INVESTIGATIONS ON THE SOLVENT EXTRACTION AND LUMINESCENCE OF LANTHANOIDS WITH MIXTURES OF HETEROCYCLIC β- DIKETONE S AND VARIOUS NEUTRAL OXO-DONORS

The thesis entitled “ Investigations on the solvent extraction and luminescence of lanthanoids with mixtures of heterocyclic β-diketone S and various neutral oxo-donors” embodies the results of investigations carried out on the solvent extraction of trivalent lanthanoids with various heterocyclic β-diketones in the presence and absence of neutral oxo-donors and also on the luminescent studies of Eu3+-heterocyclic β-diketonate complexes with Lewis bases. The primary objective of the present work is to generate the knowledge base, especially to understand the interactions of lanthanoid-heterocyclic β-diketonates with various macrocyclic ligands such as crown ethers and neutral organophosphorus extractants , with a view to achieve better selectivity. The secondary objective of this thesis is to develop novel lanthanoid luminescent materials based on 3-phenyl-4-aroyl-5-isoxazolones and organophosphorus ligands, for use in electroluminescent devices. In the beginning it describes the need for the development of new mixed-ligand systems for the separation of lanthanoids and the development and importance of novel luminescent lanthanoid- β-diketonate complexes for display devices. The syntheses of various para substituted derivatives of 4-aroyl-5-isoxazolones and their characterization by various spectroscopic techniques are described. It also investigate the solvent extraction behaviour of trivalent lanthanoids with 4-aroyl-5-isoxazolones in the presence and absence of various crown ethers such as 18C6, DC18C6, DB18C6 and B18C6. Elemental analysis, IR and H NMR spectral studies are used to understand the interactions of crown ethers with 4-aroyl-5-isoxazolonate complexes of lanthanoids. The synergistic extraction of trivalent lanthanoids with sterically hindered 1-phenyl-3-methyl-4-pivaloyl-5-pyrazolone in the presence of various structurally related crown ethers are studied. The syntheses, characterization and photyphysical properties of Eu3+-4-aroyl-5-isoxazolonate complexes in the presence of Lewis bases like trictylphosphine oxide or triphenylphosphine oxide were studied.

Growth and Characterisation of Radio Frequency Magnetron Sputttered Indium Tin Oxide Thin Films

The increasing interest in the interaction of light with electricity and electronically active materials made the materials and techniques for producing semitransparent electrically conducting films particularly attractive. Transparent conductors have found major applications in a number of electronic and optoelectronic devices including resistors, transparent heating elements, antistatic and electromagnetic shield coatings, transparent electrode for solar cells, antireflection coatings, heat reflecting mirrors in glass windows and many other. Tin doped indium oxide (indium tin oxide or ITO) is one of the most commonly used transparent conducting oxides. At present and likely well into the future this material offers best available performance in terms of conductivity and transmittivity combined with excellent environmental stability, reproducibility and good surface morphology. Although partial transparency, with a reduction in conductivity, can be obtained for very thin metallic films, high transparency and simultaneously high conductivity cannot be attained in intrinsic stoichiometric materials. The only way this can be achieved is by creating electron degeneracy in a wide bandgap (Eg > 3eV or more for visible radiation) material by controllably introducing non-stoichiometry and/or appropriate dopants. These conditions can be conveniently met for ITO as well as a number of other materials like Zinc oxide, Cadmium oxide etc. ITO shows interesting and technologically important combination of properties viz high luminous transmittance, high IR reflectance, good electrical conductivity, excellent substrate adherence and chemical inertness. ITO is a key part of solar cells, window coatings, energy efficient buildings, and flat panel displays. In solar cells, ITO can be the transparent, conducting top layer that lets light into the cell to shine the junction and lets electricity flow out. Improving the ITO layer can help improve the solar cell efficiency. A transparent ii conducting oxide is a material with high transparency in a derived part of the spectrum and high electrical conductivity. Beyond these key properties of transparent conducting oxides (TCOs), ITO has a number of other key characteristics. The structure of ITO can be amorphous, crystalline, or mixed, depending on the deposition temperature and atmosphere. The electro-optical properties are a function of the crystallinity of the material. In general, ITO deposited at room temperature is amorphous, and ITO deposited at higher temperatures is crystalline. Depositing at high temperatures is more expensive than at room temperature, and this method may not be compatible with the underlying devices. The main objective of this thesis work is to optimise the growth conditions of Indium tin oxide thin films at low processing temperatures. The films are prepared by radio frequency magnetron sputtering under various deposition conditions. The films are also deposited on to flexible substrates by employing bias sputtering technique. The films thus grown were characterised using different tools. A powder x-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive x-ray analysis (EDX) and scanning electron microscopy (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UVVIS- NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using vander Pauw four probe technique. The plasma generated during the sputtering of the ITO target was analysed using Langmuir probe and optical emission spectral studies.

