Thermal characterization of doped polyaniline and its composites with CoPc

Thermal diffusivity of the composites of camphor sulphonic acid (CSA) doped polyaniline (PANI) and its composites with cobalt phthalocyanine (CoPc) has been measured using open cell photoacoustic technique. Analysis of the data shows that the effective thermal diffusivity value can be tuned by varying the relative volume fraction of the constituents. It is seen that polaron assisted heat transfer mechanism is dominant in CSA doped PANI and these composites exhibit a thermal diffusivity value which is intermediate to that of CSA doped PANI and CoPc. The results obtained are correlated with the electrical conductivity and hardness measurements carried out on the samples.

Photothermal Investigations on certain Organic Molecules and their Plasma polymerized thin Films

Department of Physics, Cochin University of Science and Technology

Laser Induced Photothermal Investigations on Thermal and Transport Properties of Certain Selected Photonic Materials

Discovery of coherent optical sources four decades ago has revolutionized all fields of scientific development. One of the path breaking applications of lasers is the emergence of various thermo optic techniques to unravel some of the mysteries of light matter interactions.Thermo optic technique is a valuable tool to evaluate optical and thermal properties of materials in solid,liquid and gaseous states .This technique can also be employed effectively in nondestructive quality evaluation. In this doctoral thesis , the use of photothermal techniques based on photoacoustic and photothermal deflection phenomena for the study of certain class of photonics materials such as semiconductors, nano metal dispersed ceramics, composites of conducting polymers and liquid crystals is elaborated.

Studies on Electrical and Thermal Properties of Certain Selected Photonic Materials

The present thesis is centered around the study of electrical and thermal properties of certain selected photonic materials.We have studied the electrical conduction mechanism in various phases of certain selected photonic materials and those associated with different phase transitions occurring in them. A phase transition leaves its own impressions on the key parameters like electrical conductivity and dielectric constant. However, the activation energy calculation reveals the dominant factor responsible for conduction process.PA measurements of thermal diffusivity in certain other important photonic materials are included in the remaining part of the research work presented in this thesis. PA technique is a promising tool for studying thermal diffusivities of solid samples in any form. Because of its crucial role and common occurrence in heat flow problems, the thermal diffusivity determination is often necessary and knowledge of thermal diffusivity can intum be used to calculate the thermal conductivity. Especially,knowledge of the thermal diffusivity of semiconductors is important due to its relation to the power dissipation problem in microelectronic and optoelectronic devices which limits their performances. More than that, the thermal properties, especially those of thin films are of growing interest in microelectronics and microsystems because of the heat removal problem involved in highly integrated devices. The prescribed chapter of the present theis demonstrates how direct measurement of thermal diffusivity can be carried out in thin films of interest in a simple and elegant manner using PA techniques. Although results of only representative measurements viz; thermal diffusivity values in Indium, Aluminium, Silver and CdS thin films are given here, evaluation of this quantity for any photonic and / electronic material can be carried out using this technique in a very simple and straight forward manner.

Photothermal Investigations on Certain Plasma Polymerized Thin Films and Near IR Overtone Studies of Some Organic Molecules

