Chapter 2 Review of Related Literature

2.1 Conducting polymers Polymers were considered organic compounds that are good insulators until the emergence of conducting polymers. Intrinsically conducting polymers has conjugated polymers that cause electron delocalization in the backbone of the polymer. These polymers show tunable conductivity and low cost fabrication. The conjugation of pi-bond in the backbone of these polymers results in the delocalization of electrons which is the reason for its conductivity. Doping a conducting polymer relatively increases its conductivity by a magnitude of ten (10). Protonating by introduction of acidic media is one way to dope a conducting polymer. 2.2 Polyaniline

Figure 1 Chemical Structure of PAni

Polyaniline (PAni), shown in figure 1, is one of the most environmentally stable conducting polymers, thus along its straight forward synthesis makes it one of the most studied conducting polymer. PANI is cheap in fabrication and shows facile acid-base doping/de-doping chemistry. PAni chains are product of the polymerization of aniline, a derivative of benzene. There are three oxidation states of PAni namely: (1) leucoemeraldine, (2) pernigraniline, and (3) emeraldine. These states, shown in figure 2, simply differ in the ratio of the structural units found in the PAni namely: quinoid and benzenoid.

Figure 2 The threeoxidation states of PAni: (a) fully reduced leucoemeraldine base (LEB); (b) a fully oxidized pernigraniline base (PNB); and (c) a half oxidized/half reduced emeraldine base (EB) state

These two units can be transformed into each other by reduction-oxidation process. PAni is a special conducting polymer since its doped state can be controlled by acid/base reactions. Not all types of doped PAni are electrically conductive. The conductive state of PAni is the protonated form of the emeraldine base (benzenoid:quinoid = 3:1), shown in figure 3 . Counter ions which are products of protonic acid doping of PAni maintains the charge of the polymer neutral. Doped PAni has shown potential application as ammonia sensors. 2.3 Doping of PAni Doping is a process of introduction of impurities in the light of altering the properties of a substance. Doping and de-doping of PAni is reversible. The p-type doping is the common method to dope a PAni. There are two types of p-type doping namely: protonic acid doping and oxidative doping. Protonic acid doping to PAni emeraldine base form involves a donator of proton, usually HCL acid, in which these

proton bonds covalently to the imine nitrogen of the quinoid rings: converting it into benzenoid rings forming the PAni emeraldine salt form.

Figure 3 Change in the polymers backbone upon dedoping the emeraldine salt form of PAni to its emeraldine base form.

2.4 Scanning Electron Microscopy Scanning Electron Microscopy (SEM) is an imaging technique that has high magnification and smooth imaging by collecting the secondary and backscattered electrons generated when an electron beam hits a specimen. These collected electrons will be use to produce the micrographs. Reflected high energy electrons originating in the electron beam upon interaction with the specimen are called backscattered electrons which are higher in energy than the secondary electrons. They are responsible for the determination of the higher atomic number atoms in the specimen. Secondary electrons are those electrons that escape the surface of the sample after it being excited by the electron beam enough to escape the surface of the specimen. Factors for the number of

secondary electron yield includes: high atomic number targets, high angles of incidence, and topography of the sample. Due to the low energy of secondary electrons, 5eV, examined secondary electrons are produced from the surface <10 nm depth.

2.5 Fourier Transform Infrared Spectroscopy Fourier Transform - Infrared spectroscopy (FT-IR) is a spectroscopic technique involving the use of light in the infrared regions to cause molecular vibrations in the target material. This technique involves the use of Fourier Transform to convert the mathematical function of time as a function of frequency. Chemically bounded compounds have natural frequencies of the infrared region. These compounds resonate upon absorption of infrared lights. The waves are electromagnetic in nature and interact with the polarity of the chemical bonds of the molecules. If there is no polarity (dipole moment) in the molecule then the infrared interaction is inactive and the molecule does not produce any IR spectrum. This technique is based mainly in the absorption spectra transmitted by a sample after absorbing some of the frequencies in the infrared region. 2.6 UV-visible spectroscopy UV-visible spectroscopy is the study of the interaction of matter with light radiation of wavelength from 200nm to 700nm. Matter was radiated with ultraviolet light rays and visible light rays upon which were allowed to be absorbed for electronic transition. Electronic transition occurs if the energy of the photon absorbed equals the energy required for the electronic excitation of the valence electrons (outermost electron of an atom). Absorption spectrum is a non-continuous spectra coming from

an object in which the missing wavelength(s) were absorbed by the same object. UV-vis spectrometer measures the amount of percent transmitted wavelength converting it to absorbance and plot it against the wavelength. A UV-vis spectrometer determines the absorbance by comparing the intensity of light in the sample and the intensity of light transmitted by the sample.

Reynan L. Toledo MS Physics 1