Project Title

Solution phase Polymerization of Aniline with various Dopants

Project Advisor Project Members
Mohsin Hasan Ali Abbas Talha Ismail 2008-PPE-65 2008-PPE-54 2008-PPE-66

Muhammad Aamir Shehzad

DEPARTMENT OF POLYMER & PROCESS ENGINEERING, U.E.T LAHORE.

PREFACE

Thanking the ALLAH almighty who is Sovereign and his Power is Divine. Our Parents who are the Most Important Thing for us in this world and our teachers whos place is eternal in our life. This report is based on the project at Polymer Engineering Department of UET Lahore, providing necessary knowledge of experimentation. The aim to write this report is to share a meaningful material and concepts about the conductivity of Polymers.

ACKNOWLEDGEMENT

We are highly thankful to Allah for the successful completion of our mini project. During our project we have learnt about a new family of polymers which are conductive and play an important role in electronics world. We are highly thankful to Mr. Aamir Shehzad, who guided us to understand the environment and helped us to apply our knowledge and built our own experimental skills.

Abstract
In the current studies, polyaniline is prepared in solution phase, polymerized chemically in the presence of different organic and inorganic acids acting as dopant. Each sample of Polyaniline prepared using acids is characteristically studies by FTIR and DSC techniques. The conductivity of PANI is measured by 4-point probe method and results are compared.

1. Introduction
Until the early years of 20th century, polymers were being discarded and were known as electric insulators. Conducting polymers have the electronic properties of semi conductors and, at the same time the processing advantages and mechanical parameters of polymers [1]. The basic requirement for polymers to become conducting is the overlapping of molecular orbital to allow the formation of delocalized molecular wave functions and secondly, these molecular orbital must be partially filled so that there is a free movement of electrons throughout the polymeric structure [2]. The unusual electronic properties such as electrical conductivity, low ionization potential and high electron affinity are associated with the pi-electrons backbone of the conjugated polymers. The word conjugated denotes an alteration in series of single and double bonds along which, under appropriate conditions, conduction can be induced at the backbone of the polymer [3]. The fundamental process of doping is a charge-transfer reaction between an organic polymer and a dopant. When the charges are removed from a polymer upon chemical doping, geometric parameters, such as bond length and angles, change. The charge is localized over the region of several repeating units. Since the localized charges can move along the polymer chain, they are regarded as charge carriers in conducting polymers [4]. These quasi particles are classified into POLARONS,BI-POLARONS and SOLITONS according to their charge and spin. The interest in conducting polymers seems from the fact that the polymers being light in weight and readily moldable can replace the convention electrically conducting materials in electrical and electronic applications [5]. Applications The use of conducting polymers in various industries involves lower fabrication and maintenance cost with higher durability and light weight products. Among these polymers, polyaniline has immerged as promising candidate with great potential for practical uses such as in light emitting diode, transparent electrodes, electromagnetic radiation shielding, corrosion protection of metals, gas and humidity sensing, battery applications and many more.

2. Methods for synthesis of Polyaniline

General synthesis of PANI is done by direct oxidation of aniline using an appropriate chemical oxidant or by electrochemical oxidation on different electrode materials. Most of the researchers admit that the characteristics of the polymer depend upon the mode of synthesis. Chemical and electrochemical syntheses are two common modes of classical synthesis of polyaniline. 2.1.Chemical synthesis When aniline is mixed with the chemical oxidant in a reaction vessel and left for a certain period of time, the solution gradually becomes colored and a black precipitate appears [6]. Genis et al has observed that this phenomenon occurred in most of the solvents. The oxidations of aniline by a chemical oxidant could occur at ambient temperature. The reaction depends upon the temperature. The oxidation reaction of aniline can be broken down into two stages: A slow thermic stage which is dependent on Ph, temperature and concentration of reactants. Dissolved oxygen in the solvent has no influence on the reaction in contrast with other oxidizing species which decreases the induction period. II. fast exothermic stage which is temperature dependent and varies slightly with the concentration of oxidant.
I.

2.2.Electrochemical Synthesis Anodic oxidation of aniline on an inert metallic electrode is the most current method for the synthesis of PANI.

2.2.1.Advantages [7-12]

The resulting product is clean. Does not need necessary to be extracted from the initial monomer / oxidant / solvent mixture.

