JOURNAL FOR THE ADVANCEMENT OF SCIENCE & ARTS, VOL. 1, NO.

1, JANUARY JUNE 2009

Dielectric Properties of Poly (vinyl alcohol)/Polypyrrole Composite Polymer Films

1

Mohd Hamzah Harun, 2Elias Saion, 3Anuar Kassim, 4Ekramul Mahmud, 5Muhd Yousuf Hussain, and 6Iskandar Shahrim Mustafa

Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, Selangor Faculty of Science, Universiti Putra Malaysia, Serdang, Selangor 4 Faculty of Chemical Engineering, MARA University of Technology, Shah Alam, Selangor 5 Department of Physics, University of Agriculture, Faisalabad, Pakistan hamzah@nuclearmalaysia.gov.my
2, 3, 6

Abstract Polyvinyl alcohol-polypyrrole composite polymer films were synthesized by chemical oxidative polymerization. Iron (III) chloride, FeCl3 had been used at different concentrations as dopant and oxidant. Dielectric properties were measured in the frequency range from 20 Hz to 1 MHz at room temperature using HP 4284A LCR meter. Results show that the dielectric properties vary with the compositions of iron (III) chloride dopant. Keywords: Dielectric properties, poly (vinyl alcohol)/polypyrrole composite, conducting polymer

1. INTRODUCTION In the recent years conjugated conducting polymers have been the main focus of research throughout the world [1-5]. Since the discovery led by 2000 Chemistry Nobel winners, Shirakawa, MacDiarmid and Heeger [6], the perception that plastic could not conduct electricity has changed. Nowadays, conducting polymers also known as conductive plastics are being developed for many uses such as corrosion inhibitors, compact capacitors, antistatic coating, electromagnetic shielding and smart windows; which capable to vary the amount of light to pass [7]. Polypyrrole, PPy is one of this new generation of polymeric materials. It has been the main focus due to the advantage such as environmentally stable, ease to synthesis and relatively high conductivity as compared to other derivatives [8-10]. However, limitations such as insolubility and poor mechanical strength are barriers for mass production. Several attempts have been made to prepare blends or composite materials containing PPy to overcome its limitations. Polymer matrices as host material such as polyvinyl chloride (PVC), poly (methyl methacrylate) (PMMA), and poly (vinyl alcohol), (PVA) have been used in order to increase the solubility as well as the mechanical strength of polypyrrole. The dielectric behavior of polypyrrole composite films is studied in this work. PVA is incorporated that acts as host material in the conducting composite polymer containing PPy. The advantages of PVA such as high mechanical strength and water-soluble have played as

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main role for this selection as compared to other polymer matrices. The concentration of the dopant namely iron (III) chloride was varied in order to investigate the influence of dopant compositions on the dielectric properties of the composite polymer.

2. MATERIALS AND METHODS PVA (Mw: 27,000), and pyrrole (Py) monomer, supplied by Fluka, were used and pyrrole was distilled prior to use. Reagent iron (III) chloride (FeCl3) supplied by Riedel de Haen was used as received. The experiment was carried out at room temperature (27 oC). 3 g PVA was dissolved completely in 100 ml distilled under constant stirring for 1 hour while the mixture was heated up till 90 oC then the mixture was let to cool down to room temperature (24 oC) while the stirring of the mixture was carried out to ensure a homogenous composition. From the cooled mixture, 30 ml were sampled out and mixed with 1 g of pyrrole monomer already dissolved in 15 ml of distilled water. The mixture was further stirred for 5 minutes to ensure homogeneity. Finally, 0.3 g FeCl3 was added in the composite mixture as a dopant and stirred further for another 10 minutes. Various concentrations of FeCl3 (0.3 g, 0.6 g, 0.9 g, 1.2 g, 1.5g) were dissolved as stated above and in this way various samples were obtained. To cast the film, the mixture for each FeCl3 concentrations was poured in a casting glass plate 14 x 14 cm and let it dry at room temperature for 120 hours. At the expiry of this time, the films were ready which were peeled off the casting glass plate and cut into 4 x 4 cm pieces for characterization by measuring dielectric properties using Precision LCR meter HP 4284 A at frequency range 20 Hz to 1 MHz. nC4H5N(PVA)+2.25n FeCl3 -> [C4H3N0.25+ Cl0.25-]n + 2n HCl+2.25n FeCl2+ (H2O) (Benssendik et al., 1995) [10]

