International Journal of JOURNAL Electrical Engineering and Technology (IJEET), ISSN 0976 INTERNATIONAL OF ELECTRICAL ENGINEERING 6545(Print), ISSN

N 0976 6553(Online) Volume 4, Issue 2, March April (2013), IAEME & TECHNOLOGY (IJEET)
ISSN 0976 6545(Print) ISSN 0976 6553(Online) Volume 4, Issue 2, March April (2013), pp. 179-186 IAEME: www.iaeme.com/ijeet.asp Journal Impact Factor (2013): 5.5028 (Calculated by GISI) www.jifactor.com

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HUMIDITY SENSING PROPERTIES OF POLYANILINE/POTASSIUM MOLYBDATE COMPOSITES

K C Sajjan1, Muhammad Faisal2, Khened B.S3 and Syed Khasim4* Department of Physics, Veerasaiva College, Bellary-583104, Karnataka, India Department of Physics, PESIT South Campus, Bangalore-560 100, Karnataka, India 3 Deparment of Electrical and Electronics Engineering BITM, Bellary-583104, Karnataka, India 4 Department of Physics, Universityof Tabuk-71491, KSA
2 1

ABSTRACT Polyaniline (PAni) Potassium Molybdate (PM) (K2MoO4) composites were synthesized by insitu chemical polymerization of aniline in the presence of fine graded K2MoO4 particles. Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD) and Fourier Transform Infra-Red (FTIR) spectroscopy were used to characterize the PAni-PM composites. The characterization results confirm the polymerization of aniline over PM particles which results into strong interaction between PAni and PM particles. A detailed mechanism of electric transport was analyzed using DC conductivity, Humidity sensing characteristics such as variation of resistance as a function of relative humidity (RH) were analyzed for PAni-PM composites. The composite with 50 wt% of PM in PAni exhibit better humidity sensing property than pure PAni and other PAni-PM composites. KEYWORDS: Polyaniline; Polyaniline Composites; Polyaniline-Potassium Molybdate composites; Humidity sensors. 1. INTRODUCTION Humidity control and monitoring are of great interest to a wide area; these include moisture sensitive products, fresh and package food, drug storage and environmental control for valuable antiques or paintings etc [1, 2].Humidity sensors that are available in the market include dew point, infrared, catalytic and tin oxide sensors, which may be expensive, or
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require high temperature operation and consume significant amount of power and high cost of maintenance [3]. Much research has been focused on the development of humidity sensitive material [4-6]. Among these are the investigations using conducting polymers such as polypyrrole, polythiophene and polyaniline for humidity and gas sensing [7-9].Advantages with polymers as sensing materials are light weight, flexible, low cost and simple fabrication process [10]. Pure polymer, polymer blends and polymerinorganic composites have also been studied for the purposes, resulting in different degree of advancements in this area [1119]. Generally, conducting polymers behave quite similarly on exposure to humidity. A resistance decrease (or conductivity increase) is observed due to the formation of H-bonding between water molecules and the nitrogen centre of the polymer backbone. This facilitates the proton exchanges to increase the doping level of the conducting polymer and so the number of charge carriers increases, resulting in an increase in conductivity [20]. Earlier we have reported PAni/WO3 composite with better electrical and humidity sensing properties than individual polyaniline and WO3 alone [18]. In the present paper we report the detailed investigation of electrical and humidity sensing response of PAni - K2MoO4 (PAni-PM) composites. 2. EXPERIMENTAL 2.1 Synthesis of PAni- K2MoO4 composites The chemical oxidative polymerization of aniline into polyaniline was carried out using the ammonium peroxydisulphate as an oxidant in the presence of HCl as reported elsewhere including some of our previous works [7, 13, 18, 19, 21]. PAni - K2MoO4 composites were synthesized by adding different wt% (10, 20, 30, 40 and 50) of K2MoO4 during the polymerization of aniline by fixing the yield as we have reported in the preparation of PAnicomposites earlier [18, 21, 22]. The bulk samples were processed into circular pellets using a hydraulic press and coated with silver paste to provide electrical contacts for various measurements. 2.2 Characterization Surface morphology of PAni, K2MoO4 and PAni - K2MoO4 composites were investigated by Scanning electron microscopy using Philips XL30 ESEM. X-ray diffraction was carried out by X-ray powder diffraction at ambient temperature for the structural characterization of PAni, K2MoO4 and PAni - K2MoO4 composites. A Rigaku (RU-300) Xray diffractometer with Cu- K (1.54 A0) radiation was used. The FTIR spectra of PAni, K2MoO4 and PAni - K2MoO4 composites were recorded on a Perkin-Elmer 1600 spectrophotometer in KBr medium. 2.3 Measurements The Temperature dependent conductivity was recorded using two-probe method on a Keithley - 2000 multimeter, USA. . The samples in the pellet form were used for humidity sensing. The planar resistance of the sensor was recorded by controlling the humidity in a glass chamber (fig.1) at room temperature. The humidity was first lowered by keeping CaCl2 in the chamber. Controlled water vapors at room temperature were then introduced steadily
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International Journal of Electrical Engineering and Technology (IJEET), ISSN 0976 6545(Print), ISSN 0976 6553(Online) Volume 4, Issue 2, March April (2013), IAEME