The anodic oxidation of aniline is generally affected on an inert electrode material which is usually [13] Platinum Iron Copper Zinc Chrome Gold Lead

Palladium

2.2.2.Note Theoretically, two electrons are necessary for the polymerization of aniline and a certain numbers of supplementary electrons are necessary to oxidize the polymer. The rate of electro deposition of PANI in aqueous media is influenced by the anion concentration and not by the acid concentration, although acidic concentration is required for polymerization. The aniline oxidation is catalyzed by the fully oxidized from PANI i.e., pernigraniline. 2.3.Synthesis by other conventional Methods 2.3.1Gas Plasma method This method had been mainly employed for the oxidation of aniline and a few of it substituted derivatives [14-15]. 2.3.2.Advantages The monomer was polymerized in the absence of both the oxidant and the solvent. The resulting product was extremely clean. The supporting material did not need to be conducting

2.3.3.Disadvantages

The energy associated with the plasma was very high degradation of the polymer

2.4.Conduction of polyaniline through doping process: Doping is a process to enhance the conductivity of a material. Doping increases the number of charge carriers in the materials, just as an impurity does in classical inorganic semiconductors. But the process as in case of inorganic semiconductors cannot be duplicated to polymer field because the two processes are fundamentally different. In polymers, doping concentration is exceptionally high as compared to those commonly in doped inorganic semi conductors. In some cases, the dopant constitutes about 50% of the final weight of the conducting polymer composition. The system would be more appropriately described as a conducting charge transfer complex rather than a doped polymer. The doping of conjugated polymers generated high conductivities primarily by increasing the carriers concentrations. This is accomplished by oxidation or reduction with electron acceptors or donors respectively, thus resulting in positive or negative charges. For example, the polymer is oxidized by the acceptor dopant, which itself get reduced and thereby, producing a radical cation or hole in the polymer chain. If the hole can overcome,

the columbic binding energy to the acceptor anion with the thermal energy or at high dopant concentration, via screening of the coulomb charges of the anion, it moves throughout the polymer and contributes to the conductivity. Thus we can say p-type doping of the polymer produces positive charges and n-type doping produces negative charges in the resultant polymer complex. Dopant produces sites in the energy gap that lie close to the either the conduction or valence band. Conduction is due to majority carriers i.e., either electron forming n-type conductors or holes forming p-type conductors with conductivities of more than 10-7 Scm-1. True metallic behavior results, when the energy gap between filled and empty state disappears, at low levels of loading, the conductivity of the polymer dopant composite differs only slightly from that of host polymer. It has been found that the electronic structure of conducting polymers can be manipulated changes the pH of the solvent. For a particular polymer, its conductivity tends to relatively insensitive to the identity of doping agent. The most important requirement for a dopant is sufficient oxidizing or reducing power to ionize the polymer. Conventional polymers inherently have insufficient number of delocalized charge carriers. As a consequence, they must be modified so that number of charge carriers or charge carriers mobility in increased. Doping is basically quantitative and carrier concentration is directly proportional to the dopant concentration. Doping in polymers is different from doping in inorganic semiconductors. The conductivity of polymeric semiconductors depends upon many factors such as; Nature and concentration of dopants Homogeneity of doping Carriers mobility Crystallinity Morphology of polymers

Doping of conducting polymers involves random dispersion or aggregation of dopants in molar concentration in the disordered structure of entangled chains. In case of inorganic semiconductors, the doping generates either holes in the valence or electrons in the conduction band. Polymer doping leads to the conjugational defect like solitons, polarons, and bipolarons in the polymer chains. As dopants are strong oxidizing or reducing agents, so on doping positive or negative charge carriers are developed in the polyaniline [16-17]. Polyaniline + dopant Polyaniline + dopant oxidation (doped polyaniline)+ + (dopant)+ reduction (doped polyaniline)- + (dopant)+

2.5.Oxidation states of Polyaniline:

2.5.1.Emeraldine(green or blue) It is half oxidized half reduced state often referred to as emeraldine base, is either neutral or doped, with the ammine nitrogen protonated by an acid. Emeraldine base is regarded as the most useful form of polyaniline due to its high stability at room temperature and the fact that upon doping the emeraldine form of polyaniline is electrically conducting.

2.5.2.Leucoemeraldine(white or clear) It is fully reduced state. It is pure conductor, even when doped with an acid.

2.5.3.Pernigraniline(blue or violet): It is fully oxidized state. It is a poor conductor even when doped with an acid.

