample on pellet. The responses of components of exhaled breath on pellet sensor are known by injecting gases through canisters. The enclosure of the system is done in such a way that there will not be any interference of external air with the sample gas. The enclosure size is 4*4*2 inch. Electrical conductivity of pellet sensor is recorded through contacts of pellet which measures the interaction between the sample gas and the sensor. The resistance of pellet is recorded using multimeter and readings are plotted. The interval time of recording was chosen based on the time taken for the pellets resistance to revert to the original reading. All the measurements were taken at a constant temperature decided by the heater. The incandescent bulb is used as heater which operates at 3V supply. This was done to guarantee that
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

the sensor is at stable temperature. After 20 minutes of switching on the bulb, stable resistance is observed in the range of 200k to 350k. Resistance values are converted into voltage form using wheatstone bridge ranges from 0 to 5V. It is connected to the analog input port of microcontroller. Then it is displayed in 16 x 2 LCD display. In the final output display, real time voltage change of the sensor is displayed. Fig. 2 shows the sensor assembly interfaced with signal processing circuitry. The tests were repeated for samples in order to get precise results.

Figure 2: Gas sensor assembly interfaced with display 4. RESULT AND DISCUSSION The composition of exhaled breath has a great impact on response of the gas sensor. The exhaled breath contains percentage of O2, N2 and CO2. Experimentations are performed using standard gas injection and exhaled breath on MOS pellet. The responses from each of the sensors are recorded and characterization is carried out. Exhaled Breath Response on Pellet Sensor Subject is asked to inhale maximally and instructed to exhale the air in 2 blow through the mouth piece. The change in resistance is observed with respect to time and recorded. The response curve is plotted and characterization of sensor is done. Response curve for exhaled breath of three normal subjects are shown. Fig. 4, fig. 5 and fig. 6 show responses of exhaled breath injection on pellet sensor. 4.1

Figure 4: Exhaled breath response of pellet sensor for subject 1

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Figure 5: Exhaled breath response of pellet sensor for subject 2

Figure 6: Exhaled breath response of pellet sensor for subject 3 From above figures, it is seen that the resistance of the pellet increases as soon as the exhale breath is injected on the sensor, then it settled to its original value after few minute. The resistance of pellet in air (Ra) is found to be 0.22 M. The ratio of peak resistance (Rp) and resistance in air is computed. The resistance ratio value gives a reciprocal of sensitivity. The ratios of subjects are compared. It is found to be repeatable. The collected data are analyzed and tabulated to characterize the pellet sensor as shown in table 2.

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Table 2: Characteristic of pellet sensor for exhaled breath No of subject 1 2 3 4.2 Peak resistance(M) 0.37 0.45 0.40 Response time (sec) 15 10 12 Settling time(sec) 280 210 230 Preheating time(min) 20 20 20 Resistance ratio(1/sensitivity) 1.68 1.66 1.63

Pellet response for CO2 injection Standard gases are introduced on pellet sensor using gas canisters. Since exhaled breath is rich in carbon dioxide, the response of the gas is recorded on the sensor. Fig. 7 shows response of pure CO2 injection on the sensor. The gas was injected for time of 60 seconds with flow rate of 0.25 litres/min.

Figure 7: Pellet sensor response for CO2 injection It is observed that the response remains still for some time then it increases slowly to 3.8 volt. It gets saturated at that point which indicated the maximum adsorption of gas on the sensor. The pellet output voltage (Va) for CO2 in air is found to be 3.46 V and upon exposure to pure CO2 the output voltage (Vp) rises to 3.8 V. The ratio of Vp and Va is calculated. The table 4.10 shows voltage response of pellet for CO2 injection. Since there is a small change in response to CO2 injection, the voltage ratio is almost unity.

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Table 4.10: Voltage response of pellet for CO2 injection Concentration 99.9% Peak voltage 3.8 Voltage in air 3.5 Voltage ratio 1.08

4.3

Pellet response for O2 injection The response of pellet sensor for O2 injection remains constant throughout the experiment, plotted in fig. 8. The voltage response to 99.9% of O2 injection is 4.37 V. So it can be conclude that pellet sensor has no response for O2.

Figure 8: Pellet response for O2 injection

Humidity and Temperature Measurement of Exhaled Breath Exhaled breath is very rich in humidity or moisture content. To have a quantitative moisture content parameter, humidity sensor SY-HS-220 is used. Temperature change is also monitored during the experiment. This is done using temperature IC LM35 which has a linear response over wide temperature range. We place temperature IC and humidity sensor in the system enclosure. Subject is asked to inhale maximal and forcefully exhale on the sensors. Response of both the sensors is recorded and analyzed. The humidity sensor output the voltage which is then compared with its characteristic curve to know relative humidity of the sample. The characteristic curve of humidity sensor is shown in fig. 9. By comparing the sensor output with relative humidity of exhaled breath of different subjects, it is approximated that exhaled breath contains around 80% RH.

