1. bookVolume 34 (2016): Issue 4 (December 2016)
Journal Details
License
Format
Journal
eISSN
2083-134X
First Published
16 Apr 2011
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4 times per year
Languages
English
access type Open Access

TiO2/PANI nanocomposite loaded in PVA for anticorrosive applications

Published Online: 17 Nov 2016
Volume & Issue: Volume 34 (2016) - Issue 4 (December 2016)
Page range: 721 - 725
Received: 15 Dec 2015
Accepted: 06 Aug 2016
Journal Details
License
Format
Journal
eISSN
2083-134X
First Published
16 Apr 2011
Publication timeframe
4 times per year
Languages
English
Abstract

We report the morphological and electrical study of a composite of polyvinyl alcohol (PVA) and nanotitanium dioxide (TiO2-50 nm) in conducting polymer polyaniline (PANI). The composite was synthesized using in-situ polymerization technique. The composite was characterized in terms of morphology and electrical properties using scanning electron microscopy and DC electrical conductivity (𝜎dc). We observed that the DC electrical conductivity of the composite film increased with increasing the loading of nanocomposite material from 20 % to 40 % into PVA stabilizer. The DC conductivity results showed that the molecular chain contribution of the nanocomposite material (nano-TiO2+ PANI) was the prominent carrier in the composite film made of the nanocomposite and PVA stabilizer.

Keywords

Introduction

Conducting polymers have emerged as a separate class of materials with the development of new technologies and their applications in various fields. Among a number of conducting polymers, polyaniline (PANI) shows remarkable properties and thereby corresponding applications in sensors [13], solar cells 4, corrosion coatings 5, electronic devices 6, field effect transistors 7, electromagnetic shielding 8, etc. To achieve high electrical conductivities, polyaniline can be doped with protonic acids [911]. But simultaneously, other factors, like its processing [1214] and lack of solubility in common solvents, restrict its applications. The compatibility of PANI with polyvinyl alcohol (PVA) [1517], results from molecular interactions 17 which lead to a change in its specific properties associated with solubility 18, electrical conductivity [15, 19], and mechanical properties 20. PVA is soluble both in hot and cold water, which makes it a suitable material for the synthesis with PANI [21, 22]. PVA has several advantages that make it an appropriate choice to be used for developing a composite which distinguish itself from other composites like PMMA 23 and polyethylene oxide 24.

In the present study, we have synthesized the nanocomposite of nano-TiO2 and PANI which then was loaded in polyvinyl alcohol matrix. We have studied different weight percentage loading ratios, i.e. from 20 wt.% to 40 wt.% by the morphological and electrical analysis.

Experimental
Materials

The chemicals: aniline (Emerck), polyvinyl alcohol (Emerck), titanium dioxide 50 nm (SRL), HCl (Emerck), ammonium peroxodisulfate (Emerck) used in the processing of the composite were of analytical grade.

Synthesis of composite

The synthesis of nanocomposite material (TiO2/PANI) was carried out in a 250 mL round-bottom flask equipped with a stirring assembly. First, 1 g of TiO2 nanoparticles (size of 50 nm) were dispersed in 50 mL of 1N HCl solution under ultrasonic vibrations to reduce the aggregation of TiO2 nanoparticles and then 2 mL aniline were added dropwise into the solution under constant stirring. After one hour, a solution of 4.9984 g of ammonium peroxodisulphate ((NH4)2S2O8) and 1N HCl were added dropwise into the aniline and TiO2 solution. Polymerization was carried out at a temperature of 0 °C to 5 °C with controlled stirring for 5 h. Dark green TiO2/PANI composite was then filtered and washed with distilled water several times. So, the core shell nanocomposite of (TiO2/PANI) was synthesized without any surfactant. The PVA solution was prepared by dissolving PVA powder in 300 mL of distilled water at temperature of 80 °C to 90 °C under continuous stirring for 3 hours. Core shell nanocomposite (TiO2/PANI) was then added into the PVA solution at different weight percentage ratios 20 wt.% to 40 wt.% at room temperature and the mixture was continuously stirred for 10 hours. The blended solution was allowed to dry in a Petri dish under ambient temperature for four to five days. The obtained sheets of the nanocomposite materials were used in such form for characterization.