AN INVESTIGATION ON AIR-SEA INTERACTION IN THE INDIAN OCEAN DURING CONTRASTING MONSOONS

The study is undertaken with an objective to investigate the linkage between air-sea fluxes in the Indian Ocean and monsoon forcing. Since the monsoon activity is linked to fluxes, the variability of surface marine meteorological fields under the variable monsoon conditions is also studied. The very objective of the present study is to document various sea surface parameters of the Indian Ocean and to examine the anomalies found in them. Hence it is attempted to relate the anomaly to the variability of monsoon over India, highlighting the occasion of contrasting monsoon periods. The analysis of anomalies of surface meteorological fields such as SST, wind speed and direction, sea level pressure and cloud cover for contrasting monsoons are also studied. During good monsoon years, the pressure anomalies are negative indicating a fall in SLP during pre-monsoon and monsoon months. The interaction of the marine atmosphere with tropical Indian Ocean and its influence on ISMR continue to be an area of active research.

Synergistic solvent extraction of Thorium(IV) and Uranium(VI) with β-diketones in presence of oxo-donors

The thesis entitled “Synergistic solvent extraction of Thorium(IV) and Uranium(VI) with β-diketones in presence of oxo-donors” embodies the results of the investigations carried out on the extraction of thorium(IV) an uranium(VI) with heterocyclic β-diketones in the presence and absence of various macrocyclic ligands and neutral organophosphorus extractants. The objective of this work is to generate the knowledge base to achieve better selectivity between thorium(IV) and uranium(VI) by understanding the interactions of crown ethers or neutral organophosphorus extractants with metal-heterocyclic β-diketonate complexes. Para-substituted 1-phenyl-3-methyl-4-aroyl-5-pyrazolones, namely,1-phenyl-3-methyl-4-(4-fluorobenzoyl)-5-pyrazolone (HPMFBP) and 1-phenyl-3-methyl-4-(4-toluoyl)-5-pyrazolone (HPMTP) were synthesized and characterized by elemental analysis, IR and H NMR spectral data. The synthesized ligands have been utilized for the extraction of thorium(IV) and uranium(VI) from nitric acid solutions in the presence and absence of various crown ethers. Thorium(IV) and uranium(VI) complexes with HPMPP(1-Phenyl-3-methyl-4-pivaloyl-5-pyrazolone) and neutral organophosphorus extractants were synthesized and characterized by IR and P NMR spectral data to further understand the interactions of neutral organophosphorus extractants with metal-chelates. Solid complexes of thorium(IV) and uranium(VI) with para-substituted 4-aroyl-5-isoxazolones and crown ethers were isolated and characterized by various spectroscopic techniques to further clarify the nature of the extracted complexes.

Investigations on Ultrasonic Transducer Array Systems for NDE of Underwater Pipelines

The main objective of carrying out this investigation is to develop suitable transducer array systems so that underwater pipeline inspection could be carried out in a much better way, a focused beam and electronic steering can reduce inspection time as well. Better results are obtained by optimizing the array parameters. The spacing between the elements is assumed to be half the wavelength so that the interelement interaction is minimum. For NDT applications these arrays are operated at MHz range. The wavelengths become very small in these frequency ranges. Then the size of the array elements becomes very small, requiring hybrid construction techniques for their fabrication. Transducer elements have been fabricated using PVDF as the active, mild steel as the backing and conducting silver preparation as the bonding materials. The transducer is operated in the (3,3) mode. The construction of a high frequency array is comparatively complicated. The interelement spacing between the transducer elements becomes considerably small when high frequencies are considered. It becomes very difficult to construct the transducer manually. The electrode connections to the elements can produce significant loading effect. The array has to be fabricated using hybrid construction techniques. The active materials has to be deposited on a proper substrate and etching techniques are required to fabricate the array. The annular ring, annular cylindrical or other similar structural forms of arrays may also find applications in the near future in treatments were curved contours of the human body are affected.

Electrochemical Reduction and Voltammetric Determination of Metronidazole Benzoate at Modified Carbon Paste Electrode

A metalloporphyrin incorporated carbon paste sensor has been developed for the determination of metronidazole benzoate (MTZB). Zn(II) complex of 5,10,15,20-tetrakis (3-methoxy-4-hydroxy phenyl) porphyrin (TMHPP) was used as the active material. The MTZB gave a well-defined reduction peak at - 0.713V in 0.1 mol l -1 phosphate buffer solution of pH around 7. Compared with bare carbon paste electrode (CPE), the TMHPP Zn(II) modified electrode significantly enhanced the reduction peak current of MTZB as well as lowered its reduction potential. Under optimum conditions the reduction peak current was proportional to MTZB concentration over the range 1×10-3 mol1-1 to 1×10-5mol1-1. The detection limit was found to be 4.36×10-6mol1-1 . This sensor has been successfully applied for the determination of MTZB in pharmaceutical formulations and urine samples.

