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.

Realisation of a Target Classifier For Noise Sources in the Ocean

This thesis addresses one of the emerging topics in Sonar Signal Processing.,viz.the implementation of a target classifier for the noise sources in the ocean, as the operator assisted classification turns out to be tedious,laborious and time consuming.In the work reported in this thesis,various judiciously chosen components of the feature vector are used for realizing the newly proposed Hierarchical Target Trimming Model.The performance of the proposed classifier has been compared with the Euclidean distance and Fuzzy K-Nearest Neighbour Model classifiers and is found to have better success rates.The procedures for generating the Target Feature Record or the Feature vector from the spectral,cepstral and bispectral features have also been suggested.The Feature vector ,so generated from the noise data waveform is compared with the feature vectors available in the knowledge base and the most matching pattern is identified,for the purpose of target classification.In an attempt to improve the success rate of the Feature Vector based classifier,the proposed system has been augmented with the HMM based Classifier.Institutions where both the classifier decisions disagree,a contention resolving mechanism built around the DUET algorithm has been suggested.

Isp Knowledge Portal : A Resource Discovery Tool In Optics

The need to structure knowledge is as important now as it ever has been. This paper has tried to study the ISP knowledge portal to explore how knowledge on various resources and topics in photonics and related areas are organized in the knowledge portal of International School of Photonics, CUSAT. The study revealed that ISP knowledge portal is one of the best portals in the filed. It provides a model for building an effective knowledge portal in other fields

Design of a Knowledge-Based Geographic Information System

A GIS has been designed with limited Functionalities; but with a novel approach in Aits design. The spatial data model adopted in the design of KBGIS is the unlinked vector model. Each map entity is encoded separately in vector fonn, without referencing any of its neighbouring entities. Spatial relations, in other words, are not encoded. This approach is adequate for routine analysis of geographic data represented on a planar map, and their display (Pages 105-106). Even though spatial relations are not encoded explicitly, they can be extracted through the specially designed queries. This work was undertaken as an experiment to study the feasibility of developing a GIS using a knowledge base in place of a relational database. The source of input spatial data was accurate sheet maps that were manually digitised. Each identifiable geographic primitive was represented as a distinct object, with its spatial properties and attributes defined. Composite spatial objects, made up of primitive objects, were formulated, based on production rules defining such compositions. The facts and rules were then organised into a production system, using OPS5

Improved Biometric Authentication System Using Multimodal Cue Integration

Biometrics is an efficient technology with great possibilities in the area of security system development for official and commercial applications. The biometrics has recently become a significant part of any efficient person authentication solution. The advantage of using biometric traits is that they cannot be stolen, shared or even forgotten. The thesis addresses one of the emerging topics in Authentication System, viz., the implementation of Improved Biometric Authentication System using Multimodal Cue Integration, as the operator assisted identification turns out to be tedious, laborious and time consuming. In order to derive the best performance for the authentication system, an appropriate feature selection criteria has been evolved. It has been seen that the selection of too many features lead to the deterioration in the authentication performance and efficiency. In the work reported in this thesis, various judiciously chosen components of the biometric traits and their feature vectors are used for realizing the newly proposed Biometric Authentication System using Multimodal Cue Integration. The feature vectors so generated from the noisy biometric traits is compared with the feature vectors available in the knowledge base and the most matching pattern is identified for the purpose of user authentication. In an attempt to improve the success rate of the Feature Vector based authentication system, the proposed system has been augmented with the user dependent weighted fusion technique.

INVESTIGATIONS ON THE RECOVERY OF TITANIUM VANADIUM AND IRON VALUES FROM THE WASTE CHILORIDE LIQUORS OF TITANIA INDUSTRY

The thesis entitled INVESTIDGATIONS ON THE RECOVERY OF TITANIUM VANADIUM AND IRON VALUES FROM THE WASTE CHILORIDE LIQUORS OF TITANIA INDUSTRY embodies the results of the investigations carried out on the solvent extraction separation of iron (III) vanadium(V) and titanium (IV) chlorides from the waste chloride liquors of titanium minerals processing industry by employing tributylphosphate (TBT) as an extractant. The objective of this study is to generate the knowledge base to achieve the recovery of iron, vanadium and titanium cvalues from multi- metal waste chloride liquors originating from ilmenite mineral beneficiation industries through selective separation and value added material development

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.