Characterization

The morphology of the nanocomposite materials was studied using a scanning electron microscope (SEM Model: 6610 LV). The DC electrical conductivity of the composite film was investigated for different compositions of nanocomposite (TiO2/PANI) materials with a Keithley 6487 unit. For electrical study silver was used as electrode material. All measurements were performsp at room temperature.

Results and discussion

Fig. 1 shows the SEM micrographs (magnification of × 1000 to × 3000 at 5 kV) for the core-shell TiO2/PANI nanocomposite material. The SEM micrographs show that the TiO2 nanopar-ticles are fully covered with polyaniline. This could be due to the formation of the core shell structure of TiO2/PANI i.e. the formation of PANI shell on the surface of TiO2 nanoparticles which caused repulsion forces between the nanoparticles and prevented their agglomeration [25, 26]Fig. 2shows the SEM micrographs of a 40 wt.% TiO2/PANI nanocomposite loaded to PVA.The micrographs reveal that on addition of core-shell TiO2/PANI nanocomposite to PVA, a homogeneously distributed fibrous type structure has been obtained. PVA as stabilizer helped also in developing this fibrous structure due to cross linking of PANI and PVA [27]. Similar results were also reported by Somani et al. [28] for the surface of TiO2 when PANI content was high.

SEM micrographs of core-shell TiO2/PANI nanocomposite at two magnifications.

SEM micrographs of core-shell TiO2/PANI nanocomposite loaded in PVA stablizer

The DC electrical conductivity of the composite film for different compositions of nanocomposite (TiO2/PANI) materials loaded in PVA materials was investigated with a Keithley 6487 unit in which probe distance was maintained at 1 mm and film thickness was 0.745 mm. Fig. 3 shows the variation of DC electrical conductivity (log𝜎) with increasing doping concentration of core-shell TiO2/PANI nanocomposite to PVA stabilizer at room temperature in the voltage range of 10 V to 100 V. The variation of conductivity over this voltage range clearly shows that with the increase of core-shell TiO2/PANI nanocomposite loading to PVA, the conductivity increases with increasing voltage. It can be observed that at room temperature the DC conductivity of core-shell TiO2/PANI nanocomposite loaded PVA varies from 1.54 × 10-12 S/cm to 3.21 × 10-7 S/cm with increasing content of the nanocomposite from 20 wt.% to 40 wt.%. This increase in conductivity may be attributed to the increased amount of TiO2/PANI which maximizes the number of carriers. The highest number of carriers can further be attained by the delocalization effect of doping process and the formation of polarons or bipolarons in the composite structure, thereby increasing the conductivity of nanocomposite [2931]. The increase in conductivity may also be explained on the basis of good correlation (discussed later) between PANI and TiO2 [34] and thereby lower resistance and faster response which can be offered by the nanocomposite (TiO2/PANI) for the transport of electrons between conduction band of TiO2 to lower the orbitals of polyaniline [35].

Variation of log𝜎 with voltage for different composite film.

Fig. 4 shows a comparison of our results for DC conductivity (𝜎) of core-shell TiO2/PANI nanocomposite loaded in PVA from 20 wt.% to 40 wt.% with (i) PANI-HCl loaded in PVA stabilizer where PANI volume percentage varies from 20 % to 40 % [33] and (ii) PANI-SnO2 hybrid nanocomposite where SnO2 nanoparticles increases from 20 % to 40 % [32]. We have further compared the correlation coefficient from our results with PANI-PVA [33], PANI-SnO2 nanohybrid material [32] and nano-TiO2+ PANI [36]. The values of the correlation coefficients have been given in Table 1. The correlation coefficient shows that the synthesized PANI was deposited on the surface of nano-TiO2 material and formsp encapsulated structure [36]. This encapsulated nanocomposite material (nano-TiO2+ PANI) when loaded to PVA stabilizer made a conductive nanocomposite which showed a good correlation coefficient, i.e. 0.997, and forecasted correlation coefficient of 0.999 (Table 1). The DC conductivity of PANI/PCC [35] was 1.03 × 10-5 S/cm for anticorrosive performance on mild steel surfaces. Our results of DC conductivity are also in agreement with the reported ones and the reported nanocomposite loaded in PVA matrix might be explored for anticorrosive applications on steel surfaces.

Comparison of correlation coefficient for core-shell TiO2/PANI nanocomposite loaded to PVA (this work) with PANI and PVA [33], PANI-SnO2 nanohybrid material [32], nano-TiO2+ PANI [36].

