Sensors and Actuators B 143 (2010) 530–534

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Sensors and Actuators B: Chemical
journal homepage: www.elsevier.com/locate/snb

Humidity sensors based on polyaniline nanofibres
Fan-Wu Zeng a , Xiao-Xia Liu a,∗∗ , Dermot Diamond b , King Tong Lau a,b,∗
a China-Ireland Center for Advanced Materials and Sensor Development, Department of Chemistry, Northeastern University, Shenyang 110004, China b School of Chemical Sciences, National Centre for Sensor Research, CLARITY—Centre for Sensor Web Technology, Dublin City University, Glasnevin, Collins Avenue, Dublin D9, Ireland

a r t i c l e

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a b s t r a c t
Humidity sensor based on polyaniline nanofibres was fabricated and its response to humidity was investigated. It was found that the sensor behaved differently compared to commonly known conducting polymer based sensors. The sensor responded to low relative humidity (<50% RH) normally by decreasing electrical resistance with increasing humidity. However, at higher RH the sensor reversed its responses by increasing the electrical resistance with humidity. It is believed that the unique structure of nanofibres, which is more susceptible to distortion during polymer swelling, is responsible for the ‘reversed behaviour’. IR data confirmed that excess water absorption occurred and that a change in polymer oxidation state might also have taken place. © 2009 Elsevier B.V. All rights reserved.

Article history: Received 23 June 2009 Received in revised form 21 September 2009 Accepted 24 September 2009 Available online 17 October 2009 Keywords: Conducting polymer Polyaniline Humidity sensor Polymer swelling PAni nanofibres

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 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 investigation of 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 polymer–inorganic composites have also been studied for the purposes, resulting in different degree of advancements in this area [11–17]. 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 [18]. This paper reports the investigation of using polyaniline (PAni) nanofibres based sensor for humidity measurement. For the first time a reverse phenomenon was observed for the PAni sensor during exposure to controlled humidity environments. 2. Experimental 2.1. Screen-printed electrode Screen-printed electrodes (SPEs) used as substrate for PAni fabrication and for conductivity measurement were printed from Carbon/Graphite paste ink purchased from Gwent Electronic Materials Ltd. The design shown in Fig. 1 consisted of two mirror image L shape electrodes facing each other with the bending arm of one electrode on top of the other leaving a vertical distance of 0.125 m between the horizontal arms of the electrodes. The width of the electrode track was 1 mm; the outer electrode body length was 21 mm with the bending arm length of 8.5 mm. Polyaniline was fabricated directly on the electrodes to bridge across this gap as detailed below. 2.2. Sensor fabrication

∗ Corresponding author: Tel.: +35317007926; fax: +35317007995. ∗∗ Corresponding author. E-mail addresses: xxliu@mail.neu.edu.cn (X.-X. Liu), kim.lau@dcu.ie (K.T. Lau). 0925-4005/$ – see front matter © 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2009.09.050

Aniline was purified by vacuum distillation before use. PAni nanofibres film was fabricated onto the screen-printed electrodes