An Inter-digital Capacitive Electrode Modified as a Pressure Sensor

Inter-digital capacitive electrodes working as electric field sensors have been developed for touch panel applications. Evaluation circuits to convert variations in electric fields in such sensors into computer compatible data are commercially available. We report development of an Interdigital capacitive electrode working as a sensitive pressure sensor in the range 0-120 kPa. Essentially it is a touch/proximity sensor converted into a pressure sensor with a suitable elastomer buffer medium acting as the pressure transmitter. The performance of the sensor has been evaluated and reported. Such sensors can be made very economical in comparison to existing pressure sensors. Moreover, they are very convenient to be fabricated into sensor arrays involving a number of sensors for distributed pressure sensing applications such as in biomedical systems.

Studies on the Quality of Rainwater at Various Land Use Locations and Variations by Interaction with Domestic Rainwater Harvesting Systems

The present study focused on the quality of rainwater at various land use locations and its variations on interaction with various domestic rainwater harvesting systems.Sampling sites were selected based upon the land use pattern of the locations and were classified as rural, urban, industrial and sub urban. Rainwater samples were collected from the south west monsoon of May 2007 to north east monsoon of October 2008, from four sampling sites namely Kothamangalam, Emakulam, Eloor and Kalamassery, in Ernakulam district of the State of Kerala, which characterized typical rural, urban, industrial and suburban locations respectively. Rain water samples at various stages of harvesting were also collected. The samples were analyzed according to standard procedures and their physico-chemical and microbiological parameters were determined. The variations of the chemical composition of the rainwater collected were studied using statistical methods. It was observed that 17.5%, 30%, 45.8% and 12.1% of rainwater samples collected at rural, urban, industrial and suburban locations respectively had pH less than 5.6, which is considered as the pH of cloud water at equilibrium with atmospheric CO,.Nearly 46% of the rainwater samples were in acidic range in the industrial location while it was only 17% in the rural location. Multivariate statistical analysls was done using Principal Component Analysis, and the sources that inf1uence the composition of rainwater at each locations were identified .which clearly indicated that the quality of rain water is site specific and represents the atmospheric characteristics of the free fall The quality of harvested rainwater showed significant variations at different stages of harvesting due to deposition of dust from the roof catchment surface, leaching of cement constituents etc. Except the micro biological quality, the harvested rainwater satisfied the Indian Standard guide lines for drinking water. Studies conducted on the leaching of cement constituents in water concluded that tanks made with ordinary portland cement and portland pozzolana cement could be safely used for storage of rain water.

Mercuric Chloride Catalysed Solvolysis of Benzyl Chloride in Water & Highly Aqueous Organic Solvent Systems

Kinetics of mercuric chloride catalysed solvolysis of benzyl chloride have been studied in water. 10% aq. ethanol, 10,20 and 30% aq. acetone and 20% aq. DMSO. The results confirm the operation of a mass law effect.

DNA Interaction and Catalytic Activity Studies of Some New Transition Metal Complexes of Schiff Bases Derived from Quinoxaline

In this thesis we report the synthsis and characterisation of new transition metal complexes of Pd(II),Cu(II),Ru(II) and Ir(III) of Schiff bases derived from quinoxaline-2-carboxaldehyde/3-hydroxyquinoxaline-2-carboxaldehyde and 5-aminoindazole.6-aminoindazole or 8-aminoquinoline.The complexes have been characterised by spectral and analytical data.Pd(II) and Cu(II) form square planar complexes and Ru(III) and Ir(III) form ctahedral complexes with these Schiff bases.The DNA binding properties of theses synthesised complexes have been studied by various methods including electronic absoption spectroscopy,cyclic voltammetry,different pulse voltammetry and circular dichroism spectra were used.Gel electrophoresis experiments were also performed to investigate the DNA cleavage of theses complexes.Furthermore Ru(III) and Ir(III) complexes find application as oxidation and hydogenation catalsts. The studies on catalytic activities has been presented.The metal complexes presented in this thesis assure significance as they contribute to the development of new DNA binding agents and antibacterial and anticancer drugs.

Photoemission optogalvanic studies with copper as target electrode

Photoemission optogalvanaic (POG) effect has been observed by irradiating copper target electrode, in a nitrogen discharge cell using 1.06 μm and frequency doubled 532 nm Nd:YAG laser pulse. Measurement of the nature of the variation of POG signal strength with 532 nm laser fluence confirms the two photon induced photoelectric emission from copper. However, using 1.06 μm laser pulses thermally assisted photoemission is observed.

Solvent Effect on Absolute Fluorescence Quantum Yield of Rhodamine 6G Determined Using Transient Thermal Lens Technique

Dual beam thermal lens tecbnique is successfully employed for the determination of absolute Fluorescence quantum yield of rhodamine 6G lnser dye in different solvents. A 532 nm radiation from a Q-switched Nd:YAG laser was used for the excitation purpose. The fluorescence quantum yield values are found to be strongly influenced by environmental effects. It has been observed that fluorescence yield is greater for rhodamine 6G in ethylene glycol system than in water or in methanol. Our results also indicate that parameters like concentration of the dye solution, aggregate formation and excited state absorption affect the absolute values of fluorescence yield significantly.