SampleCorrelation coefficientForecasted correlation coefficient
This work0.9970.999
[33]0.9140.914
[4]0.9990.999
[3]0.999980.99998

Comparison of DC conductivities of different composite materials.

Conclusions

We have synthesized the core-shell nanocomposite of nanotitanium dioxide in polyaniline. The flexible and conductive films have been prepared with blending of different percentages of core-shell TiO2/PANI composite in water soluble polymer PVA. We have observed regular shape and fibrous structure of PANI-TiO2-PVA composite film. The DC electrical conductivity of this composite material was found to increase from 1.54 × 10-12 S/cm to 3.21 × 10-7 S/cm with increasing amount of the nanocomposite (from 20 wt.% to 40 wt.%). Looking at the electrical results and comparing them with other materials of similar kind, these compositions may be explored for electrical, electronics-related and anticorrosive applications.

SEM micrographs of core-shell TiO2/PANI nanocomposite at two magnifications.
SEM micrographs of core-shell TiO2/PANI nanocomposite at two magnifications.

SEM micrographs of core-shell TiO2/PANI nanocomposite loaded in PVA stablizer
SEM micrographs of core-shell TiO2/PANI nanocomposite loaded in PVA stablizer

Variation of log𝜎 with voltage for different composite film.
Variation of log𝜎 with voltage for different composite film.

Comparison of DC conductivities of different composite materials.
Comparison of DC conductivities of different composite materials.

Comparison of correlation coefficient for core-shell TiO2/PANI nanocomposite loaded to PVA (this work) with PANI and PVA [33], PANI-SnO2 nanohybrid material [32], nano-TiO2+ PANI [36].

SampleCorrelation coefficientForecasted correlation coefficient
This work0.9970.999
[33]0.9140.914
[4]0.9990.999
[3]0.999980.99998

Nasirian S., Moghaddam H.M., Polymer, 55(2014), 1866.NasirianS.,MoghaddamH.M.,Polymer552014186610.1016/j.polymer.2014.02.030Search in Google Scholar

Srivastava S., Kumar S., Singh V.N., Singh M.,Vijay Y.K., Int. J. Hydrogen Energ., 36 (2011), 6343.SrivastavaS.,KumarS.,SinghV.N.,SinghM.,VijayY.K.,Int. J. Hydrogen Energ362011634310.1016/j.ijhydene.2011.01.141Search in Google Scholar

Patil D.S., Shaikh J.S., Dalavi D.S., Kalagis.S., Patil P.S., Mater. Chem. Phys., 128 (2011), 449.PatilD.S.,ShaikhJ.S.,DalaviD.S.,KalagiS.S.,PatilP.S.,Mater. Chem. Phys128201144910.1016/j.matchemphys.2011.03.029Search in Google Scholar

Xiao Y., Lin J.Yu., Wang W.Y., Tai S.Y., Yue G.,Wu J., Electrochim. Acta, 90 (2013), 468.XiaoY.,LinJ.YU.,WangW.Y.,TaiS.Y.,YueG.,WuJ.,Electrochim. Acta90201346810.1016/j.electacta.2012.12.055Search in Google Scholar

Mostafaei A., Nasirpouri F., Prog. Org. Coat., 77(2014), 146.MostafaeiA.,NasirpouriF.,Prog. Org. Coat77201414610.1016/j.porgcoat.2013.08.015Search in Google Scholar

Ramamurthy P.C., Malshe A.M., Harrellw.R., Gregory R.V., Mcguire K., Rao A.M., Solid State Electron., 48 (2004), 2019.RamamurthyP.C.,MalsheA.M.,HarrellW.R.,GregoryR.V.,McguireK.,RaoA.M.,Solid State Electron482004201910.1016/j.sse.2004.05.051Search in Google Scholar

Mostafaei A., Zolriasatein A., Prog. Nat. Sci-Mater., 22 (2012), 273.MostafaeiA.,ZolriasateinA.,Prog. Nat. Sci-Mater22201227310.1016/j.pnsc.2012.07.002Search in Google Scholar

Sudha J.D., Sivakala S., Patel K., Radhakrish-Nan N.P., Compos. Part A- Appl. S., 41 (2010), 1647.SudhaJ.D.,SivakalaS.,PatelK.,Radhakrish-nanN.P.,Compos. Part A- Appl. S412010164710.1016/j.compositesa.2010.07.015Search in Google Scholar