for increasing the humidity inside the chamber from 20 to 95 % RH. Relative humidity inside the chamber was monitored and measured by a standard pre-calibrated humidity meter Mextech-DT-615.

Fig. 1 - set-up designed for humidity sensing 3. RESULTS AND DISCUSSION 3.1 Scanning Electron Microscopy The SEM of PAni - K2MoO4 composite with 50 wt% of K2MoO4 in PAni is shown in Fig. 2(b) which reveals the presence of K2MoO4 particles uniformly distributed throughout the PAni sample. The presence of capillary pores as seen from this figure facilitates the sensing mechanism for PAni - K2MoO4composites.Figure 2(b) shows the SEM of pristine PAni. The SEM shows the formation of a spongy amorphous structure. Theparticle formation in polyaniline takes place by heterogeneous nucleation.

Fig. 2 SEM ofa)PAni - K2MoO4 composite with 50 wt% of K2MoO4b) pristine PAni

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As a result granular coral like structures are formed. As a characteristic of polyaniline, secondary nucleation [23] also takes place because of which the granular coral-like particles come together to form aggregates. 3.2 X-Ray Diffraction Analysis Fig. 3 shows the x-ray diffraction patterns of (a) pristinePAni, (b) K2MoO4 and (c)PAni - K2MoO4 composite with 50 wt% of K2MoO4 in PAni. The two broad peaks between 2 = 20o to 30o are characteristic semi crystalline peaks of polyaniline [7, 13, 18, 19, 21] as shown in Fig. 3(a) which confirms that the PAni synthesized in the present work has a short range alignment of polymer chains. Fig. 3(b) represents the XRD pattern of K2MoO4. The characteristic peaks between 2 = 25o to 32o confirms the monoclinic crystalline nature for K2MoO4. The XRD pattern of PAni - K2MoO4 composite (with 50 wt% of K2MoO4 in PAni) is shown in Fig. 3(c). The presence of characteristic peaks of K2MoO4 in this figure confirms that the K2MoO4 has retained its structural characteristics in the composite form.

Fig. 3 X-ray diffraction patterns of (a) pristine PAni (b) K2MoO4 (c) PAni - K2MoO4 composite with 50 wt% of K2MoO4 3.3 Fourier Transform Infra Red spectroscopy The FTIR Spectra of pristine PAni, K2MoO4 and PAni - K2MoO4 composite with 50 wt% of K2MoO4in PAni is shown in Fig. 4 . Fig. 4(a) represents the FTIR spectra of pure polyaniline with prominent peaks around 1400 cm-1 to 1600 cm-1 results due to the stretching of C=N and C=C of quinoid and benzonoid rings [22]. The broad peaks between 900cm-1 to 1200cm-1 is due to C-N and C-C stretching frequencies [22]. The sharp and prominent peak around 900cm-1 in the FTIR spectra of K2MoO4 shown in Fig. 4(.b) is a characteristic peak for molybdate ascribed due to M-O-H bending mode formed due to the overlapping of molybdate and potassium [24]. The weaker bands around 3500cm-1 is due to OH stretching frequency and hence shows the presence of lattice water [24]. In the FTIR spectra of PAniK2MoO4 composite as shown in Fig. 4(c), the composite has retained all the prominent peaks that were observed in pure PAni and the prominent peaks of K2MoO4 disappears after the
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composite formation clearly suggests the binding of organic-inorganic components. Hence the FTIR spectra of the composite clearly suggest the formation of strong bonding mechanism between PAnichains and K2MoO4 particles.

