Synthetic Metals 162 (2012) 10521058

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Effects of different nucleating particles on aniline polymerization

Mara H. Lissarrague a,b , Melisa E. Lamanna b , Norma B. DAccorso b , Silvia Goyanes a,
a b

LP&MC, Departamento de Fsica, FCEyN UBA, and IFIBA CONICET, Ciudad Universitaria 1428, Ciudad Autnoma de Buenos Aires, Argentina CIHIDECAR-CONICET, Departamento de Qumica Orgnica, FCEyN UBA, Ciudad Universitaria 1428, Ciudad Autnoma de Buenos Aires, Argentina

a r t i c l e

i n f o

a b s t r a c t
Hybrid materials were developed via in situ oxidative polymerization of aniline in presence of 0.5 wt% of nano-/micro-particles. Polymerization was carried out in hydrochloric acid (HCl) medium. Four types of particles were used (aluminum powder 140 mesh, carbon nanotubes and quartz dust in two sizes, 400 and 140 mesh). Polyaniline and hybrid materials were characterized by spectroscopic techniques (UVVis, FT-IR), thermal analyses (TGA, DSC), morphological studies (FE-SEM); electrical conductivity and wear resistance measurements. The most promising hybrids were obtained by the incorporation of aluminum (140 mesh) or quartz 400 mesh powders. In both cases, electrical conductivity was similar to the one measured for PANI but up to 40% higher wear resistance. 2011 Elsevier B.V. All rights reserved.

Article history: Received 6 September 2011 Received in revised form 11 November 2011 Accepted 20 December 2011

Keywords: PANI Hybrid materials Electrical conductivity Wear resistance

1. Introduction The hybrid inorganicorganic systems represent a new class of materials that may combine desirable physical properties characteristic of both their organic and inorganic components within a single composite. The use of conductive polymers as the organic component of such hybrid materials has received much attention because of its wide applications scope [1]. Among conducting polymers, polyaniline (PANI) has been widely studied because it is well known as being a promising material for various applications due to its good conductivity, electrochemical activity, redox reversibility, easy doping and dedoping process, thermal and environmental stability, and biocompatibility [2,3]. Due to the latter property, PANI probes to be a tempting substitute for metal llers, specially, in biomedical applications [4,5] where biocompatible and conductive composites are needed. The advantages of PANI, compared to most other conductive polymers, are its easy preparation procedure in acidic aqueous solutions, an inexpensive monomer and high stability. It was demonstrated that PANI lm on stainless steel is stable in aggressive environment and the passive layers underlying the PANI lms have higher chromium-content compared with the air-formed or anodically formed oxide lms on stainless steel [6]. The corrosion protection of steel by PANI lm in the acid media is due to passivity protection connected with excess oxidative charge stored in PANI layer [7].

Corresponding author at: Int. Giraldes 2160, Pabelln 1, Cdad. Universitaria, Ciudad Autnoma de Buenos Aires, Argentina. Tel.: +54 011 4576 3353. E-mail address: goyanes@df.uba.ar (S. Goyanes). 0379-6779/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2011.12.018

In recent years, it has been investigated the possibility of PANI coatings on llers like clay, silica, silicates, carbon black, poly(methyl methacrylate) [8]. In particular, PANI was polymerized in the presence of BaTiO3 nanoparticles to produce nanohybrid conductors [9], as well as with SnO2 nanoparticles to produce gas sensors [10], and with (Ti,Sn)O2 to produce coreshell nanoparticles [11]. Also, PANI-Ag hybrid have attracted considerable interests because of their potential in technological applications in the eld of the electronic industry of transducers, actuators, sensors, batteries and biomaterials [12,13], as a consequence of these applications a large amounts of llers were reported [8,14]. Taking into account that PANI has poor mechanical properties it is possible to improve and modify them by incorporating micro and nanosized particles to it. In our knowledge, using PANI as the polymeric matrix and nano-/microsized llers as reinforcement for mechanical properties has not been extensively studied. Indeed, it is known that the presence of small amounts of single or multi-wall carbon nanotubes during PANI polymerization, affect to the material morphology [15,16]. It has been reported previously that PANI properties depends highly on the reaction conditions, i.e. starting pH, reaction temperature, type of acid employed, etc. [17]. In particular, it is acknowledged the time dependence of the polymer chain growth. It is also well known that at lower reaction time, the only products are non-conducting oligomers while, when increasing reaction time, emeraldine salt is obtained. It is also known that the addition of micro/nanoparticles to the reaction media, may affect the nal properties of the obtained material. Zarbin and co-workers reported studies focused on reaction time dependence of different properties of PANI-Ag nanoparticles hybrid [13]. However, in our

