A.

C Electrical Conductivity for Polyaniline Prepered in Different Acidic Medium

INTERNATIONAL JOURNAL OF BASIC AND APPLIED SCIENCE

Insan Akademika Publications

P-ISSN: 2301-4458 E-ISSN: 2301-8038 Vol. 01, No. 02 Oct 2012

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A.C Electrical Conductivity for Polyaniline Prepered in Different Acidic Medium

Salma M. Hassan 1, Amera Ghareeb Baker 2, and Harith I. Jafaar 3
1, 3 2

Department of Physics, College of Science, University of Baghdad-Iraq

agba1966@yahoo.com

Department of Physics, Faculty of Science and Health, University of Koya

Key words
Doped Polyaniline, FT-IR studied, A.C Electrical Propertiesed

Abstract:
Polyaniline was prepared in different acidic medium at room temperatuer. The out put of polymerization was characterization by FT-IR. The A.C electrical properties were studied. A.C conductivity ac() is found to vary as s in the frequency range (100Hz-10MH), the value of (S) was found to be less than unity (S<1), the dielectric constant (1) and dielectric loss (2) have been determined for bulk polyaniline. Both (1) and (2) decrease with the increase of the frequency.
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Introduction

Electrically conducting polymers described as a new class of synthetic metals reached a high interest in the last years, confirmed by the 2000 Nobel Prize in chemistry for the discovery and development of conductive polymers (Heeger, 2001). Polyaniline is one of the most studied material because of its high conductivity upon doping with acids, well behaved electrochemistry, and easy preparation under reproducible conditions by both electro polymerization and chemically oxidation of aniline, chemical and electrical stability, and good environmental stability (Huang & Kaner, 2004; Catedral, et. al., 2004; Hosseini, et. al., 2006; Sharma, 2006; Hosseini, et. al., 2009; Reddya, et. al, 2009; Vivekanandan, et. al., 2011; Zareh, et. al., 2011; and Bitencourt, et. al., 2012). A key property of a conductive polymer is the presence of conjugated double bonds along the backbone of the polymer. In conjugation, the bonds between the carbon atoms are alternately single and double. Every bond contains a localized sigma ( ) bond which forms a strong chemical bond. In addition, every double bond also contains a less strongly localized pi ( ) bond which is weaker. However, conjugation is not enough to make the polymer material conductive. In addition and this is what the dopant does charge carriers in the form of extra electrons or holes have to be injected into the material. A hole is a position where an electron is missing. When such a hole is filled by an electron jumping in from a neighboring position, a new hole is created and so on, allowing charge to migrate a long distance. The conducting mechanisms are well understood by considering their conjugated carbon backbones the conducting
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mechanism in the polyaniline forms is more complex and not very well established. Polyaniline acts as an electrically conductive material only in the protonation form of emeraldine salt. It can changes the electronic conductivity about (10) orders of magnitude, passing from insulator state ( emeraldine base with <10-10 S/cm) to metallic conduction (emeraldine salt with ~10-1-102 S/cm), depending upon the protonation degree (Ali, et. al., 2007; Detsri & Dubas, 2009; and Dumitrescu, 2009). These properties are optimal at stoechiometrical ratio between the oxidant, hydrochloric/ sulfuric acid and aniline (da-Silva, et. al., 2005; and Hdeshmukh, et. al., 2007). Controlling the pH, doping level and polyanilines polymerization conditions, we assume that is possible to change the morphology and thus the physic-chemical properties of polymer.

Fig.1: Polyaniline as Emeraldine Salt (ES), in sulfuric acid media.

The aspect which attracted our interest is the protonated structure of polyaniline in the acidic media, Fig.1 Polyaniline in its sulfonated form shows a close structure with the ion conducting polymers, where the inorganic anions are represented by HSO4 - species. In the emeraldine salt (ES), the HSO4 -species are ionically bonded with the -NH groups presented in the polymer chain. Actually, these kinds of bonds are very weak and can be removed very easy by changing the systems pH. By supplementary doping of polyaniline in sulfuric acid media, actually we introduced multiple charge carriers which determine an improvement of the electrical conduction along the polymer chain. Moreover, we assume that the total conduction in SPANI is given by summing the electrical conduction and ionic conduction that occurs by sulfonic groups on the aromatic rings.

Fig.2: The designed transition of electron conducting PANI (ES) to -SO3 doped polyaniline (SPANI).

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Hasan, et. al.