2.6.Conditions required for the synthesis of Polyaniline: High purity of monomers, chemicals and solvents are required for obtaining high quality polymer. The polymerization should be strictly controlled Environment for polymerization should be inert and dry because a slight variation in the polymerization may alter the nature of polyaniline obtained Polyaniline should be kept in a dark, cooled and dry place as the chances are like PANI may undergo isomerization under light and heat

2.7.Chemical Synthesis of Polyaniline

Prepare 100ml of 0.5M aniline salt of respective by dissolving aniline in 1.0M respective in volumetric flask of 200ml. Prepare the solutions of 100ml of 0.5M (100-11.4g) Ammonium peroxydisulfate (APS) in aqueous medium. Keep both solutions for 15mints at room temperature (20-24) 0C. Solution of initiator was mixed with monomer in a separate beaker, briefly stirred (20 hr) and left at rest to polymerize for 24 hrs. PANI precipitates were collected on a filter paper on next day. Polyaniline (emeraldine) salt powder was dried in oven and kept in desiccators [18]. Molarity of Aniline Molarity of APS Acid Name Molarity of acid Amount of APS Amount of Aniline Amount of acid (100XmL) 8.47 5.44 6.78 5.75 9.90 13.8 4.3 8.06 Temp Conditions0C Initial Final 21 21 23 21 21 19 21 21 20 20 21 21 20 20 19 23

S r #

1 2 3 4 5 6 7 8

0.4M 0.4M 0.4M 0.4M 0.4M 0.4M 0.4M 0.4M

0.5M 0.5M 0.5M 0.5M 0.5M 0.5M 0.5M 0.5M

HCl H2SO4 HNO3 CH3COOH Methacrylic Acid Silisic Acid Formic Acid p-Toluene Sulfoiic Acid

0.1M 0.1M 0.1M 0.1M 0.1M 0.1M 0.1M 0.1M

11.4g 11.4g 11.4g 11.4g 11.4g 11.4g 11.4g 11.4g

7.44 mL 7.44 mL 7.44 mL 7.44 mL 7.44 mL 7.44 mL 7.44 mL 7.44 mL

Table 2.1. Recipe of PANI Synthesis

3.Results and Discussion

3.0Chemical Characterization
3.1.FTIR Results for verification of PANI

This analysis is preceded by using the Jasco Spectra Manager of type FT/IR 4100. The experimental procedure is adopted according to FT/IR4000, 6000 Operating Manual. First of all, pellets of the samples are made; one of the reference materials (KBr) and other were of our samples of PANI with different dopants (acids). Then testing is being done on these pallets. The procedure includes: Weigh 200mg of pure KBr (reference material) and grind it to complete powder form. Place the sample in between the two dies and pressurize it to about 60 MPa. Turn on the pump and wait for about 15 minutes to obtain a good and uniform shaped pellet. Similarly, weigh another 200mg of KBr and add only some particles of the sample into it. Prepare this pellet by the same procedure as above. Place pure KBr pellet into the sample holder and go to the software. Click B for the background history of reference material. If transmittance is greater than 100% then use baseline selection to stay within the range (i.e. 100).Then place second pallet into the sample holder and press the button S for the sample measurement. Save the graph of wave number versus transmittance. For the peaks selection, click on the peak selection button and add all the sharp peaks that are headed down showing the functional groups present in the sample.

3.1.1.FTIR Analysis for PANI with HCl Graph 3.1. FTIR result of PANI doped with Hydrochloric Acid

Sr # 1 2 3 4 5 6 7 8 9 10

Wave number(cm-1) 619.038 780.065 889.987 1124.3 1395.25 1640.16 2358.52 2598.6 2911.02 3749.9

Functional Group Alkyl halide(C-Br) Alkyl halide(C-Cl) Aromatics Aliphatic amines(C-N) Aromatics alkenes Nitrile(C triple bond) Aldehyde Alkanes Alcohol, phenols

Table 3.1. wave number against functional group FTIR results at wave numbers 780.065cm-1 and 889.987cm-1 prove the formation of PANI by using HCl acid as a dopant.

3.1.2.FTIR Analysis for PANI with Nitric Acid Graph 3.2. FTIR result of PANI doped with Nitric Acid

Sr # 1 2 3 4 5 6 7 8 9 10

Wave number(cm-1) 613.252 775.244 816.706 1144.55 1400.07 1478.17 1577.49 2364.3 2593.79 3119.3

Functional Group Alkynes Alkyl halide(C-Cl stretch) Alkyl halide(C-Cl stretch) Alkyl halide(CH2-X) Aromatics Aromatics Aromatics Nitrile(C triple bond ) Aldehyde Aromatics

Table 3.2. wave number against functional group

FTIR results at wave numbers (1400.07, 1478.17, 1577.49 and 3119.3) cm-1 and 2364.3cm-1 prove the formation of PANI by using nitric acid as a dopant.