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knowledge there are no quantitative studies on how PANI properties are inuenced by continuing the reaction above the reaction time at which emeraldine salt is obtained. The main goal of this work was to obtain hybrid materials with similar or higher conductivity than that of PANI, improved wear resistance and higher glass transition temperature which would allow a wider range of application. In rst place, it was studied the inuence of reaction time on electrical conductivity and glass transition temperature. Having chosen the optimal reaction time, polymerization was carried out in presence of nano-/microparticles with different mechanical properties: aluminum (high ductility), quartz (high abrasion and hardness) and multi walled carbon nanotubes (MWCNT), in a low percent ller weight respect to monomer weight. Taking into account that the hydrophobic/hydrophilic character of the nucleating particle affects de reaction media, both types of surfaces were studied: while aluminum and quartz particles are hydrophilic, MWCNTs are hydrophobic. Finally, as a smaller particle size provides a higher nucleating surface area, two quartz powders with different particle size distribution were used to study how this parameter affects PANI hybrids properties. 2. Experimental 2.1. Reagents All the reagents: aniline, ammonium persulfate (APS), hydrochloric acid (HCl) were obtained from commercial suppliers (Aldrich Co). They were used without further purication. Two Quartz powders with different particle size distribution Q140 and Q400 (with particle-size <100 m and <38 m respectively); aluminum particles smaller than 100 m and carbon nanotubes (MWCNT) with a Gaussian distribution of outer diameter between 14 and 36 nm and length greater than 1 m, were used as nucleating agents. 2.2. Polymerization of aniline Solution A: aniline (1.82 mL, 20 mmol) in 20 mL water were added 20 mL of hydrochloric acid 1 M (20 mmol) and 10 mL of hydrochloric acid (10 M). Solution B: APS (5.71 g, 25 mmol) was dissolved in water (50 mL) [18]. Both colorless solutions (A and B) were kept at room temperature for an hour. Then, solutions A and B ([aniline]/[APS] molar ratio was 1:1.25) were mixed and remained at room temperature on ultrasonic bath during 10 min in all cases, and then continuing the reaction under constant magnetic stirring in the cases where the reaction was held for 24, 48 and 72 h. The green precipitated product (PANI-emeraldine) was ltered under vacuum and washed with water and HCl 0.2 M. The product was dried under vacuum. It is interesting to note that the synthesis was performed in a hydrochloric acid medium (1 M); in consequence it is assumed that the counterions are chlorides. This same procedure was followed in order to obtain the PANI hybrids by adding 0.5% of the nucleating agent 10 min before starting the reaction. The polymerization was nished at 48 h. When adding MWCNTs extra precautions were needed in order to avoid agglomeration. As Chakraborty et al. have reported [19], cetyl trimethylammonium bromide (CTAB) was used as surfactant in the following relationship: 1 mol of MWCNT by 19 mol of CTAB. 2.3. Characterization UVVis spectra were performed with a Shimatzu UV-1800 spectrophotometer, using isopropanol as solvent. Fourier transformed infrared spectra (FT-IR) were performed with Nicolet 510 P equipment using KBr pellets. Thermogravimetry analysis (TGA) was performed in a TGA-51 Shimadzu thermogravimetric analyzer. The

temperature range was 30700 C at a heating rate of 10 C/min with applied air ux of 50 mL/min (40 psi N2 , 10 psi O2 ), mass sample of 58 mg. Thermal analyses were performed at a heating rate of 5 K/min under nitrogen with a DSC TA Instrument Q-20 calibrated with indium. SEM images of all the samples were studied in order to determine the inuence on morphology of the different nucleating particles using a eld emission scanning electron microscopy (FE-SEM Zeiss LEO 982 GEMINI). Moreover, optical microscopy (Olympus BX60M Microscope) was used to visualize agglomerates and these nucleating particles. A four-point probe set up, built in our laboratory, and a Keithley 199 System DMM/Scanner multimeter were used to measure conductivity on PANI and PANI hybrids pellets. The employed multimeter automatically calculates resistance in the four-point probe conguration. Resistivity was calculated using the relation: = R. A L (1)

where R is the resistance of the pellet calculated by the instrument, A the electrode surface, and L the electrode spacing. Conductivity was calculated using the relationship: = 1 (2)

