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.

Fabrication of Potentiometric Sensors for the Determination of Lanthanide Ions

In many fields such as earth science biology, environment and electronics, the knowledge about elemental distributions and chemical speciation is important. The determination of metal levels especially the toxic ones both in the environment and in biological materials are increasingly demanded by the society.Ion selective sensors have become one of the most effective ad powerful means for analytical scientists for the trace level monitoring of metal ions. The wide range of applications ,low material requirements and simplicity of analytical procedure have not only brought ion-selective electrodes in to the lime light of analytical chemistry,but have promoted their use as tools for physiologists,medical researchers,biologists,geologists,environmental protection specialists etc.Potentiometric ion-selective sensors have been developed for the determination of lanthanide ions such as La3+,Nd3+,Pr3+,Sm3+, and Gd3+.The sensors fabricated include both PVC membrane sensor and chemically modified carbon paste sensor. A set of 10 sensors have been developed. The response parameters of all the sensors have been studied and the sensors were applied as an indicator electrode in the potentiometric titration and for the determination of metal ions in real samples.

Catalysis by Transition Metal Modified Ceria and Ceria-Zirconia Mixed Oxides Prepared via Sol-Gel Route

The aim of catalysis research is to apply the catalyst successfully in economically important reactions in an environmentally friendly way. The present work focuses on the modification of structural and surface properties of ceria and ceria-zirconia catalysts by the incorporation of transition metals. The applications of these catalysts in industrially important reactions like ethylbenzene oxidation, alkylation of aromatics are also investigated.Sol-gel method is effective for the preparation of transition metal modified ceria and ceria-zirconia mixed oxide since it produces catalyst with highly dispersed incorporated metal. Unlike that of impregnation method plugging of pores is not prominent for sol-gel derived catalyst materials. This prevents loss of surface area on metal modification as evident for BET surface area measurements.The powder X-ray diffraction analysis confirms the cubic structure of transition metal modified ceria and ceria-zirconia catalysts. The thermal stability is evident from TGA/DTA analysis. DR UV-vis spectra provide information on the coordination environment of the incorporated metal. EPR analysis ofCr, Mn and Cu modified ceria and a ceria-zirconia catalyst reveals the presence of different oxidation states of incorporated metal.Temperature programmed desorption of ammonia and thermogravimetric desorption of 2,6-dimethyl pyridine confirms the enhancement of acidity on metal incorporation. High a-methyl styrene selectivity in cumene cracking reaction implies the presence of comparatively more number of Lewis acid sites with some amount of Bronsted acid sites. The formation of cyclohexanone during cyclohexanol decomposition confirms the presence of basic sites on the catalyst surface.Mn and Cr modified catalysts show better activity towards ethylbenzene oxidation. A redox mechanism through oxometal pathway is suggested.All the catalysts were found to be active towards benzylation of toluene and a-xylene. The selectivity towards monoalkylated products remains almost 100%. The catalytic activity is correlated with the Lewis acidity of the prepared systems.The activity of the catalysts towards methylation of phenols depends on the strength acid sites as well as the redox properties of the catalysts. A strong dependence of methylation activity on the total acidity is illustrated.

Vanadia Supported on Rice Husk Silica Promoted Rare Earth Oxides

The selective oxidation of alkylaromatics is one of the main processes since the reaction products are important as intermediates in numerous industrial organic chemicals. Side-chain oxidation of alkyl aromatic compounds catalyzed by heterogeneous catalysts using cleaner peroxide oxidants is an especially attractive goal since classical synthetic laboratory procedures preferably use permanganate or acid dichromate as stoichiometric oxidants. In spite of many studies, there are very few which use hydrogen peroxide as a source of oxygen in the C-H activation of alkanes. Eflective utilization of ethylbenzene, available in the xylene stream of the petrochemical industry to more value added products is a promising one in chemical industry. The oxidation products of ethylbenzene are widely employed as intermediates in organic, steroid and resin synthesis.

Surface electron properties and catalytic activity of rare earth oxides

The rare earths have provided fascinating field for chemists confronted with problems of their separation and purification. The rare earths become available in relatively pure form in recent years due to the development of efficient separation methods, largely as a byproduct of the atomic energy programmes of various countries. The rare earths often called lanthanides from La (Z=57) to Lu (Z=7l) display subtle variation of properties through the series, while the differences become appreciable for the elements that are farther apart.

Studies on the catalysis by sulfated mixed oxides of tin with some rare earth elements

A comparative study of acid-base properties and catalytic activity of Sn-La and Sn-Sm mixed oxides and their corresponding sulfate modified analogues are reported in this thesis. The catalytic activity and product selectivity in the decomposition of alcohols are correlated with the acid-base and redox properties of the catalyst systems under study The effect of catalyst preparation, pretreatment and various reaction parameters on the catalytic activity of sulfate modified oxides is investigated in the oxidative dehydrogenation reactions The experimental conditions are optimised to synthesise industrially important organic chemicals viz. 2,6 xylenol, o-cresol, N-methylanilne and N,N-dimethylaniline employing the mixed oxide systems. The effect of sulfate treatment on the catalytic activity of these systems in the alkylation reactions of phenol, anisole and aniline is also investigated and the merits and demerits of sulfate treatment are highlighted.