3.1.3.FTIR Analysis for PANI with Sulfuric Acid Graph 3.3. FTIR result of PANI doped with Sulfuric Acid

Sr # 1 2 3 4 5 6

Wave number(cm-1) 623.859 775.244 1144.55 1395.25 1473.35 1582.31

Functional Group Alkynes Aromatics Alkyl halide Alkanes Aromatics Aromatics

7 8 9 10

2369.12 2603.43 2884.99 3416.28

Nitrile Aldehyde Alkanes Alcohol, phenol

Table 3.3. wave number against functional group

FTIR results at wave numbers (775.244, 1473.35 and 1582.31) cm-1 prove the formation of PANI by using sulfuric acid as a dopant.

3.1.4.FTIR Analysis for PANI with Acetic Acid Graph 3.4. FTIR result of PANI doped with Acetic Acid

Sr # 1 2

Wave number(cm-1) 613.252 1014.37

Functional Group Alkyl halide Aliphatic amines

3 4 5 6 7 8 9

1118.51 1197.58 1400.07 1644.98 2364.3 3448.1 3739.3

Aliphatic amines Aliphatic amines Aromatics Alkanes Nitrile Alcohol, phenol Alcohol, phenol

Table 3.4. wave number against functional group

FTIR results at wave numbers 1400.07cm-1 prove the formation of PANI by using acetic acid as a dopant.

3.1.5.FTIR Analysis for PANI with Methacrylic Acid Graph 3.5. FTIR result of PANI doped with Methacrylic Acid

Sr #

Wave number(cm-1)

Functional Group

1 2 3 4 5 6 7 8 9 10

629.644 780.065 931.45 1124.3 1191.79 1280.5 1389.46 1624.73 2926.45 3234.04

Alkyl halide(C-Br stretch) Aromatics Carboxylic acid Aliphatic amines(C-N stretch) Aliphatic amines(C-N stretch) Aromatic amines(C-N stretch) Alkanes Primary amines Alkanes Carboxylic acid

Table 3.5. wave number against functional group

FTIR results at wave numbers (780.065 and 1280.5) cm-1 prove the formation of PANI by using methacrylic acid as a dopant.

3.1.6.FTIR Analysis for PANI with Silisic Acid Graph 3.6. FTIR result of PANI doped with Silisic Acid

Sr # 1 2 3 4 5 6 7 8 9 10

Wave number(cm-1) 660.5 764.637 894.809 1030.70 1243.86 1306.54 1452.14 2864.74 3239.82 3749.90

Functional Group Alkynes Aromatics + alkyl halide Primary amines Aliphatic amines Aliphatic amines Alcohols Aromatics Alkanes Alcohols, phenols Alcohols, phenols

Table 3.6. wave number against functional group

FTIR results at wave numbers (764.637 and 1452.14) cm-1 prove the formation of PANI by using Silisic acid as a dopant.

3.2. Thermal Analysis of PANI 3.2.0.DSC Analysis for Transition Temperatures of PANI Figure presents the DSC plot of doped PANI sample doped with HCl. Sample shows two endothermic peaks one at around 100-150C and another at around 200-350C. The first endothermic peak may be due to the loss of the loosely associated moisture and the second for the loss of relatively strongly bonded water molecules often termed as bound water, which acts as a secondary dopant. The result reflects that in presence of aromatic dopants, bond formation of water molecules with the backbone nitrogen of the polymers is much less when compared with those of inorganic or aliphatic dopants. This may due to the bulky size of the aromatic dopants(benzene ring), which prevents the bond formation of water molecules with the backbone nitrogen present on the polymer.

Graph 3.7. DSC result of pure PANI doped with HCl

3.2.1.DSC analysis of PANI with hydrochloric Acid

DSC mW 0.00

-10.00

-20.00 0.00

0 238.67x10 C

100.00 T emp[C]

200.00

Graph 3.8. DSC result of PANI doped with Nitric Acid DSC result of PANI doped with HCl reveals that there are some small endothermic peaks at temperatures about 140C and 215C. The first endothermic peak may be due to the loss of the loosely associated moisture and the second for the loss of relatively strongly bonded water molecules which acts as a secondary dopant. There is no exothermic peak present here means crystallization effect is very less. There is another sharp peak at extreme lower right corner represents melting temperature Tm i.e. 238.87C.