For wear resistance measurements, it was employed the ball cratering micro-scale wear test proposed by Kassman et al. [20]. A CALOTEST devise was used [21]. The calculation of the wear coefcient was done using the Archards equation for sliding wear [22]: V =kSN (3)

k = wear coefcient, V = Wear volume, S = distance of sliding. Every characterization was performed according to the usual procedure for hybrid materials study. For each one, measurements were performed over ve different samples of each hybrid material. In UVVis and TG analysis, the ve curves obtained showed no signicative differences between each other. In the other cases, i.e. electrical conductivity, wear resistance and density, the reported values are accompanied by their corresponding error bars. These values are due to measurements performed over ve different pellets fabricated for each polymerization time and hybrid material. To obtain these pellets, 600700 mg of PANI and PANI hybrid powder (measured with 0.1 mg error) were pressed under 113.0 kPa (measured with a torquimeter resolution 0.5 kPa) inside a pillbox of 22.48 mm diameter. The reported value for each condition is the average of measurements performed on ve different pellets. The error bars correspond to the statistic error. 3. Results and discussion 3.1. PANI The dependence of the electrical conductivity ( ) with reaction time is shown in Fig. 1. As it can be seen, the material obtained after only 10 min of polymerization has already high conductivity, in the same order of magnitude than that corresponding to 48 h. However, it is important to notice that there exists an increase in conductivity till 48 h reaction time after which there are no further variations. It is well known that the electrical conductivity of PANI depends on molecular weight chains, oxidation state, percentage of doping and dopant type [17,23]. The fact that PANI achieves a high conductivity value at 10 min reaction time indicates that the molecule attains a certain denite size at this moment, which shows little variations at longer polymerization periods of time [17]. Indeed, this can be attributed to the fact that long-range delocalization of an electron cloud due to

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the samples obtained at different polymerization time. This result shows that at 10 min, the chain length achieved is sufcient to show a Gaussian behavior, i.e. the chain has the necessary length to behave like a polymer [25].