Dominant partial least square factors of consumer purchase behaviour of passenger cars

Globalization and liberalization, with the entry of many prominent foreign manufacturers, changed the automobile scenario in India, since early 1990’s. World Leaders in automobile manufacturing such as Ford, General Motors, Honda, Toyota, Suzuki, Hyundai, Renault, Mitsubishi, Benz, BMW, Volkswagen and Nissan set up their manufacturing units in India in joint venture with their Indian counterpart companies, by making use of the Foreign Direct Investment policy of the Government of India, These manufacturers started capturing the hearts of Indian car customers with their choice of technological and innovative product features, with quality and reliability. With the multiplicity of choices available to the Indian passenger car buyers, it drastically changed the way the car purchase scenario in India and particularly in the State of Kerala. This transformed the automobile scene from a sellers’ market to buyers’ market. Car customers started developing their own personal preferences and purchasing patterns, which were hitherto unknown in the Indian automobile segment. The main purpose of this paper is to develop a model with major variables, which influence the consumer purchase behaviour of passenger car owners in the State of Kerala. Though there are innumerable studies conducted in other countries, there are very few thesis and research work conducted to study the consumer behaviour of the passenger car industry in India and specifically in the State of Kerala. The results of the research contribute to the practical knowledge base of the automobile industry, specifically to the passenger car segment. It has also a great contributory value addition to the manufacturers and dealers for customizing their marketing plans in the State

Acid base and catalytic properties of Zr02 - Y203 systems

The surface acidity and basicity of mixed oxides of Zr and Y and their mixed oxides have been determined by titration method using Hammett indicators. The acid base properties are evaluated on a common scale of acid strength. Liquid phase reduction of cyclohexanone has been selected as a model reaction to correlate catalytic activity.

Information Discovery in Distributed Systems-A Novel Concept Based on Modelling of Information Elements

Sharing of information with those in need of it has always been an idealistic goal of networked environments. With the proliferation of computer networks, information is so widely distributed among systems, that it is imperative to have well-organized schemes for retrieval and also discovery. This thesis attempts to investigate the problems associated with such schemes and suggests a software architecture, which is aimed towards achieving a meaningful discovery. Usage of information elements as a modelling base for efficient information discovery in distributed systems is demonstrated with the aid of a novel conceptual entity called infotron.The investigations are focused on distributed systems and their associated problems. The study was directed towards identifying suitable software architecture and incorporating the same in an environment where information growth is phenomenal and a proper mechanism for carrying out information discovery becomes feasible. An empirical study undertaken with the aid of an election database of constituencies distributed geographically, provided the insights required. This is manifested in the Election Counting and Reporting Software (ECRS) System. ECRS system is a software system, which is essentially distributed in nature designed to prepare reports to district administrators about the election counting process and to generate other miscellaneous statutory reports.Most of the distributed systems of the nature of ECRS normally will possess a "fragile architecture" which would make them amenable to collapse, with the occurrence of minor faults. This is resolved with the help of the penta-tier architecture proposed, that contained five different technologies at different tiers of the architecture.The results of experiment conducted and its analysis show that such an architecture would help to maintain different components of the software intact in an impermeable manner from any internal or external faults. The architecture thus evolved needed a mechanism to support information processing and discovery. This necessitated the introduction of the noveI concept of infotrons. Further, when a computing machine has to perform any meaningful extraction of information, it is guided by what is termed an infotron dictionary.The other empirical study was to find out which of the two prominent markup languages namely HTML and XML, is best suited for the incorporation of infotrons. A comparative study of 200 documents in HTML and XML was undertaken. The result was in favor ofXML.The concept of infotron and that of infotron dictionary, which were developed, was applied to implement an Information Discovery System (IDS). IDS is essentially, a system, that starts with the infotron(s) supplied as clue(s), and results in brewing the information required to satisfy the need of the information discoverer by utilizing the documents available at its disposal (as information space). The various components of the system and their interaction follows the penta-tier architectural model and therefore can be considered fault-tolerant. IDS is generic in nature and therefore the characteristics and the specifications were drawn up accordingly. Many subsystems interacted with multiple infotron dictionaries that were maintained in the system.In order to demonstrate the working of the IDS and to discover the information without modification of a typical Library Information System (LIS), an Information Discovery in Library Information System (lDLIS) application was developed. IDLIS is essentially a wrapper for the LIS, which maintains all the databases of the library. The purpose was to demonstrate that the functionality of a legacy system could be enhanced with the augmentation of IDS leading to information discovery service. IDLIS demonstrates IDS in action. IDLIS proves that any legacy system could be augmented with IDS effectively to provide the additional functionality of information discovery service.Possible applications of IDS and scope for further research in the field are covered.

Characterisation of the acid-base properties of pillared montmorillonites

Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed reactions.

Characterization of Selected Photonic Materials and Systems Using Photoacoustic Technique