Xiaoxuan LI, Electrochim. Acta, 545 (2009), 634.XiaoxuanLI,Electrochim. Acta5452009634Search in Google Scholar

Wang J., Zhang K., Zhao L., Chem. Eng. J., 239 (2014), 123.WangJ.,ZhangK.,ZhaoL.,Chem. Eng. J239201412310.1016/j.cej.2013.11.006Search in Google Scholar

Long Y., Chen Z., Wang N., Zhang Z., Wan M., Physica B, 325 (2003), 208.LongY.,ChenZ.,WangN.,ZhangZ.,WanM.,Physica B325200320810.1016/S0921-4526(02)01526-0Search in Google Scholar

Yang D., L.W., Goering R., Mattes B.R., Synthetic Met., 159 (2009), 666.YangD.,L.W.,GoeringR.,MattesB.R.,Synthetic Met159200966610.1016/j.synthmet.2008.12.013Search in Google Scholar

Jaymand M., Prog. Polym. Sci., 38 (2013), 287.JaymandM.,Prog. Polym. Sci38201328710.1080/03632415.2013.808509Search in Google Scholar

Bhadra S., Khastgir D., Singha N.K., Lee J.H., Prog. Polym. Sci., 34 (2009), 783.BhadraS.,KhastgirD.,SinghaN.K.,LeeJ.H.,Prog. Polym. Sci34200978310.1016/j.progpolymsci.2009.04.003Search in Google Scholar

Arenas M.C., Sanchez G.O., Martinez-A., Castano V.M., Compos. Part B- Eng., 56 (2014), 857.ArenasM.C.,SanchezG.O.,MartinezA.,CastanoV.M.,Compos. Part B- Eng56201485710.1016/j.compositesb.2013.09.010Search in Google Scholar

Li Y., Ying B., Hong L., Yang M., Synthetic Met., 160 (2010), 455.LiY.,YingB.,HongL.,YangM.,Synthetic Met160201045510.1016/j.synthmet.2009.11.031Search in Google Scholar

Mirmohseni A, Wallace G.G., Polymer, 44 (2003), 3523.MirmohseniA,WallaceG.G.,Polymer442003352310.1016/S0032-3861(03)00242-8Search in Google Scholar

Gangopadhyay R., De A., Ghosh G., Synthetic Met., 123 (2001), 21.GangopadhyayR.,DeA.,GhoshG.,Synthetic Met12320012110.1016/S0379-6779(00)00573-7Search in Google Scholar

Dutta P., Biswas S., Ghosh M., De S.K., Chat-Terjee S., Synthetic Met., 122 (2001), 455.DuttaP.,BiswasS.,GhoshM.,DeS.K.,Chat-terjeeS.,Synthetic Met122200145510.1016/S0379-6779(00)00588-9Search in Google Scholar

Zhang Z., Wan M., Synthetic Met., 128 (2002), 83.ZhangZ.,WanM.,Synthetic Met12820028310.1016/S0379-6779(01)00669-5Search in Google Scholar

Irimia-Vladu M., Fergus J.W., Synthetic Met., 156 (2006), 1401.Irimia-vladuM.,FergusJ.W.,Synthetic Met1562006140110.1016/j.synthmet.2006.11.005Search in Google Scholar

Patil D.S., Shaikh J.S., Dalavi D.S., Kalagi S.S., Patil P.S., Mater. Chem. Phys., 128 (2011), 449.PatilD.S.,ShaikhJ.S.,DalaviD.S.,KalagiS.S.,PatilP.S.,Mater. Chem. Phys128201144910.1016/j.matchemphys.2011.03.029Search in Google Scholar

Jeevananda T., Siddaramaiah, Eur. Polym. J., 39 (2003), 569.JeevanandaT.,SiddaramaiahEur. Polym. J39200356910.1016/S0014-3057(02)00272-0Search in Google Scholar

Devendrappa H., Subba Rao U.V., Ambika Prasad M.V.N., J. Power Sources, 155 (2006), 368.DevendrappaH.,Subba raoU.V.,Ambika prasadM.V.N.,J. Power Sources155200636810.1016/j.jpowsour.2005.05.014Search in Google Scholar