22. Zero percent humidity was maintained using CaCl2 or activated molecular sieve.2. 57. CH3 COONa. NaCl. Humidity control The humidity level was controlled by saturated salt solutions prepared from LiCl.125 m gap. The PAni microaggregate sensor exhibited high resistance of over 80 k . For reference. 84.22]. which would be expected to enhance the movement of charge carriers to achieve high conductivity. A solution of 0. the polymer chains within the micro aggregated polymer film were much less orderly and less tightly packed together. The solution was dropped onto and bridged the insulate gap of SPE before dried in an oven at 80 ◦ C for 24 h.4. the sensor was exposed to the headspace of the saturated salt solutions for 10 min or until equilibrium was reached.-W. Results and discussion The gas sensor based on PAni nanofibres was fabricated directly onto the screen-printed electrodes using chemical deposition method.5 M (NH4 )2 S2 O8 was added into equal volume of a 0.3. then dried overnight in ambient conditions and stored at room temperature before use. PAni powder was also prepared using known method [21. Two probes method was employed for the measurement.3. tightly packed polymer chains.4 M aniline solution under constant stirring for 5 h between 0 and 5 ◦ C. KI. 32. These important characteristics of nano structures are expected to give enhanced sensor performance with respect to sensitivity and response time. Zeng et al.0 M HCl to clean off residue species.8. Measurement procedure The resistance of the PAni films was measured with an UT70d Multimeter (Shanghai.0 M hydrochloric acid solution and 0. Very high conductivity was observed from the PAni nanofibres based sensor at around 6 k measured across 0.3. using chemical deposition method [19. a conventional micro aggregate PAni sensor was prepared from PAni powder synthesized from conventional chemical method. 2. 75.F. respectively. These observations support the predictions that within nanofibres membrane.20]. Scanning electron microscopic images of (a) the PAni nanofibres and (b) the conventional PAni films fabricated across the screen-printed carbon-paste electrodes. MgCl2 . the mobility of the charge carriers along individual polymer chains and across neighbouring chains is high as a result of geometrically ordered.3 and 95%. It can be seen from the SEM image (Fig. The data was logged and stored in the PC directly before processing using Microsoft ExcelTM . Screen-printed carbon electrodes (SPEs). Fig. 2.6.8.4 M iron (III) chloride in 1. 0.5. These two types of sensors responded to a change in humidity rapidly over the headspace of sealed saturated salt solutions. 68.2 g of PAni powder was dissolved in dimethylformamide (DMF). The film is also porous and contains large amount of void space which is expected to facilitate gas diffusion. Then the PAni coated SPE was soaked in 1. During measurement. 43. K2 CO3 . whereas the nano fibrous structure provides large surface area for gas sorption.0 M hydrochloric acid were mixed together. On the other hand. the mixture was drop-coated across the insulated gap on the SPE and left for 8 h at room temperature for reaction to proceed. 3.2 M aniline in 1. China) connected to a PC via RS232 connection. 1. For comparison. 2.0 M HCl for 5 min and rinsed with 1. The electrode was then soaked in EtOH for 5 min and rinsed with copious of EtOH. Some fibres are clearly shown to be branched. Mg(NO3 )2 . resulting in more structural defects that inhibited the movements of the charge carriers. Fig. / Sensors and Actuators B 143 (2010) 530–534 531 KCl and K2 SO4 which correspond to RH of 11. The baseline conductivity of the sensors was measured after being stored in dry atmosphere overnight over CaCl2 . The dark greenish PAni was then filtered and washed with distilled water before drying in an oven at 80 ◦ C for 24 h. 2b shows that the sensor film is composed of micro granule aggregates which are similar to those reported in literatures [6]. 2a) that the film is composed of interconnected nanofibres. Fig. . Equal volumes of 0.