The photoacoustic investigations carried out on different photonic materials are presented in this thesis. Photonic materials selected for the investigation are tape cast ceramics, muItilayer dielectric coatings, organic dye doped PVA films and PMMA matrix doped with dye mixtures. The studies are performed by the measurement of photoacoustic signal generated as a result of modulated cw laser irradiation of samples. The gas-microphone scheme is employed for the detection of photoacoustic signal. The different measurements reported here reveal the adaptability and utility of the PA technique for the characterization of photonic materials.Ceramics find applications in the field of microelectronics industry. Tape cast ceramics are the building blocks of many electronic components and certain ceramic tapes are used as thermal barriers. The thermal parameters of these tapes will not be the same as that of thin films of the same materials. Parameters are influenced by the presence of foreign bodies in the matrix and the sample preparation technique. Measurements are done on ceramic tapes of Zirconia, Zirconia-Alumina combination, barium titanate, barium tin titanate, silicon carbide, lead zirconate titanateil'Z'T) and lead magnesium niobate titanate(PMNPT). Various configurations viz. heat reflection geometry and heat transmission geometry of the photoacoustic technique have been used for the evaluation of different thermal parameters of the sample. Heat reflection geometry of the PA cell has been used for the evaluation of thermal effusivity and heat transmission geometry has been made use of in the evaluation of thermal diffusivity. From the thermal diffusivity and thermal effusivity values, thermal conductivity is also calculated. The calculated values are nearly the same as the values reported for pure materials. This shows the feasibility of photoacoustic technique for the thermal characterization of ceramic tapes.Organic dyes find applications as holographic recording medium and as active media for laser operations. Knowledge of the photochemical stability of the material is essential if it has to be used tor any of these applications. Mixing one dye with another can change the properties of the resulting system. Through careful mixing of the dyes in appropriate proportions and incorporating them in polymer matrices, media of required stability can be prepared. Investigations are carried out on Rhodamine 6GRhodamine B mixture doped PMMA samples. Addition of RhB in small amounts is found to stabilize Rh6G against photodegradation and addition of Rh6G into RhB increases the photosensitivity of the latter. The PA technique has been successfully employed for the monitoring of dye mixture doped PMMA sample. The same technique has been used for the monitoring of photodegradation ofa laser dye, cresyl violet doped polyvinyl alcohol also.Another important application of photoacoustic technique is in nondestructive evaluation of layered samples. Depth profiling capability of PA technique has been used for the non-destructive testing of multilayer dielectric films, which are highly reflecting in the wavelength range selected for investigations. Eventhough calculation of thickness of the film is not possible, number of layers present in the system can be found out using PA technique. The phase plot has clear step like discontinuities, the number of which coincides with the number of layers present in the multilayer stack. This shows the sensitivity of PA signal phase to boundaries in a layered structure. This aspect of PA signal can be utilized in non-destructive depth profiling of reflecting samples and for the identification of defects in layered structures.

Transition metal complexes of quinoxaline based Schiff base ligands: Synthesis,characterization and catalytic activity study

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.The convenient route of synthesis and thermal stability of Schiff base complexes have contributed significantly for their possible applications in catalysis,biology,medicine and photonics.Significant variations in cataltytic activity with structure and type are observed for these complexes.The thesis deals with synthsis and characterization of transition metal complexes of quinoxaline based Schiff base ligands and their catalytic activity study.The Schiff bases synthesized in the present study are quinoxaline-2-carboxalidine-2-amino-5-methylphenol,3-hydroxyquinoxaline-2-carboxalidine-2-amino-5-methylphenol,quinoxaline-2-aminothiophenol.They provide great structural diversity during complexation.To the best of our knowledge, the transition metal complexes of quinoxaline based Schiff bases are poorly utilised in academic and industrial research.

Studies on some new Schiff base complexes of ruthenium and neodymium

In the present study an attempt has been made to synthesize some simple complexes of multidentate ligands. Analogous zeolite encapsulated complexes were also synthesized and characterized. Immobilization on to polymer supports through covalent attachment is expected to solve the problem of decomposition of many complexes during catalytic reaction. Hence the work is also extended to the synthesis and characterization of some polymer supported complexes of Schiff base Iigands. All the three types of synthesized complexes, simple, zeolite encapsulated and polystyrene anchored, were subjected to catalytic activity study towards catechol-oxidation reaction. A selected group of complexes were also screened for their catalytic activity towards phenol-oxidation reaction. Biological screening of the synthesized ligands and neat complexes were done with a view to establish the effect of complexation on biological systems.

Tropical Mesoscale Convective Systems and Associated Energetics : Observational and Modeling Studies

The main purpose of the thesis is to improve the state of knowledge and understanding of the physical structure of the TMCS and its short range prediction. The present study principally addresses the fine structure, dynamics and microphysics of severe convective storms.The structure and dynamics of the Tropical cloud clusters over Indian region is not well understood. The observational cases discussed in the thesis are limited to the temperature and humidity observations. We propose a mesoscale observational network along with all the available Doppler radars and other conventional and non—conventional observations. Simultaneous observations with DWR, VHF and UHF radars of the same cloud system will provide new insight into the dynamics and microphysics of the clouds. More cases have to be studied in detail to obtain climatology of the storm type passing over tropical Indian region. These observational data sets provide wide variety of information to be assimilated to the mesoscale data assimilation system and can be used to force CSRM.The gravity wave generation and stratosphere troposphere exchange (STE) processes associated with convection gained a great deal of attention to modem science and meteorologist. Round the clock observations using VHF and UHF radars along with supplementary data sets like DWR, satellite, GPS/Radiosondes, meteorological rockets and aircrafl observations is needed to explore the role of convection and associated energetics in detail.