Kim B.-S., Lee K.-T., Huh P.-H., Lee D.-H., Jo N.-J., Lee J.-O., Synthetic Met., 159 (2009), 1369.KimB.-S.,LeeK.-T.,HuhP.-H.,LeeD.-H.,JoN.-J.,LeeJ.-O.,Synthetic Met1592009136910.1016/j.synthmet.2009.03.012Search in Google Scholar

Li X., Wang D., Luo Q., An J., Yanhong W., Cheng G., J. Chem. Technol. Biot., 83 (2008), 158.LiX.,WangD.,LuoQ.,AnJ.,YanhongW.,ChengG.,J. Chem. Technol. Biot83200815810.1002/jctb.1798Search in Google Scholar

Gangopadhyay R., De A., Synthetic Met., 132 (2002), 21.GangopadhyayR.,DeA.,Synthetic Met13220022110.1016/S0379-6779(02)00212-6Search in Google Scholar

Somani P.R., Marimuthu R., Mulik U.P., Sainkar S.R., Amalnerkar Prak D.P., Synthetic Met., 106 (1999), 45.SomaniP.R.,MarimuthuR.,MulikU.P.,SainkarS.R.,Amalnerkar prakD.P.,Synthetic Met10619994510.1016/S0379-6779(99)00081-8Search in Google Scholar

Kymakis E., Alexandou I., Amaratunga G.A.J., Synthetic Met., 127 (2002), 59.KymakisE.,AlexandouI.,AmaratungaG.A.J.,Synthetic Met12720025910.1016/S0379-6779(01)00592-6Search in Google Scholar

Maminya Y.P., Davydenko V.V., Pissis P., Lebedev E.V., Eur. Polym. J., 381(2002), 887.MaminyaY.P.,DavydenkoV.V.,PissisP.,LebedevE.V.,Eur. Polym. J3812002887Search in Google Scholar

Hung J.C., Adv. Polym. Tech., 21 (4) (2002), 299.HungJ.C.,Adv. Polym. Tech214200229910.1002/adv.10025Search in Google Scholar

Khuspe G.D., Navale S.T., Chougule M.A., Sen Shashwati, Agawane G.L., Kim J.H., Patil V.B., Synthetic Met., 178 (2013), 1.KhuspeG.D.,NavaleS.T.,ChouguleM.A.,SenSHASHWATIAgawaneG.L.,KimJ.H.,PatilV.B.,Synthetic Met1782013110.1016/j.synthmet.2013.06.022Search in Google Scholar

Dutta P., Biswas S., Ghosh M., De S.K., Chatterjee S., Synthetic Met., 122 (2001), 455.DuttaP.,BiswasS.,GhoshM.,DeS.K.,ChatterjeeS.,Synthetic Met122200145510.1016/S0379-6779(00)00588-9Search in Google Scholar

Li X.-W., Wang G.-C., Li X.-X., Lu D.-M., Appl. Surf. Sci., 229 (2004), 395.LiX.-W.,WangG.-C.,LiX.-X.,LuD.-M.,Appl. Surf. Sci229200439510.1016/j.apsusc.2004.02.022Search in Google Scholar

Senarathna C.K.G., Mantilaka M.M.M.G.P.G., Nirmalpeiris T.A., Pitawala H.M.T.G.A., Karunaratne D.G.G.P., Rajapakse R.M.G., Electrochim. Acta, 117 (2014), 460.SenarathnaC.K.G.,MantilakaM.M.M.G.P.G.,NirmalpeirisT.A.,PitawalaH.M.T.G.A.,KarunaratneD.G.G.P.,RajapakseR.M.G.,Electrochim. Acta117201446010.1016/j.electacta.2013.11.137Search in Google Scholar

Li X., Wang G., Li X.-X., Lu D., Appl. Surf. Sci., 229 (2004), 395.LiX.,WangG.,LiX.-X.,LuD.,Appl. Surf. Sci229200439510.1016/j.apsusc.2004.02.022Search in Google Scholar

Srivastava S., Kumar S., Singh V.N., Singh M., Vijay Y.K., Int. J. Hydrogen. Energ., 366 (2011), 343.SrivastavaS.,KumarS.,SinghV.N.,SinghM.,VijayY.K.,Int. J. Hydrogen. Energ3662011343Search in Google Scholar

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