e. but this equilibrium is also affected by its immediate environment. Unexpected behaviour was observed from the PAni nanofibres based humidity sensor. H-bondings between polymer chains through water molecules have also been suggested to contribute to the conductivity increase. –NH2 + – etc. the observed sensor response to water vapour resulted from more complex phenomena. this reversible chemical reaction quickly establishes equilibrium. (a) Response profile of PAni nanofibres to increasing humidity level. 70 to 100% RH. both sensors reached 95% response (electrical resistance change) at approximately 6 min. the water molecules absorbed into the PAni matrix act as a source of proton which can either increase the doping level of the polymer and/or conduct charge themselves through the network of absorbed water molecules.-W.6 ohm/RH) before levelling off. 3. When the PAni nanofibres based sensor. A much larger change was therefore observed from a conventional PAni based sensor compared to one that was based on PAni nanofibres. indicating more efficient charge transportation occurred with increasing humidity. The point of inflexion was found to be at ca. The electrical resistance of the film decreased initially with increasing RH from 0% to 52%. i. These charged or polar sites would help to shift the equilibrium towards the formation of proton through charge interactions and H-bonding. by further increasing the RH from 50% to 84%.) within the PAni emeraldine salt membrane. 3b where a plot of 1/R (which is directly related to conductivity of the PAni film) versus %RH is shown. These two phenomena are controlled by the partition coefficient (K) between the water vapour and the polymer . (b) Expansion of the response profile highlighted in (a). For the first time. (b) A plot of resistance versus relative humidity. for full sensor calibrations an exposure time of 10 min was used.24. 4a and b presents a response profile obtained from a sensor prepared from micro aggregate PAni. 0 to 30% RH (R2 = 0. In reality. It was believed that the conductivity increase of PAni membrane in the presence of water vapour (humidity) was due to ‘proton effect’ [23]. and finally followed by a sharp decrease from ca. The inset in (b) is the plot of 1/R to RH to give an indication of conductance change of the PAni nanofibres during exposure to humidity. 4.994. 3a) was observed. The inset is the linear logarithmic plot obtained from the same data. Zeng et al. These effects are again clearly revealed in the inset of Fig. –N . Consequently. 4b with R2 value of 0. slope = 1. NH+ –. which was in the emeraldine salt form. 52% RH. The mechanisms for conductivity increase in conducting polymers due to the presence of humidity have already been discussed by various workers [18. where the electrical resistance followed a logarithmic decrease with increasing RH. A linear log(R) versus %RH plot was obtained as shown in the inset of Fig. This sensor behaved as normally expected of a PAni humidity sensor.25]. Water molecules are ionisable. The plot shows an initial linear conductivity increase from ca. and dissociate into proton (H+ ) and hydroxyl ions (OH− ): H2 O H+ + OH− (pK a = 7.532 F. This phenomenon occurred only to the PAni nanofibres based sensors and the processes were completely reversible. a bimodal resistivity change (Fig. Under the experimental conditions only natural diffusion could take place. Fig. When the RH was further increased from 85% to 97%. The main factors that are generally accepted are the ‘proton effect’ described above that would increase the film conductivity. [H+ ] = [OH− ] at pH 7) At a given pH. / Sensors and Actuators B 143 (2010) 530–534 Fig.26 k /% RH. Hence. repeatable and reproducible for different sensors prepared in the same way. was exposed to various humidity levels. Then. There are plenty of charged sites and H-bond accepting/donating sites (–NH–. and the swelling of the polymer through absorption of water molecule that would reduce the conductivity of the film. (a) Response profile of conventional PAni film to humidity. a huge resistance jump ( R = ∼100%) was observed. Fig. it was observed that an unexpected increase in film resistance of moderate magnitude occurred. two different modes of conductivity behaviours were observed for a single continuous PAni film.994 and a slope of −1.