Photothermal effect refers to heating of a sample due to the absorption of electromagnetic radiation. Photothermal (PT) heat generation which is an example of energy conversion has in general three kinds of applications. 1. PT material probing 2. PT material processing and 3. PT material destruction. The temperatures involved increases from 1-. 3. Of the above three, PT material probing is the most important in making significant contribution to the field of science and technology. Photothermal material characterization relies on high sensitivity detection techniques to monitor the effects caused by PT material heating of a sample. Photothermal method is a powerful high sensitivity non-contact tool used for non-destructive thermal characterization of materials. The high sensitivity of the photothermal methods has led to its application for analysis of low absorbance samples. Laser calorimetry, photothermal radiometry, pyroelectric technique, photoacoustic technique, photothermal beam deflection technique, etc. come under the broad class ofphotothermal techniques. However the choice of a suitable technique depends upon the nature of the sample, purpose of measurement, nature of light source used, etc. The present investigations are done on polymer thin films employing photothermal beam deflection technique, for the successful determination of their thermal diffusivity. Here the sample is excited by a He-Ne laser (A = 6328...\ ) which acts as the pump beam. Due to the refractive index gradient established in the sample surface and in the adjacent coupling medium, another optical beam called probe beam (diode laser, A= 6500A ) when passed through this region experiences a deflection and is detected using a position sensitive detector and its output is fed to a lock-in amplifier from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the signal is suitably analysed for determining the thermal diffusivity.The production of polymer thin film samples has gained considerable attention for the past few years. Plasma polymerization is an inexpensive tool for fabricating organic thin films. It refers to formation of polymeric materials under the influence of plasma, which is generated by some kind of electric discharge. Here plasma of the monomer vapour is generated by employing radio frequency (MHz) techniques. Plasma polymerization technique results in homogeneous, highly adhesive, thermally stable, pinhole free, dielectric, highly branched and cross-linked polymer films. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer.Near IR overtone investigations on some organic molecules using local mode model are also done. Higher vibrational overtones often provide spectral simplification and greater resolution of peaks corresponding to nonequivalent X-H bonds where X is typically C, N or O. Vibrational overtone spectroscopy of molecules containing X-H oscillators is now a well established tool for molecular investigations. Conformational and steric differences between bonds and structural inequivalence ofCH bonds (methyl, aryl, acetylenic, etc.) are resolvable in the higher overtone spectra. The local mode model in which the X-H oscillators are considered to be loosely coupled anharmonic oscillators has been widely used for the interpretation of overtone spectra. If we are exciting a single local oscillator from the vibrational ground state to the vibrational state v, then the transition energy of the local mode overtone is given by .:lE a......v = A v + B v2 • A plot of .:lE / v versus v will yield A, the local mode frequency as the intercept and B, the local mode diagonal anharmonicity as the slope. Here A - B gives the mechanical frequency XI of the oscillator and B = X2 is the anharmonicity of the bond. The local mode parameters XI and X2 vary for non-equivalent X-H bonds and are sensitive to the inter and intra molecular environment of the X-H oscillator.

Design and fabrication of a photothermal spectrometer and investigations of multilayer thin films"

In this work we present the results of our attempt to build a compact photothermal spectrometer capable of both manual and automated mode of operation.The salient features of the system include the ability to analyse thin film, powder and polymer samples. The tool has been in use to investigate thermal, optical and transport properties. Binary and ternary semiconducting thin films were analysed for their thermal diffusivities. The system could perform thickness measurements nondestructively. Ion implanted semiconductors are widely studied for the effect of radiation induced defects. We could perform nondestructive imaging of defects using our spectrometer.The results reported in his thesis on the above in addition to studies on In2S3 and transparent conducting oxide ZnO have been achieved with this spectrometer. Various polymer samples have been easily analysed for their thermal diffusivities. The technique provided ease of analysis not achieved with conventional techniques like TGA and DSC. Industrial application of the tool has also been proved by analyzing defects of welded joints and adhesion of paints. Indigenization of the expensive lock-in-amplifier and automation has been the significant achievement in the course of this dissertation. We are on our way to prove the noise rejection capabilities of our PC LIA.

Thermal characterization of nanocrystalline porous CePO4 ceramics

A laser-induced photoacoustic technique was employed to investigate thermal transport through nanocrystalline CePO4 samples prepared via the sol–gel route. Evaluation of thermal diffusivity was carried out using the one-dimensional model of Rosencwaig and Gersho for the reflection configuration of the photoacoustic method. Structural analyses of samples revealed that they are nanoporous in nature, possessing micron-sized grains. Analysis of results shows that thermal diffusivity value varies with sintering temperature. Results are explained in terms of the variation in porosity with sintering temperature and the effects of various scattering mechanisms on the propagation of phonons through the nanoporous ceramic matrix. Further analyses confirm that apart from porosity, grain boundary resistance and interface thermal resistance influence the effective value of thermal diffusivity of the samples under investigation.

Lithium Containing Complex Metal Oxides and Metal phosphates:Investigations on their synthesis and various characterizations for rechargeable lithium battery applications