3. RESULTS AND DISCUSSION Dielectric Permittivity Study

PVA-PPy-FeCl3
1.0E-07

Relative permittivity, '

1.0E-08 1.0E-09 1.0E-10 1.0E-11 1.0E-12 1.0E-13 1.0E+01

0.3g 0.9g 1.5g

0.6g 1.2g

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

frequency (Hz)

(a)

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PVA-PPy-FeCl3 0.3g
1.0E-07 1.0E-08

0.6g 1.5g

0.9g

1.2g

Dielectric loss, "

1.0E-09 1.0E-10 1.0E-11 1.0E-12 1.0E-13 1.0E-14 1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

frequency (Hz)

(b) Figure 1: a) Relative permittivity and (b) loss factor for composite films of polypyrrole at different concentrations of FeCl3 dopant. The dielectric parameter as a function of frequency is described by the complex permittivity in the form

* ( ) = '( ) "( )

(1)

where the real part () and imaginary part () are the components for the energy storage and energy loss, respectively, in each cycle of the electric field. For the dielectric characteristics of irradiated and unirradiated composite samples, the measured capacitance, C() was used to calculate the dielectric constant, () using the following expression:

' ( ) = C ( )

d A

(2)

where d is sample thickness and A is surface area of the sample. whereas for dielectric loss, ():

" ( ) = '( ). tan ( )

where tan is tangent delta.

(3)

Then from the calculated data, we can find dielectric modulus. In complex form dielectric modulus is:

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JOURNAL FOR THE ADVANCEMENT OF SCIENCE & ARTS, VOL. 1, NO. 1, JANUARY JUNE 2009

M* =

1 = M '+ iM " *

(4)

where M and M are the real and imaginary part of dielectric modulus. The formula to calculate dielectric modulus are given by: M '=

' ( ' + "2 )

2

(5)

M"=

" ( ' + "2 )

2

(6)

From the imaginary part of electrical modulus, M, the relaxation time of the orientation of dipoles can be obtained. The peak for angular frequency, p can be obtained from the graph M versus log frequency.

(7)

Figure 1 shows the relative permittivity, and loss factor/permittivity, for PVA-PPy-FeCl3 composite polymer films. All graphs shown are not adhere with Deybe model. The dielectric permittivity as depicted in figure 1(a) decreases with the increasing of frequency. This may be attributed to the tendency of dipoles in polymeric samples to orient themselves in the direction of the applied field. However at the high frequency range (1x104 Hz to 1x106 Hz), the decreasing trend seems not too sharp as compared for lower frequency region. This trend is observed for all graphs for different concentration of dopants. It could be explained by dipoles orientation, which difficult to rotate at high frequency range. On the other hand, the high value of at low frequency might be due to the electrode effect and interfacial effect of the sample [11]. The variation of dielectric loss with frequency for PVA-PPy-FeCl3 at different concentration of dopants is as depicted in figure 1(b). It is clear from the graph that dielectric loss decreases with frequency. The larger value of loss factor or dielectric loss at low frequency could be due to the mobile charges within the polymer backbone. The higher value of the dielectric loss for the higher concentration of dopant can be understood in terms of electrical conductivity, which is associated with the dielectric loss. On the other hand, the mobile charges i.e. polarons that belong to conducting PPy and free ions that come from iron (III) chloride increase at higher concentration of the dopant thus also influence lower value of at high frequency [11]. Moreover, PVA exhibits flexible polar side groups with polar bond as the bond rotating having intense dielectric -transition [12]. Thus there is a change in the chemical composition of the polymer repeated unit due to the formation of hydrogen bonds with hydroxyl groups in the polymerization process, which in turn makes the polymer chain flexible and hence enhances the electrical conductivity.