/ Sensors and Actuators B 143 (2010) 530–534 533 Scheme 1. respectively. 5 presents the FTIR data obtained from the PAni nanofibres based sensor before and after exposure to high humidity levels. The nanofibres.B. A probable explanation is that the emeraldine salt state was partially converted to leuco-emeraldine salt state by excess water molecules absorbed into the matrix (see Scheme 1). [4] S. Our results have indicated that the overall PAni nanofibres conductivity is a combined result of ‘proton effect’ and ‘swelling effect’. Conclusions This study has shown that PAni nanofibres based humidity sensor behaved very differently to conventional conducting polymer based sensors. are expected to offer stronger interactions. The observed behaviour from the PAni nanofibres based sensor to water vapour may likely be due to its unique structural arrangements. These behaviours have seriously restricted the usefulness of PAni nanofibres based sensors as humidity sensor.L. The benzenoid–NH+ –quinoid vibrations occurred at 1128 cm−1 indicating conductive emeraldine form. The appearance of the quaternary ammonium band at 2306 cm−1 may support this. K. This peculiar behaviour is believed to be due to the distortion of the nano structure by the absorbed water molecules. However.87 when dry to 0. This is in line with the expectations that high sensitivity can be achieved with vastly increased surface area and structured conformation. higher resistance). Whereas at higher RH.Y. This coefficient is a constant that represents. Fig. References [1] E. It is believed that polymer swelling was the main cause for the electrical resistance increase observed from the PAni nanofibres based sensor exposed to high RH. Although beyond the scope of this paper. Combating humidity—the hidden enemy in manufacturing. this particular behaviour may be useful in other area such as humidity controllable micro actuator. 5. The micro aggregate PAni sensor performed much better as a humidity sensor. China (project number: 20052016). 4. with their increased surface area. 14 (4) (1994) 28–31. Actuators B 104 (2005) 217–222. 5a (PAni under dry condition) shows a typical IR spectrum for emeraldine salt form with quinoid ring stretching at 1614–1641 cm−1 and benzenoid stretching at 1384–1465 cm−1 . Strong peak observed at 3491 cm−1 was typically the N–H stretching with ring C–H vibrations at 2854–2923 cm−1 . one would expect the size of active surface area to play an important part in the sensor response. National Natural Science Foundation of China (50973013) and the China-Ireland Collaboration Funding (cofunded by SFI. or potentially as sensor for organic acids because the ‘reverse effect’ also occurred when the sensor was exposed to acetic acid vapour for a considerable period of time (data not shown). Rev. at a given temperature and at equilibrium. and the reduction in N–H stretching. i. Sens. Khijwania. This caused the polymer chains to distort and to increase the packing disorder. Lett. Fig.F. polymer swelling caused the sensor to ‘reverse’ its responses and an increase in sensor resistance was observed. An evanescent-wave optical fiber relative humidity sensor with enhanced sensitivity. At low RH where proton effect was believed to dominate a decrease in electrical resistance was observed. being structurally disordered. Sens. Sens. strongly suggested that polymer swelling from water absorption. This could be due to water forming H-bonding to the nitrogen centre to restrict the N–H stretching. Natural Science Foundation of Liaoning Province. [2] C.96 when exposed to 68% and 97% RH. This might be indicating that a partial chemical reduction occurred. The electronic nose using conducting polymer sensors. alkanes. Humidity sensors: a review. J. Peaks at 713–881 cm−1 were the bending of aromatic C–H and absorption at 604 cm−1 being the ring deformation.-W. and hence sensitivity. membrane. The benzenoid to quinoid ratio increased from 0. Therefore. but yet this was not observed from our works. IR spectra for PAni nanofibres based sensor after exposed to different RH. several spectral changes occurred. therefore resulting in restricted charge carrier movements (i. Singh. RCS and CMOST). . This presence of excess water molecules at high (97%) RH. The author (KTL) also thank DCU fellowship award for financial support. Hodgins. was responsible for the large increase in the electrical resistance. [3] D. Sens. On exposure of the PAni nanofibres based sensor to high level of water vapour ca.92 and 0. G. aromatics and specifically amines. Acknowledgments We gratefully acknowledge financial support from National Natural Science Foundation of China (project number: 50372011). Srinivasan. 17 (1997) 291–298. FTIR data supported this hypothesis and also showed that there were other phenomena occurring at high RH. 68–97%. A reduction of N–H stretching and C–H vibrations at 3491 cm−1 and 2854–2923 cm−1 were observed.P. 3 (2005) 1–15.e. Bracken. it is worth mentioning that the PAni nanofibres based sensor is very sensitive to other non proton-donating volatile organic compounds such as alcohols.K. Fig. Rev. The micro aggregated PAni sensor. the ratio between the concentration of the water vapour absorbed into the polymer (Cs ) and the water vapour concentration in gas phase (Cg ). did not suffer as much from this. Lee.e. K = Cs /Cg . Peaks at 1588 and 3741 cm−1 (bending and asymmetric modes of water) appeared indicating that significant amount of water was absorbed [26]. Zeng et al. Lee. Structure of PAni leuco-emeraldine salt and emeraldine salt. possibly due to the nitrogen centre being H-bonding to water. drug release etc.

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