An investigation on the preparation and properties of some transparent conducting oxides and lead selenide thin films”

The investigation of physical properties of matter has progressed so much during the last hundred years. Today physics is divided in to a large distinct group of special branches. These branches are distinguished by the particular area studied, method of investigation and so on. An independent and important branch that has developed is the physics ofthin films.Any object in solid or liquid form with one of its dimensions very much smaller than that of the other two may be called a thin film. It is having only one common property, namely, one of their dimensions is very small, though all their physical properties may be different. Thin layers of oil, floating on the surface of water, with their fascinating colours, have attracted men’s curiosity from time immemorial. The earliest application of thin films was the protective coatings in the form of paints. A thin layer of tin has been used from ancient times to protect copper utensils from corrosion. Indium thin films are used in certain applications on account of their good lubricating property. Relay contacts are coated with thin films of rare earth metals in order to prevent burning due to arcing. Hard coatings are also available using diamond like carbon (i-carbon). The basic properties of thin films are of considerable interest because of their potential applications in various fields of science and technology

Development of p-type transparent semiconducting oxides for thin film transistor applications

Semiconductor physics has developed significantly in the field of re- search and industry in the past few decades due to it’s numerous practical applications. One of the relevant fields of current interest in material science is the fundamental aspects and applications of semi- conducting transparent thin films. Transparent conductors show the properties of transparency and conductivity simultaneously. As far as the band structure is concerned, the combination of the these two properties in the same material is contradictory. Generally a trans- parent material is an insulator having completely filled valence and empty conduction bands. Metallic conductivity come out when the Fermi level lies within a band with a large density of states to provide high carrier concentration. Effective transparent conductors must nec- essarily represent a compromise between a better transmission within the visible spectral range and a controlled but useful electrical con- ductivity [1–6]. Generally oxides like In2O3, SnO2, ZnO, CdO etc, show such a combination. These materials without any doping are insulators with optical band gap of about 3 eV. To become a trans- parent conductor, these materials must be degenerately doped to lift the Fermi level up into the conduction band. Degenerate doping pro- vides high mobility of extra carriers and low optical absorption. The increase in conductivity involves an increase in either carrier concen- tration or mobility. Increase in carrier concentration will enhance the absorption in the visible region while increase in mobility has no re- verse effect on optical properties. Therefore the focus of research for new transparent conducting oxide (TCO) materials is on developing materials with higher carrier mobilities.

Contact potential induced enhancement of magnetization in polyaniline coated nanomagnetic iron oxides by plasma polymerization

The present work derives motivation from the so called surface/interfacial magnetism in core shell structures and commercial samples of Fe3O4 and c Fe2O3 with sizes ranging from 20 to 30 nm were coated with polyaniline using plasma polymerization and studied. The High Resolution Transmission Electron Microscopy images indicate a core shell structure after polyaniline coating and exhibited an increase in saturation magnetization by 2 emu/g. For confirmation, plasma polymerization was performed on maghemite nanoparticles which also exhibited an increase in saturation magnetization. This enhanced magnetization is rather surprising and the reason is found to be an interfacial phenomenon resulting from a contact potential.

SOL-GEL Lanthanum Phosphate, Composite and coating for functional Applications.

Lanthanum phosphate is one among the lanthanide family of “Rare Earths” following the periodic table of elements. Known under the generic name, Monazite, the rare earth phosphates have melting points above 1900 °C, high thermal phase stability, low thermal conductivity and thermal expansion coefficient similar to some of the high temperature oxides like alumina and zirconia.

Microwave Plasma Assisted ALD Development for the Deposition of Gate Oxides & ALD of High-k Dielectrics

The semiconductor industry's urge towards faster, smaller and cheaper integrated circuits has lead the industry to smaller node devices. The integrated circuits that are now under volume production belong to 22 nm and 14 nm technology nodes. In 2007 the 45 nm technology came with the revolutionary high- /metal gate structure. 22 nm technology utilizes fully depleted tri-gate transistor structure. The 14 nm technology is a continuation of the 22 nm technology. Intel is using second generation tri-gate technology in 14 nm devices. After 14 nm, the semiconductor industry is expected to continue the scaling with 10 nm devices followed by 7 nm. Recently, IBM has announced successful production of 7 nm node test chips. This is the fashion how nanoelectronics industry is proceeding with its scaling trend. For the present node of technologies selective deposition and selective removal of the materials are required. Atomic layer deposition and the atomic layer etching are the respective techniques used for selective deposition and selective removal. Atomic layer deposition still remains as a futuristic manufacturing approach that deposits materials and lms in exact places. In addition to the nano/microelectronics industry, ALD is also widening its application areas and acceptance. The usage of ALD equipments in industry exhibits a diversi cation trend. With this trend, large area, batch processing, particle ALD and plasma enhanced like ALD equipments are becoming prominent in industrial applications. In this work, the development of an atomic layer deposition tool with microwave plasma capability is described, which is a ordable even for lightly funded research labs.