The work presented in the thesis is centered around two important types of cathode materials, the spinel structured LixMn204 (x =0.8to1.2) and the phospho -oIivine structured LiMP04 (M=Fe and Ni). The spinel system LixMn204, especially LiMn204 corresponding to x= 1 has been extensively investigated to understand its structural electrical and electrochemical properties and to analyse its suitability as a cathode material in rechargeable lithium batteries. However there is no reported work on the thermal and optical properties of this important cathode material. Thermal diffusivity is an important parameter as far as the operation of a rechargeable battery is concerned. In LixMn204, the electronic structure and phenomenon of Jahn-Teller distortion have already been established theoretically and experimentally. Part of the present work is an attempt to use the non-destructive technique (NDT) of photoacoustic spectroscopy to investigate the nature of the various electronic transitions and to unravel the mechanisms leading to the phenomenon of J.T distortion in LixMn204.The phospho-olivines LiMP04 (M=Fe, Ni, Mn, Co etc) are the newly identified, prospective cathode materials offering extremely high stability, quite high theoretical specific capacity, very good cycIability and long life. Inspite of all these advantages, most of the phospho - olivines especially LiFeP04 and LiNiP04 show poor electronic conductivity compared to LixMn204, leading to low rate capacity and energy density. In the present work attempts have been made to improve the electronic conductivity of LiFeP04 and LiNiP04 by adding different weight percentage MWNT .It is expected that the addition of MWNT will enhance the electronic conductivity of LiFeP04 and LiNiP04 with out causing any significant structural distortions, which is important in the working of the lithium ion battery.

Thermal transport properties of selected ferroelectrics, mixed valance perovskites and dielectric ceramics using photopyroelectric technique

Photothermal spectroscopy is a group of high sensitivity methods used to measure optical absorption and thermal characteristics of a sample.The basis of photothermal spectroscopy is a photo-induced change in the thermal state of the sample.Light energy absorbed and not lost by subsequent emission results in sample heating.This heating results in a temperature change as well as changes in thermodynamic parameters of the sample which are related to temperature.Measurements of the temperature,pressure,or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic methods.This is a more direct measure of optical absorption than optical transmission based spectroscopies.Sample heating is a direct consequence of optical absorption and so photothermal spectroscopy signals are directly dependent on light absorption.Scattering and reflection losses do not produce photothermal signals.Subsequently,photothermal spectroscopy more accurately measures optical absorption in scattering solutions,in solids,and at interfaces.This aspect makes it particularly attractive for application to surface and solid absorption studies,and studies in scattering media.

Studies on ASE, Lasing and NLO characteristics in Certain Laser Dyes

Observing the wide possibilities of fluorescent dyes, an exhaustive investigation is done in laser dyes mainly focusing on Coumarin 540 which has a very strong emission in the green region. The photophysics of the dye is studied in detail in a good number of solvent environments. The results of the amplified spontaneous emission and lasing behaviour in both dye solution and different polymer solid state matrices and the ptotostability of the these matrices are investigated using the photoacoustic technique and the same are also included in this thesis. The energy transfer behaviour in dye mixtures which could be utilized for laser studies and bio-analysis are also presented. The nonlinear characterization of Coumarin540 forms the last part of the experimental investigations presented in the thesis.

" Studies on Laser induced Phatothermal Phenomena in Selected Organic Compounds and Fullerenes"

In the pre—laser era it was difficult to believe that the optical properties of a medium depend upon the intensity of the radiation incident on it. The basis for this conclusion is that the electric field strength associated with the conventional light sources used before the advent of lasers was much smaller than (103 V/cm) the field sttrengths of atomic or interatomic fields (2 107 —- 10” V/cm). The radiation with such low intensity is not able to affect atomic fields to the extent of changing optical parameters. The invention of laser in 1960 was a turning point. The high degree of coherence of the laser radiation provides high spatial concentration of optical power. With the availability of the femtosecond lasers it has become possible to get extremely high peak powers 2 1013 W/cmz). At such high fields, the relationship between electric ‘polarization P and the electric field strength E ceases to be linear and several nonlinear effects begin to occur. Nonlinear absorption, a branch of nonlinear optics, refers to the interaction between radiation and matter accompanied by absorption of more than one photon. Nonlinear absorption has acquired great importance after the invention of high power lasers. One of the objectives of the present work is to investigate the nonlinear absorption processes occurring in fullerene, selected organic solvents and laser dyes. Fullerenes and laser dyes were chosen because of their highly nonlinear behaviour. Fullerenes, the most beautiful among molecules, offer fascinating field of research owinglto their significant structural properties. As toluene, benzene and carbon disulphide are themost widely used solvents for fullerenes, it seems important to study the nonlinear properties of these liquids as well. Like fullerenes, laser dyes also possess highly delocalized 7r electrons which are responsible for their nonlinear absorption. Dye lasers were the fulfillment of an experimenter’s pipe dream - to have a laser that is easily tunable over a wide range of wavelengths. A better understandingof the photophysical properties of laser dyes can significantly enhance the development and technology of dye lasers. We studied the nonlinear absorption properties of two rhodamine dyes to have some insight into their nonlinear optical properties.