Fig. 4 - FTIR Spectra of (a) pristine PAni , (b)K2MoO4 and (c)PAni - K2MoO4 composite with 50 wt% of K2MoO4

3.4 Electrical Properties 3.4.1 DC Conductivity Fig. 5shows the variation in dc conductivity dcas a function of temperature for PAni (inset) and PAni - K2MoO4 composites. The conductivity dc is found to increase with increase in temperature. The dc conductivity is seen to be of three phases. In the first phase where the temperature range is 20 - 100 0C, the conductivity values are almost constant and in the second phase where the temperature range is 100 - 160 0C it increases slowly and in the last phase where temperature is in the range160 - 180 0C, a linear increment in the conductivity is observed. This behavior is perhaps due to thermally assisted hopping of polarons from one localized state to another that can be confirmed by Mott theory. The increase in conductivity is due to the variation in distribution of K2MoO4 particles, which may support more number of charge carriers to hop between favorable localized sites causing increase in conductivity. The variation of conductivity depends on the content of K2MoO4 in PAni as shown in Fig. 6. In this figure dc for all the composites as a function ofwt% of K2MoO4 in PAni at 3 different temperaturesis shown. From these plots it is clear that at all temperatures, the dc of these composites increases with increasing content of K2MoO4, as the K2MoO4 content in PAni increases, it leads to the formation of more number of conducting islands and a strong coupling interactions between PAni chain and K2MoO4 particles, leading to increase in macroscopic conductivity.

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Fig. 5 - Variation of dc as a function of temperature Fig. 6 - Variation of dc conductivity with forPAni - K2MoO4 composites concentration of K2MoO4
3.5 Humidity sensing properties The variations in the resistance as a function of relative humidity (RH) value for PAni K2MoO4 in the form of pellets for five different weight percent of K2MoO4 (10, 20, 30, 40 and 50 wt%) are shown in Fig. 7. A laboratory set-up is designed for humidity sensing (as shown in Fig 1) in which the humidity is first lowered by introducing CaCl2 in the chamber [18, 19]. Then the water vapors are introduced in the chamber with the help of air compressor which is attached to a flask containing water in order to increase humidity inside the chamber from 20 to 95% RH. The change in the resistance was monitored for the composites as the relative humidity in its surrounding was varied. The resistance of the composite was observed to decrease with increase in the relative humidity(RH%). The resistance change becomes quite significant with increase in content of K2MoO4 in PAni. The decrease in resistance with increase in relative humidity is because of adsorption of water molecules by the pellet surface. Typically on exposure to water vapor, polyaniline becomes protonated, and an increase in conductivity is observed. The humidity sensing property of polyaniline to water vapor can be regarded as electron hopping assisted by proton transfer mechanism and capillary condensation of water molecules into the sample surface [25, 26]. At low humidity, under dry conditions the mobility of the K2MoO4 ion is restricted and the polymer chains would tend to curl up into compact coil form. On the contrary, at high humidity, the polymer absorbs water molecules and followed by the uncurling of the compact coil, forms into straight chains that are aligned with respect to each other. This geometry of the polymer is favorable for enhanced mobility of the K2MoO4 ion or the charge transfer across the polymer chains and hence the conductivity increases [17, 18]. Fig 8 shows the variation of resistance with weight percent of K2MoO4 in PAnifor 5 fixed relative humidity of 30, 45, 60, 75 and 90 % RH, where it was observed that as weight percent of K2MoO4 in PAni increases the resistance decreases, hence conductivity increases. This could be due to an increase in the disorderliness of the composite with increasing amount of K2MoO4 which is also seen from SEM. This increase in disorderedness causes higher capillary action and more amount of water being swallowed which results into increase in conductivity. The composite with 50 wt% of K2MoO4 in PAni shows significant reduction in resistance indicating its potential to be used as a polymer based humidity sensor.
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Fig. 7 - Resistance as a function of relative humidity weight (RH) value for PAni - K2MoO4 composites CONCLUSIONS