3.2. Nano and micro hybrids Polymerization in presence of micro- and nano-llers does not change the dependence of electrical conductivity with reaction time. Moreover, when using quartz powder 400, conductivity values obtained are similar to those presented in Fig. 1. It is very interesting to notice that adding a nucleating agent to the reaction media affects neither the fact that at the tenth minute the glass transition temperature saturates or that it gets the same value at every reaction-time. However Tg depends on whether a nucleating agent is used or not. For example, in PANI-Q400 Tg is (142 1) C 16 degrees higher than PANIs Tg . From PANI electrical conductivity data, 48 h was considered as the optimal reaction time. Then, this polymerization time was used to perform a comparative analysis of the different PANI hybrids properties. Taking into account that llers could play an important role in polymer morphology, a FE-SEM study was made. Fig. 3 shows the micrograph of the different PANI hybrids. As can be seen in Fig. 3a, PANI has the classical irregular morphology in agreement with what is reported in the literature [18]. The granular structure is predominant, also being possible to nd nanotubes and nanosheets. At rst sight, in Fig. 3bd this morphology does not seem to be modied by the addition of aluminum or quartz particles independently of their size, as they seem to display a structure similar to the one identied in PANI. However, an image analysis, using Sion Image software, showed a slight increase in the number of nanobers. When analyzing PANI-MWCNT hybrid, shown in Fig. 3e, a nanobrillar structure is clearly the preferred one. This observation is in agreement with what was reported by Jimnez et al. for MWCNTs [16] and by Zhang et al. for SWCNTs [15]. According to Jimnez et al. [16], this nanobers may have two different natures: (a) selfstanding PANI nanobers, of similar origin of the ones observed in the other micrographs, but with an increase in the length of the nanobers; (b) PANI wrapped CNTs, i.e. a PANI layer deposited over the CNT surface, explained by the preferential growth of polyaniline on the nanotubes surface. Even though, an exhaustive search was performed by FE-SEM, it was not easy to nd unwrapped MWCNTs. Fig. 3f shows a micrograph of the only area where there seems to be a partially wrapped MWCNT. In Fig. 4 the FTIR spectra of the hybrid composites is shown. In all the spectra is observed the characteristic PANI structure bands (solid lines): the band at 824 cm1 due to out of plane bending vibration of C H bond of p-disubstituted benzene rings; the main peaks at 1587 cm1 and 1497 cm1 correspond to quinone- and benzene-ring stretching deformations, respectively. These relative lower frequencies of benzenoid and quinoid ring stretching are due to the salt formation with HCl [26]. The absorption band at 1306 cm1 corresponds to -electron delocalization induced by protonation [27]. The band characteristic of the conducting protonated form is observed at 1250 cm1 and interpreted as a C N+ stretching vibration in the polaron structure [28]. The 1140 cm1 band is assigned to a vibration mode of the NH+ structure, which is formed during protonation [29]. The band at 1378 cm1 is attributed to a C N stretching in the neighborhood of a quinonoid ring. The 1308 cm1 band is assigned to the C N stretch of a secondary aromatic amine whereas, in the region of 10101170 cm1 , the aromatic C H in-plane bending modes are usually observed. Out-of-plane deformations of C H on 1,4-disubstituted rings are located in the region of 800880 cm1 [27,30].

Fig. 1. Reaction-time dependence of PANIs electrical conductivity.

the formation of a conjugated double bond does not occur until the molecule attains a denite size [23]. Taking into account that the protonation of the polymer chain helps to form the polaron structure where current is carried by holes, this parameter had to be controlled. Then, the acid concentration employed was enough to dope the largest polymers chains as well as the shortest, so the doping percentage was the maximum for each sample. However, other parameter that could modify the electrical conductivity is the oxidation state, which may change during the polymerization time. Through the analysis of the UVVis spectra of PANI samples at different reaction times (Fig. 2), it is possible to identify the characteristic transitions of PANI namely: 320 nm, 415 nm and 850 nm. According to Zarbin and co-workers [24] these bands were attributed to *, polaron * and polaron transitions, respectively. It was observed a decrease in the intensity of the band at 320 nm associated to a diminution in the amount of quinonic structures, suggesting that the oxidation state change leading to differences in the electrical conductivity with polymerization time. Also, an increase intensity of the band around 415 nm was observed as the reaction time increase, indicating an increase in electron delocalization. On the other hand, the polaron transition band decreased as the polymerization time increased. On the other hand, from DSC analysis glass transition temperature was estimated to be (126 1) C, the same for each one of

Fig. 2. UVVis spectra of PANI polymerized at different reaction time.

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Fig. 3. FE-SEM micrographs of (a) PANI, (b) PANI-Q400, (c) PANI-Al, (d) PANI-Q140, (e) PANI-MWCNT, (f) inset PANI-MWCNTs where an unwrapped or partially wrapped MWCNT was found.

The band at about 1140 cm1 , due primarily to C H in-plane deformation, has been used by Chiang and MacDiarmid [29] as a measure of the extent of electron delocalization in the polymer. The intensity of this peak is therefore to be considered as a measure of the degree of doping of the polymer backbone [29]. It was observed that all the hybrids showed a similar prole which also agrees with the one that was previously reported for PANI [28]. However, some bands were only observed in the hybrid samples indicating that the ller affects the interaction between the polymer chains (dash lines Fig. 4: 1674, 1552, 1407, 861 cm1 ). As we described above, the band around 1400 cm1 is attributed to a C N stretching in the neighborhood of a quinonoid ring, this one has more intensity in PANI-MWCNT and in PANI than in the others. The addition of nucleating particles to the reaction media during polymerization affects weakly the electrical conductivity values, as it can be seen in Table 1. The reasons for the differences in conductivity showed in Table 1 are associated with several variables. One of them could be the spatial distribution uctuations of polymer chains, as a consequence of the different PANI chains arrange

due to the ller presence. Another one is the delocalization and the hopping, intra-chain or inter-chain, of the carriers through polaron lattice [23]. The UVVis spectra of all hybrids and PANI are shown in Fig. 5. These spectra show differences in the relative intensities between the bands around 320 nm and 415 nm. In the cases of PANI and PANI-Q400 with comparable conductivity values, the intensity between both bands is similar. Meanwhile PANI-Al and PANI-Q140 show that the intensity of band at 320 nm is higher than the