Experimental Part

The preparation of (PANI) is based on the oxidation of (0.2M) aniline hydrochloride with (0.25M) ammonium peroxy disulfate in aqueous medium. The pure sample was prepared in distilled water and the doped samples with (2) molarities of HCl and H2SO4 aqueous solution .To prepared sample doped with (2M), aniline hydrochlorid in (1M) aqueous solution in a volumetric flask to (50 ml) of solution, ammonium pexroy disulfate is similarly dissolved in (1M) HCl also to (50 ml) of solution both solution are mixed at room temperature in a rounder, and gentle stirring to polymerize the mixture, and left the rest to the next day. The (PANI) precipitate is collected on a filter and washed with three (100 ml) of (0.2M) HCl, and (150M) of acetone. Polyaniline (emeraldine) hydrochloride powder is dried in air for about one hour then in vacuum oven about (80 C) for (6 hours) the average yield is (1.85gm). In the same way we prepared polyaniline doped in H2So4 (SPANI). The A.C electrical measurements are used to investigate polyaniline samples doped during polymerization with various acidic medium of HCl and H2SO4. The polyaniline powder was thoroughly grounded in a mortar to obtain very fine particles, and then it was compressed under a pressure of (10 tone) in the form of a pellet. The resulting pellet has a diameter of (1.3cm and thickness of 1.88-1.79mm). To improve the electrical contact the faces of the pellet were coated with aluminum by thermal evaporation. The LCR meter models (HP-4274A and HP-4275A) were used for the ac measurements. The sample was placed in a holder specially designed to minimize stray capacitance. The range of frequency was (100Hz-10MHz). The measurement give as, the specimen capacitance (C), dissipation factor (D) and resistance (R).
The total conductivity was calculated from the following equation: t() = d/RA where (d) is the thickness of the sample and (A) is the cross-section area. The A.C conductivity ac () was calculated by using the relation: tot( ) = ac() +dc Where dc is the D.C. conductivity. The dielectric constant (1) was calculated from the equation: 1 = dCp/A where () is the permittivity of free space. The dielectric loss (2,) as calculated from the equation: 2 = 1tan, where =90 ...(4) ...(3) ...(2) ...(1)

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3
3.1

Results and Discussion

Time of Polymerization

The oxidation of aniline was found to be exothermic reaction. The temperature of reaction changes with time of polymerization. Fig.3 shows the reaction temperature with time of polymerization for polyaniline samples for doped polymer at room temperature. From this figure it can distinguish three stages, first stage (induction period), the temperature stays virtually constant, the reaction mixture becomes blue as oligomeric intermediates are produced. When the polymerization has started, the temperature increases, as shown in stage two, when polymerization propagate, the color of the mixture turns to dark green, and the consistency becomes that of a slurry. In stage three the temperature decreases and reaches the saturation, the reaction will be in the termination step (post - polymerization period).The difference in polymerization time is strongly depending on the temperature of used aqueous solution. The room temperature polymerization is completed within 30 minutes.

35 33 31 29 Temperatuer(C) 27 25 23 21 19 17 15 0 5 10 15 time(min) 20 25 30 35 water 2M H2SO4 2M HCl

Fig.3: The variation time of polymerization as a function of reaction temperature for doped polyaniline in different acidic medum.

From Fig.3, we notice that the reaction of polyaniline doped in HCl is more active, and that will reflected on the yield and average moleculoer weight .

3.2

Fourier Transform Infrared ( FT-IR)

Fig.4 shows the FT-IR for pure polyaniline, from the spectrum, it can distinguish between benzenoid rings and quiniod rings in the 1300-1600 cm-1 region of the spectrum. The most pertinent FT-IR data for polyaniline in a potassium bromide (KBr) matrix are listed in Table 1. The band characteristic of the conducting protonated form is found about 1226cm-1 and the band at 1144 cm-1 be assigned to a vibration mode of a protonated imines group (Mirmohseni, et. al., 2008).

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Table 1: List of the observed beak in the polyaniline samples in (KBr) matrix (Noor, 2005) Peak (cm-1) 586-800 1144 1296 1473 1558-1566 Assignment C-Cl Aromatics out of plain bend C-N Imines bending C-N stretch of benzenoid ring C-C benzenoid ring stretch(N-B-N) C=C stretch of quinoid ring (NQN)

Fig.4: The FT-IR spectrum for pure polyaniline

Fig.5: The FT-IR for SPANI

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3.3

Electrical Properties

The A.C conductivity for the common polymer is changes with the frequency according to the following formula (Joshi & Sinha, 2007): ac()=t d.c =As ...(5)

Where (A) is a constant independent on temperature, ( =2**f) and (s) is the frequency exponent. Fig.6 shows the frequency depends on the total conductivity (t) measured for pure polyaniline and doped with (2M) of HCl and H2 So4 samples at room temperature. It was observed that the (t,) increased with the angular frequency. The sample doped in HCl have higher conductivity from the other samples because the rate of polymerization is higher in HCl, thats mean the molecular weight of prepared polymer increased and effected on the number of polaron in polymer chain and that produced increasing in conductivity. The A.C conductivity is obtained by subtracting the A.C conductivity from the total conductivity measured according to Equation (5). Fig.7, shows the dependence of A.C conductivity on the frequency. From the figure it is clear that a.c increases with increases in the frequency. The frequency exponent (s), can be calculated from the slope of the straight lines in Fig.7, the exponent (s) is less than unity. The general values of (s) appear to be consistent with a hopping process of charge carriers (protons) between polymer chains.