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Electrical Modulus Study

PVA-PPy-FeCl3 2.00E+23 1.60E+23 1.20E+23 M' 8.00E+22 4.00E+22 0.00E+00 1.00E+01 0.3g 0.6g 0.9g 1.2g 1.5g

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

Frequency (Hz)

(a)

PVA-PPy-FeCl3 6.00E+22 0.3g 5.00E+22 4.00E+22 0.6g 0.9g 1.2g 1.5g

M"

3.00E+22 2.00E+22 1.00E+22 0.00E+00 1.00E+01

1.00E+02

1.00E+03

1.00E+04

1.00E+05

1.00E+06

Frequency (Hz)

(b) Figure 2: a) Real dielectric modulus and b) Imaginary dielectric modulus of PVA-PPy-FeCl3 composite polymer films Figures 2 (a) and (b) show the calculated value of real and imaginary part of electrical modulus for composite films at different concentration of dopants. The value at low frequency region (below 1x104 Hz for real modulus and 1x103 Hz for imaginary modulus) indicates the removal of electrode polarization [11, 13]. The spectrum of M() shows an asymmetric peak approximately centered in the dispersion region of M (). The peak shifts to higher frequency with the increasing of dopant concentrations. From the graph, it also shows that the height of the peak decreases with the dopant concentration as

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relaxation time decreases. Note that the frequency at the peak of M() is the relaxation frequency, p as tabulated in the inset in figure 2 (b). Table 1 shows the relaxation time, for polypyrrole composite film at different concentration of the dopants. The relaxation times were obtained from renowned Havriliak Negami relationship [12] where ( =1/p), p is the peak of the angular frequency and is the relaxation time. From the whole data, one can conclude that with the increasing amount of the dopant, the relaxation time is relatively reduced although it does not change for the whole samples as it is might be due to intrinsic behavior of the sample. These results confirm the explanation for the dielectric constant and dielectric loss characteristics as relaxation times decreases with the increasing composition of the dopant. Relaxation time (x10-5 Hz-1) 1.22 1.59 0.16 0.04 0.02

Dopant composition (g) 0.3 0.6 0.9 1.2 1.5

Table 1: Relaxation time, for PVA-PPy-FeCl3 composite polymer films 5. CONCLUSION The present communication shows that the dopant composition has great influence on the trend and magnitude of dielectric properties. The results also show that the composite polymer films have both electric and electronic properties. The composite polymer films exhibit the combination of intrinsic dielectric anisotrophy as a result of the competition of free charges mainly polaron in polypyrrole and electronic polarization corresponded to PVA matrix. Relaxation times become shorter as the composition of dopant is increased indicates that multiple path of the system to be relaxed due to high availability of free charges.

6. ACKNOWLEDGEMENT The first author acknowledges constructive discussion with all supervisors and all research fellows in Biophysics Lab, UPM. Technical support and facilities from MINT is greatly appreciated and finally, financial support from Malaysian government through IRPA program (IRPA No. 09-02-0275-EA001) is gratefully acknowledged.

7. REFERENCES [1] Kinlen, P J, Silverman, D C and Jeffreys, C R (1997) Corrosion Protection Using Polyaniline Coating Formulations. Synthetic Metals 85, 1327-1332. [2] Kuhn, H H, Child, A D and Kimbrell, W C (1995) Toward Real Applications of Conductive Polymers. Synthetic Metals 71, 2139-2142.

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[3] Dutta, P, Biswas, S and De, S K (2002) Dielectric Relaxation in Polyaniline-Polyvinyl alcohol Composites. Materials Research Bulletin 37, 193-200. [4] Bredas J L, Chance, R R.and Silbey, R (1982) Comparative theoretical study of the doping conjugated polymers; Polarons in polyacetylene and polyparaphenylene. Physical Review B 26, 5843-5854. [5] Clarke, T C, Geiss, R H, Kwak, J F and Street, G B (1978) Highly conducting transition metal derivatives of polyacetylene. Journal of Chemical Society Chemical Communication 338, 489-490. [6] Shirakawa, H, Louis, E J, MacDiarmid, A G, Chiang C K and Heeger, A J (1977) Synthesis of Electrically Conducting Organic Polymers: Halogen Derivatives of Polyacetylene, (CH)x, Journal of Chemical Society of Chemical Communication, 474, 578-580. [7] Bengt, N and Krutmeijer E (2000). The Nobel Prize in Chemistry, 2000: Conductive Polymers (Advanced Information), pp 1-15. The Royal Swedish Academy of Science. [8] Hamzah, H M, Saion E and Kassim, A, (2004), AC Conductivity Measurement of PVAPPY Conducting Polymer Composites, 6th Putra Physics Seminar Proceedings, 248-261. [9] Hamzah, H M, Saion E, Yahya, N, Kassim, A and Ekramul, M, (2003), The Study of Conductivity of Polypyrrole Conducting Polymer, 5th Putra Physics Seminar Proceedings, 73-76. [10] Benseddik, E, Makhlouki, M, Bernede, J C, Lefrant, S and Pron, A (1995) XPS studies of environmental stability of polypyrrole-poly(vinyl alcohol) composites. Synthetic Metals 72, 237-242. [11] Dutta, P, Biswas, S and De, S K (2002) Dielectric Relaxation in Polyaniline-Polyvinyl alcohol Composites. Materials Research Bulletin 37, 193-200. [12] Singh, K P and Gupta, P N (1998). Study of Dielectric Relaxation in Polymer Electrolytes. European Polymer Journal 34, 1023-1029. [13] Migahed, M D, Ishra, M, Fahmy, T and Barakat, A (In Press) Electric modulus and AC Conductivity Studies in Conducting PPy Composite Films at Low Temperature. Journal of Physics and Chemistry in Solids.