Table 1 Electrical conductivity of PANI and PANIller hybrids polymerized 48 h. Material PANI PANI-Al PANI-Q140 PANI-Q400 PANI-MWCNT (S/cm) 0.60 0.70 0.17 0.57 0.23 0.03 0.05 0.03 0.05 0.04

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Fig. 6. Thermogravimetric analysis of PANI and PANI hybrids.

Fig. 4. FT-IR spectra of PANI and PANI hybrids.

signal at 415 nm. It should be noted that, even though aluminum and Quartz 140 particles have similar size distribution, the hybrid PANI-Al has similar conductivity to PANI while PANI-Q140 is much smaller. This difference is linked to the ller electrical characteristic. While quartz is an insulating material, aluminum is a conductor that contributes to the formation of conductive pathways. On the other hand, for the same materials type, size particle matters. It is important to notice that while PANI-Q140 hybrid conducts less than PANI, PANI-Q400 hybrid has similar conductivity to PANI. This can be attributed to the small particle size which allows better packing of PANI. The result obtained for PANI-MWCNT conductivity was not expected. Due to the higher surface area; its hydrophobicity, which led to a homogeneous polymerization with a tubular nanostructure; it was expected that conductivity should have been higher than the one of PANI. However, the use of a surfactant which is closely bond to the MWCNTs might obstruct conduction pathways along the MWCNTs and the PANI. On the other hand the UVVis spectrum of this hybrid shows similar intensity in the bands at 320 nm and 415 nm but a hypsochromic shift respect to the corresponding PANI bands. It should be emphasized that the addition of only a 0.5% of a ller relative to monomer concentration, not only changes electrical conductivity but also thermal degradation. In Fig. 6 it can be seen the thermogravimetric analysis for PANI and PANI hybrids. Since in

Fig. 5. UVVis spectra of PANI and PANIller hybrids polymerized 48 h.

the region between 50 and 120 C it was registered a weight loss due to the presence of moisture in the samples, the curves were normalized to the quantity of material at 120 C. From Fig. 6 it can be observed that the highest weight loss occurred between 350 and 670 C while small weight losses were observed between 130 and 230 C due to the loss of hydrochloric acid. As described by Tsai et al. [31] after losing its doping agent, PANI became emeraldine base and four different degradation mechanisms could be identied. Between 520 and 740 C there was a cleavage reaction that produced aniline, ammonia along with other oligomers. The remaining structures are merged to form carbazole units which were broken down releasing hydrogen at higher temperatures. The oxidized repeated units undergo another cleavage reaction below 650 C which leads to regroup to form pyridine type heterocycles. Above 730 C these structures nally break down into ammonia, acetylene and methane. TGA analysis of PANI-MWCNT hybrid showed that the weight loss due to the loss of hydrochloric acid was partially hidden by a higher weight loss which Chakraborty et al. [19] assigned to CTAB loss. This result conrmed the presence of surfactant in the sample and therefore justied the reduction in this sample conductivity compared with neat PANI. It is important to note that degradation rate for PANI-MWCNT was slower than those observed for the other hybrids. On the other hand, PANI-Q400 had a slightly greater stability as the largest weight loss began at the highest temperature which was due to a greater amount of polymer anchored to quartz particles. As was expected, PANI showed the highest degradation rate. This effect could be explained taking into account that the difference between the nucleating particles and the polymer conductivity. It can be concluded that a higher specic surface area implies a decrease in the rate of decomposition of polymer chains, due to an increase in the quantity of polymer anchored to nucleating centers of polymerization. The difference observed between PANIQ400 and PANI-Q140 was due to the different distribution of the nucleating particles in each PANI hybrid as consequence of the difference in the particle size, and also to the number of nucleating centers anchored on the surface. Another interesting result is that the addition of very small amounts of nano-/microsized llers leads to an increase in glass transition temperature (Tg ), as can be seen in Table 2. This variation may be attributed to the large particlepolymer interface, where the anchored polymer chains have lower mobility than those that are not bounded to the particle, making necessary a larger amount of energy to produce this transition. Taking into account that MWCNTs have the largest surface area, PANI-MWCNTs should have the largest Tg . However, the increment observed in Tg was not what