4.4

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Figure 9: Characteristic curve of SY-HS-220 humidity sensor The conclusion matches with the theory. Fig. 10, fig. 11 and fig. 12 show sensor output, indicating the sensor output voltage increases and then decays with time. The humidity sensor voltage output is compared with its standard chart to know relative humidity of the sample. During exhalation, temperature increases by just 1o degree.

Figure 10: Subject 1 exhaled breath response 88% RH

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

Figure 11: Subject 2 exhaled breath response 81% RH

Figure 12: Subject 3 exhaled breath response 84% RH The humidity sensor is characterized for exhaled breath response and tabulated, shown in table 3. It can be observed that the value is quite repeated for exhaled breath response of all normal subjects. Table 3: Characteristic of humidity sensor for exhaled breath Peak voltage (V) Relative Response time Humidity(%) (sec) 2.74 2.51 2.57 88 81 84 5 4 4

No of subject 1 2 3

Settling time (min) 12 10 11

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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 6, September October (2013), IAEME

5. CONCLUSION The proposed system is noninvasive and low cost system model for exhaled breath analysis. Pellet sensor has shown good stability for exhaled breath injection. The resistance of the pellet sensor increases as exhaled breath is injected on the sensor and is found to be stable. The pellet sensor is characterized by sharp change in resistance with constant resistance ratio and rapid settling time. The sensitivity of sensor remains constant for normal exhaled breath exposure. The sensor gives a small rise in output voltage when exposed to CO2 injection and unresponsive for injection of O2 gas. The humidity level of normal exhaled breath is calculated and results are accurate. Hence, the study revealed that the electrical resistivity increases when exposed to normal exhaled breath in the surrounding air of the sensor. In future, the sensor performance for normal exhaled breath and exhaled breath of diseased subjects can be compared. Disease detection can be possible based on the comparison as sensor performance would be different for diseased exhaled breath injection. 6. REFERENCES [1] Dongmin Guo, David Zhang, Fellow, IEEE, Naimin Li, Lei Zhang, Member, IEEE, and Jianhua Yang, A Novel Breath Analysis System Based on Electronic Olfaction IEEE Transactions on Biomedical Engineering, Vol. 57, No. 11, Nov 2010, 2753-2763. [2] Todor A. Popov, Human exhaled breath analysis, Annals of Allergy, Asthma & Immunology, Vol. 106,451 456 June 2011 [3] Anton Amann , Guy Poupart , Stefan Telser , Maximilian Ledochowski, Alex Schmid, Sergei Mechtcheriakov, Applications of breath gas analysis in medicine, International Journal of Mass Spectrometry, Vol 239, 227233, October 2004 [4] Darryl Hill, Russell Binions, Breath Analysis for Medical Diagnosis, INTERNATIONAL JOURNAL ON SMART SENSING AND INTELLIGENT SYSTEMS, VOL. 5, NO. 2, JUNE 2012. [5] K. Namjou, C. B. Roller, and G. McMillen, Breath-Analysis Using Mid-Infrared Tunable Laser Spectroscopy, IEEE SENSORS 2007 Conference 1337-1340 [6] Joanne H. Shorter, David D. Nelson, J. Barry McManus, Mark S. Zahniser, and Donald K. Milton, Multicomponent Breath Analysis With Infrared Absorption Using RoomTemperatureQuantum Cascade Lasers, IEEE SENSORS JOURNAL, VOL. 10, NO. 1, JANUARY 2010 76-84 [7] Michael J. Thorpe, David Balslev-Clausen, Matthew S. Kirchner, and Jun Ye, Cavityenhanced optical frequency comb spectroscopy: application to human breath analysis, Optical Society of America, February 2008, Vol. 16, No. 4 [8] George F. Fine, Leon M. Cavanagh, Ayo Afonja and Russell Binions, Metal Oxide SemiConductor Gas Sensors in Environmental Monitoring, IEEE Sensors, Vol 10, 5469-5502 June 2010 [9] T. A. Miller, S. D. Bakrania, C. Perez, M. S. Wooldridge, Nanostructured Tin Dioxide Materials for Gas Sensor Applications, Functional Nanomaterials, American Scientific Publishers, 2006 [10] Matthias Batzill, Ulrike Diebold, The surface and materials science of tin oxide, Progress in Surface Science vol. 79, 47154, 2005. [11] Kavita L.Awade, Emerging Trends of Nanotechnology in Biomedical Engineering, International Journal of Electronics and Communication Engineering & Technology (IJECET), Volume 1, Issue 1, 2010, pp. 25 - 32, ISSN Print: 0976- 6464, ISSN Online: 0976 6472.

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