3.2.2.DSC analysis of PANI with Sulfuric Acid

DSC mW 0.00

-10.00

-20.00

0 247.59x10 C

100.0 0 T e m p[C]

20 0.00

Graph 3.8. DSC result of PANI doped with Sulfuric Acid DSC result of PANI doped with sulfuric acid reveals that there are some small endothermic peaks at temperatures about 85C and 140C. The first endothermic peak may be due to the loss of the loosely associated moisture and the second for the loss of relatively strongly bonded water molecules which acts as a secondary dopant. There is no exothermic peak present here means crystallization effect is very less. There is another sharp peak at extreme lower right corner represents melting temperature Tm i.e. 247.59C

3.2.3.DSC analysis of PANI with Nitric Acid

DSC mW 0.00

-5.00

-10.00

-15.00

0 238.21x10 C

0.00

100.00 Te m p[C]

200.00

Graph 3.9. DSC result of PANI doped with Nitric Acid DSC result of PANI doped with nitric acid reveals that there are some small endothermic peaks at temperatures about 95C and 135C. The first endothermic peak may be due to the loss of the loosely associated moisture and the second for the loss of relatively strongly bonded water molecules which acts as a secondary dopant. There is a small exothermic peak present at 180185C which shows some extent of crystallization. There is another sharp peak at extreme lower right corner represents melting temperature Tm i.e. 238.2C.

3.2.4.DSC analysis of PANI with Acetic Acid

DSC mW 0 .0 0

-1 0 .0 0

-2 0 .0 0

0 240.18x10 C

0 .0 0

1 0 0 .0 0 T e m p C] [

2 0 0 .0 0

Graph 3.10. DSC result of PANI doped with Acetic Acid DSC result of PANI doped with acetic acid reveals that there are some small endothermic peaks at temperatures about 120C and 195C. The first endothermic peak may be due to the loss of the loosely associated moisture and the second for the loss of relatively strongly bonded water molecules which acts as a secondary dopant. There is no exothermic peak present here means crystallization effect is very less. There is another sharp peak at extreme lower right corner represents melting temperature Tm i.e. 240.18C.

3.2.5.DSC analysis of PANI with Acetic Acid

DSC mW 0.00

-5.00

-10.00

169.47 0 C x10

0.00

50.00

100.00 Temp [C]

150.00

Graph 3.11. DSC result of PANI doped with HCl DSC result of PANI doped with acetic acid reveals that there are some small endothermic peaks at temperatures about 100C and 160C. The first endothermic peak may be due to the loss of the loosely associated moisture and the second for the loss of relatively strongly bonded water molecules which acts as a secondary dopant. There is no exothermic peak present here means crystallization effect is very less. There is another sharp peak at extreme lower right corner represents melting temperature Tm i.e. 169.47C

3.2.6.DSC analysis of PANI with Methacrylic Acid

DSC mW 0 .0 0

-1 0 .0 0

-2 0 .0 0

0 247.59x10 C

1 0 0 .0 0 T e m p C] [

2 0 0 .0 0

Graph 3.12. DSC result of PANI doped with Methacrylic Acid DSC result of PANI doped with Silisic acid reveals that there are some small endothermic peaks at temperatures about 90C and 120C. The first endothermic peak may be due to the loss of the loosely associated moisture and the second for the loss of relatively strongly bonded water molecules which acts as a secondary dopant. There is no exothermic peak present here means crystallization effect is very less. There is another sharp peak at extreme lower right corner represents melting temperature Tm i.e. 247.5C 3.3. Solubility Analysis of PANI We checked the solubility of all samples of PANI doped with different organic and inorganic acids. We found that all samples are soluble except HCl doped sample in various solvents given

below. The solubility increases with an increase in Temperature. The PANI can be recovered by evaporating the solvents. I. Ethyl alcohol II. Acetone 3.4.Electrical Characterization of PANI
3.4.1.Conductivity

The conductivity of samples of PANI is measured by Four-Probe instrument which gave the values of voltage corresponding to the current passed through the samples. The samples for this test must have diameter above 8.4mm. For the safe ends, we prepared the samples having diameter 14mm each. By using the equipment mentioned above, we collected the current-voltage values. Then measured the thickness of the pellets and spacing between two probes because t/s defines the applicability of certain equation for calculating the resistivity, the reciprocal of Conductivity, where d/s suggests the thickness correction factor, multiplied by the answer of resistivity. Diameter of the sample, d= 14mm Thickness of the sample, t= (2-5) mm Spacing between 2 probes, s= 0.28mm Since d/s= 14/2.8= 5.0 So the correction factor a is 0.7419 Equation for resistivity of Samples is given as;
=2as(V/I)

Where = resistivity (cm). Current and voltage, V & I are the average values of n=100, V and I values. By using the above mentioned equation, we calculated the Conductivity of PANI samples which are listed below. Serial # 1 2 3 4 PANI with respective Acid Hydrochloric acid Sulfuric Acid Nitric Acid Acetic Acid Conductivity (cm)-1 4.98*10-4 9.27*10-3 5.31*10-4 7.78*10-5

5 6

Methacrylic Acid Formic Acid

7.37*10-5 1.05*10-12

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