M.H. Lissarrague et al. / Synthetic Metals 162 (2012) 10521058 Table 2 Tg of PANI and its hybrids. Material PANI PANI-Al PANI-Q140 PANI-Q400 PANI-MWCNT Tg ( C) 126 140 147 142 130 1 1 1 1 1

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was expected, due to the 8% of CTAB that remained in the sample, as it was conrmed by TGA. This surfactant acted as a plasticizer, lowering Tg . Finally, the wear resistance also improves in most hybrids synthesized compared to neat PANI, as can be observed in Fig. 7. Adding MWCNTs or quartz powder with particle size <38 m, improves wear resistance in approximately 50%. The use of this aluminum powder also improves wear resistance. Similarly to what is observed in conductivity measurements, using a quartz powder with grater particle size (<100 m) slightly worsens wear resistance. However, the uncertainty in the calculation of the latter result, led to the belief that the wear resistance is actually the same as the one of PANI. An easy way of understanding these last results is by analyzing the density and afterwards the porosity of the pellets fabricated for conductivity and wear coefcient measurements. These results can be seen in Fig. 8. The composite porosity, , dened as the cavity or hole volume fraction, Vh /V, where Vh is the volume of the holes in the sample, and V the sample volume, was calculated according to what was reported previously by Zilli et al. [32].

From these results it can be established that PANI-MWCNTs porosity is lower compared to the one calculated for PANI while for PANI-Q400 and PANI-Al it is slightly higher. This can be explained by considering; quartz and aluminum surfaces are hydrophilic contrary to MWCNT surface which is hydrophobic, making it more compatible with PANI. For PANI-Q140 the number of holes is greater due to the larger particle size, which does not allow a good packing of the pellet as it was stated previously. Even though aluminum particles are also large; the ductility of this material allows their deformation during pellet compression. The addition of a ller led to an increase in wear resistance, except in the case of Q140 (quartz powder with particle size distribution <100 m). Despite having improved wear resistance, MWCNTs were unable to enhance conductivity due to the requirement of a surfactant in a large %, in order to achieve a homogeneous dispersion of his particles in the reaction media. The hybrid synthesized with Q400 (quartz powder with particle size <38 m) and aluminum particles maintained conductivity in a value similar to that of PANI. In conclusion, we have synthesized two PANI hybrids with similar conductivity to PANI but enhanced wear resistance. It is interesting to notice that same result has been achieved using both ceramic and metallic microparticles, which are expected to show dissimilar thermal behavior and also different applications, even though these has not been studied in this work. 4. Conclusions New hybrid materials were performed from PANI polymerization in presence of particles with very different chemical nature, such as MWCNT, quartz 140 mesh, quartz 400 mesh and aluminum powder. The last two hybrids showed: an electrical conductivity similar to the one of PANI; improvements in the wear resistance (up to 50%); the increment in Tg values (10%); degradation temperature increased (25 C); altogether provide a wider range of application. On the other hand, the results of this study lead us to conclude that the addition of a nucleating agent to the reaction modies neither the dependence of Tg nor the electrical conductivity with polymerization time. Finally, it was shown how the determination of porosity (parameter unexplored in the polymers area) is important to understand the results of wear and electrical conductivity through the packing. Acknowledgements The authors wish to thank the nancial support of UBACyT (20020100100350 and 200220100100142) and CONICET (PIP 20080064 and PIP 11220090100699). References
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Fig. 7. Wear coefcient results of PANI and PANI hybrids.

Fig. 8. Density and

(hybrid porosity/PANI porosity), of PANI and PANI hybrids.

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