Fig. 8 - Variation of resistance with percent of K2MoO4 in PAni

This paper presents hitherto unreported humidity sensing and electrical properties of polyaniline- Potassium molybdate composites synthesized by insitu chemical polymerization technique. The characterization results such as SEM shows the formation of uniform, spongy, amorphous surface morphology with capillary pores which is suitable for humidity sensing application. The XRD spectrum of composite shows the presence of prominent peaks corresponds to K2MoO4 indicates the crystalline nature of composite in spite polyaniline being amorphous. The FTIR spectrum reveals the formation of composite with strong interactions between PAnichains and K2MoO4 particles. The composite exhibit better electrical properties than pristine PAni as analyzed through DC conductivities. The electrical properties in these composites show a strong dependence on content of K2MoO4 in PAni with a well observed percolation phenomenon. PAni - K2MoO4 composites exhibit pronounced change in resistivity with changing humid environment. The resistivity change with varying humidity depends on content of K2MoO4 in PAni. The composite with 50 wt% of K2MoO4 in PAnishows pronounced reduction in resistivity indicating the potential of this material to be used as a humidity sensor for practical applications. REFERENCES [1] E. Bracken, Sens. Rev. 17 (1997) 291298. [2] C.Y. Lee, G.B. Lee, Sens. Lett. 3 (2005) 115. [3] D. Hodgins, Sens. Rev. 14 (4) (1994) 2831. [4] S.K. Khijwania, K.L. Srinivasan, J.P. Singh, Sens. Actuators B 104 (2005) 217222. [5] Z.M. Rittersma, Sens. Actuators A 96 (2002) 196210. [6] Z. Chen, C. Lu, Sens. Lett. 3 (2005) 274295. [7] N. Parvatikar, S. Jain, S.V. Bhoraskar, M.V.N.A. Prasad, J. Appl. Polym. Sci. 102 (2006) 55335537. [8] T. Maddanimath, I.S. Mulla, S.R. Sainkar, K. Vijayamohanan, K.I. Shaikh, A.S. Patil, S.P. Vernekar, Sens. Actuators B 81 (2002) 141151.
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[9] A.G. MacDiarmid, Synth. Met. 84 (1997) 2734. [10] G. Harsanyi, Sens. Rev. 20 (2000) 98105. [11] R. Nohria, R.K. Khillan, Y. Su, R. Dikshit, Y. Lvov, K. Varahramyan, Sens. Actuators B 114 (2006) 218222. [12] DewyaniPatil, PradipPatil, You-KyongSeo, Young Kyu Hwang, Sens. Actuators B 148 (2010) 4148. [13] N. Parvatikar, S. Jain, C.M. Kanamadi, B.K. Chougule, S.V. Bhoraskar, M.V.N.A. Prasad, J. Appl. Polym. Sci. 103 (2007) 653658. [14] S.T. McGovern, G.M. Spink, G.G. Wallace, Sens. Actuators B 107 (2005) 657665. [15] M.L. Singla, S. Awasthi, A. Srivastava, Sens. Actuators B 127 (2007) 580585. [16] M. Wan, Z.X. Wei, Z.M. Zhang, L.J. Zhang, K. Huang, Y.S. Yang, Synth. Met. 135 (2003) 175176. [17] S. Jain, S. Chakane, A.B. Samui, V.N. Krishnamurthy, S.V. Bhoraskar, Sens. Actuators B 96 (2003) 124129. [18] N. Parvatikar, S. Jain, S. Khasim, M. Revansiddappa, S.V. Bhoraskar, M.V.N. Ambika Prasad, Sens. Actuators B 114 (2006) 599603. [19] Machappa T, M. Sasikala, Koppalkar R. Anilkumar and M. V. N. Ambika Prasad, Sensors and Transducers Journal 107 (2009) 77-85. [20] J.P. Travers, M. Necheschein, Synth. Met. 21 (1987) 135141. [21] Muhammad Faisal and Syed Khasim, Advanced Materials Research Vols. 488-489 (2012) 557-561. [22] Syed Khasim, S C Raghavendra, M Revanasiddappa, K C Sajjan, Mohana Lakshmi and Muhammad Faisal, Bull. Mater.Sci 34(7) (2011) 1557-1561. [23] Dan Li and Richard B. Kaner, J. Am. Chem. Soc. 128(3) (2006) 968 975. [24] A. Nilchi, B. Maalek, A. Kanchi, M.G. Maragheh, A. Bagheri, Radiat. Phys. Chem.75 (2006) 301308 [25] ShabnamVirji, Richard B. Kaner, and Bruce H. Weiller, J. Phys. Chem. B 110(44) (2006) 22266-22270. [26] N. Yamazoe, Y. Shimizu, Sens. Actuators B 10 (1986) 379. [27] Khened B.S, Machappa.T, M.V.N. Ambika Prasad and Sasikala. M., Impedance Spectroscopic Studies On Pani/Ceo2 Composites International Journal of Electrical Engineering & Technology (IJEET), Volume 4, Issue 1, 2013, pp. 1 - 8, ISSN Print : 09766545, ISSN Online: 0976-6553. [28] Sandeep Dhariwal, Vijay K. Lamba and Ritu Vijay, Analyzing The Transport Properties Of Metallic Swcnt Interconnects Between Gold Electrodes International journal of Electronics and Communication Engineering &Technology (IJECET), Volume 3, Issue 2, 2012, pp. 451 - 460, ISSN Print: 0976- 6464, ISSN Online: 0976 6472.

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