-2

2M .H2SO4 2M,HCl 0M,Water

-4

Ln a.c (.cm)-1

-6

-8

-10 4 6 8 10 12 14 16 18 20

Ln (Hz)
Fig.6: The variation of A.C electrical conductivity as a function of angular ferquency

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Ln tot (.cm)-1

2M,HCl 2M,H2SO4 0M,water

-2
y = 0.6499x - 14.345

-4

-6

y = 0.5271x - 14.538

-8
y = 0.4375x - 14.285

-10 12 14 16 18 20

Fig.7: The variation of a.c conductivity as a function of angular ferquency.

In Table 2, listed the value of exponential factor. The frequency exponent (s) can be calculated from the slope of the straight lines in Fig.7, the exponent (s) is less than unity. The general values of (s) appear to be consistent with a hopping process of charge carriers (protons) between polymer chains.

Table 2: The value of exponential factor Samples PANI pure 2H 2 SO4 M 2 HCl M S factor 0.437 0.527 0.649

3.4

Frequency Dependence on Dielectric Constant

The dielectric constant, was calculated from the measured value of capacitance in the range of frequency 100Hz-10MHz. Fig.8, shows the variation of capacitance with angular frequency at room temperature. The figure shows that for all samples the capacitance is increasing with decrease of frequency. This behavior can be appropriately explained on the basis of charge carriers being blocked at the cathode. The space charge layer eventually leads to a substantial increase in capacitance (Joshi & Sinha, 2007). Fig.9, shows the frequency dependence on (1), it is clear from the figure (1) decreases with the increase in frequency. The decrease of (1) with frequency can be explained as follows: at low frequencies, (1) for polar materials are due to the contribution of multi-component of polarize ability deformational polarization (electronic, ionic, orientation, and interfacial).When the frequency is increased, the dipole will no longer be able to rotate sufficiently rapidly. So their oscillations being to be lag behind those of the field. As the frequency is further increased, the dipole will be completely unable to follow the field and the orientation stopped, so (1) decreases at a higher frequency approaching a constant value due to the interfacial polarization (Joshi & Sinha, 2007).

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1.E-08
2M, HCl 0M,water 2M,H2SO4

8.E-09

capacitance ( F )

6.E-09

4.E-09

2.E-09

0.E+00 5 7 9 11 13 15 17 19

Ln(H
Fig.8: The variation capacitance with angular frequency at room temperature

8.E+06

2M,Hcl 2M.H2SO4 0M,water

Dielectric cinstant 1

6.E+06

4.E+06

2.E+06

0.E+00 5 9

Ln(H

13

17

21

Fig.9: The variation of dielectric constant 1 with angular frequency at room temperature 3.5 Frequency Dependence of Dielectric Loss

The dielectric loss, 2, was measured as a function of frequency. Fig.10, shows the dependence of (2) on the frequency at room temperature. It is observed from the figure that (2) is found to be decreases with the increases in the frequency with the temperature. The origins of the dielectric losses are the conduction losses (Zareh, et. al., 2011).

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1.6E+09
2M,H2S04 2M,HCl 0M,water

1.2E+09

Dielectric Losses 2

8.0E+08

4.0E+08

0.0E+00 5 7 9 11 13 15 17 19

Ln(Hz
Fig.10: The variation dielectric losses 2 with angular frequency at room temperature 3.6 Physical Properties of Prepared Polyaniline

In our study some of physical properties of polyaniline were measured. It can be classified this polymer and it can be enhanced electrical and optical properties and solubility. Table 3, listed some properties of prepared polyaniline

Table 3: Properties of prepared polyaniline Density (gm/cm3) 1.329 1.840 1.955 Refractif index (n) at 293K 1.429 1.44 1.433 Avarge Molcular weight M 40539.46 65218.75 76221.86

Samples

Solubility Disolve partial in stroung Solvint like (DMF) Disolve partial in water Disolve in stroung Solvint like (DMF

Pure PANI 2H 2 SO4 M 2 HCl M

Conclusion

A.C conductivity of polyaniline prepared pure and doped with different acidic medium of HCl and H2 So4 at room temperature was measured as a function of frequency in compressed pellet with evaporated ohmic Al electrodes. The a.c conductivity was found to be vary as s in the frequency range ( 100Hz-10MHz), the frequency exponent (s) was less than unity and decreases with the increase in the temperature indicating a dominant barrier hopping mechanism. The dielectric constant (1) was found to be decrease with increase in the frequency. The dielectric loss (2) was also found to be decreased with increase in the frequency. The polyaniline prepared in H2 So4 was improving the enhanced solubility which dissolvent partially in water.

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Rereferces
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Zareh, E. H.; Moghadam, P. N.; Azariyan, E.; and Sharifian, I. (2011). Conductive and Biodegradable Polyaniline/Starch Blends and Their Composites With Polystyrene, Iranian Polymer Journal, 20(4), 319-328.

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