Mohd Hamzah bin Harun (born November 24th 1979, in K. Terengganu) completed his BSc. (Instrumentation Science) at Universiti Putra Malaysia and graduated with MSc. (Applied Radiation Physics) from the same campus. He is now working as Research Officer in Malaysian Nuclear Agency. His research interests are in surface finishing by UV curing technology, development of conducting polymers and carbon nanotube nanocomposites by mean conventional chemical technique and radiation technique. Prof. Dr. Elias Saion (born in 1952, in Tangkak, Johor) is currently serving as a professor of Applied Radiation at UPM. He received his BSc. in Physics from UKM in 1975. After joining UPM later, then he went to University of Surrey in where he obtained his MSc. in Medical Physics three years later. After appointed as lecturer in late 1978, he continued his study at St. Andrews University in 1985 and then graduated in 1989 with a title of PhD (Radiation Biophysics). After concentrating and excelled in research projects he was appointed as a full professor in 2006. His research activities have been primarily

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concerned with interactions of ionising radiation with matter including sediment samples, polymer gel dosimeters for radiotherapy treatment planning, radiation synthesis of ionic and conducting polymers, radiation grafting polymer membranes for fuel cell and radiation synthesis of metal and metallic oxide nanoparticles. He enjoys imparting knowledge and experience to postgraduate students from within the country and from different nationalities including Saudi Arabia, Jordan, Indonesia, Iran, Iraq, Pakistan, Sudan and Yemen. He is the author and co-author for over 200 articles and also author and co-author for books (7 books and 9 chapters in books). Prof. Dr. Anuar Kassim (born 1951, in Melaka) is currently serving as a professor in the Department of Chemistry, UPM. He received his BSc. (Chemistry) from UKM in 1975. He then joined UPM in and successfully obtained PhD. Degree in Electrochemistry in 1980 from University o Salford. He was appointed as full professor in 2004. His research interests are in Electroanalytical and Materials Chemistry. His current R&D projects include Conducting Polymers and Cosmetic Application of Dihydroxystearic acid (DHSA) and derivatives. He has published more than hundred articles in local and international journal as well as in seminars and conferences respectively. He has supervised twenty postgraduate students (MSc. and PhD.) from different nationalities. H.N.M. Ekramul Mahmud, Ph.D (UPM). has been serving as a lecturer in the Faculty of Chemical Engineering, University Technology MARA (UITM), Shah Alam since 2006. His research interests include Preparation and Characterization of Conducting Polymers, Removal of Heavy Metals from Wastewater, and, Biomass Conversion to Liquid Fuels.

Prof. Dr. Muhammad Yousuf Hussain, a former PhD. student in UPM. He completed his PhD. in 2007 in Fuel Cell technology. He is now serving as Head of Physics Department in University of Agriculture, Pakistan. His research interests include Direct Methanol Fuel Cell, Radiation Technology for Polymers and Dosimeters.

Mr. Iskandar Shahrim Mustafa (born April 3, 1979, in Ipoh, Perak) completed his BSc (Hons) Material Science at Universiti Putra Malaysia in 2002 and graduated with MSc (Applied Radiation) Medical Physics from Universiti Putra Malaysia in 2006. He was a lecturer with Centre of Foundation Studies for Agricultural Science, UPM from 2006-2008. He lectures subjects related to Physics and Agricultural Science. In addition to his lecturing duties, he has been actively publishing journals and presenting conferences. At present, he is a PhD scholar under Universiti Sains Malaysia focusing on Radiation Science (Biophysics and Medical Physics).