Geochemistry of transition, non-transition and rare-earth elements in the surficial sediments of continental shelf of Kerala and an annex to the Cochin estuarine system

The metals present in the surface sediments have high demand on a global perspective, and the main reservoir of these elements is believed to be the ocean floor. A lot of studies on metals are going on throughout the world for its quantification and exploitation. Even though, some preliminary attempts have been made in selected areas for the quantitative study of metals in the western continental shelf of India, no comprehensive work has been reported so far. The importance of this study also lies on the fact that there has not been a proper evaluation of the impact of the Great Tsunami of 2004 on the coastal areas of the south India. In View of this, an attempt has been made to address the seasonal distribution, behavior and mechanisms which control the deposition of metals in the sediments of the western continental shelf and Cochin Estuary, an annex to this coastal marine region.Surface sediment samples were collected seasonally from two subenvironemnts of southwest coast of India, (continental shelf of Kerala and Cochin estuarine system), to estimate the seasonal distribution and geochemical behavior of non-transition, transition, rare-earth elements, Th and U. Bottom water samples were also taken from each station, and analysed for temperature, salinity and dissolved oxygen, hence the response of redox sensitive elements to oxygen minimum zone can be addressed. In addition, other sedimentary parameters such as sand, silt, clay fractions, CaCO3 and organic carbon content were also estimated to evaluate the control factors on level of metals present in the sediment. The study used different environmental data analysis techniques to evaluate the distribution and behavior of elements during different seasons. This includes environmental parameters such as elemental normalisation, enrichment factor, element excess, cerium and europium anomalies and authigenic uranium.

Photosensitivity of Laser Dye Mixtures in Polymer Matrix – A Photoacoustic Study

Laser induced photoacoustic (PA) technique is used in the study of photostability of polymethyl methacrylate (PMMA) films doped with Rhodamine 6G -Rhodamine B dye system. Energy transfer from a donor molecule to an acceptor molecule in a dye mixture affects the output of the dye system. Details of investigations on the role of laser power, modulation frequency and the irradiation wavelength on the photosensitivity of the dye mixture doped PMMA films are presented.

Synthesis and Characterisation of Thermoplastic Ionomers based on Natural Rubber

Chemically modified novel thermo-reversible zinc sulphonated ionomers based on natural rubber (NR), radiation induced styrene grafted natural rubber (RI-SGNR), and chemically induced styrene grafted natural rubber (CI-SGNR) were synthesized using acetyl sulphate/zinc acetate reagent system. Evidence for the attachment of sulphonate groups has been furnished by FTIR spectra. which was supplanted by FTNMR results. Estimation of the zinc sulphonate group was done using spectroscopic techniques such as XRFS and ICPAES. The TGA results prove improvement in the therrno-oxidative stability of the modified natural rubber. Both DSC and DMTA studies show that the incorporation of the ionic groups affect the thermal transition of the base polymer. Retention of the improved physical properties of the novel ionomers even after three repeated cycles of mastication and molding at 120 degree C may be considered as the evidence for the reprocessabiJity of the ionomer. Effect of both particulate (carbon black. silica & zinc stearate) and fibrous fillers (nylon & glass) on the properties of the radiation induced styrene grafted natural rubber ionomer has been evaluated. Incorporation of HAF carbon black results in maximum improvement in physical properties. Silica reinforces the backbone chain and weakens the ionic associations. Zinc stearate plays the dual role of reinforcement and ptasticization. The nylon and glass filled lonorner compounds show good improvement in the physical properties in comparison with the neat ionomer. Dispersion and adhesion of the fillers in the ionomer matrix has been amply supported by their SEM micrographs. Microwave probing of the electrical behavior of the 26.5 ZnSRISGNR ionomer reveals that the maximum relative complex conductivity and the complex permittivity appear at the frequency of 2.6 GHz. The complex conductivity of the base polymer increases from 1.8x 10.12 S/cm to 3.3xlO·4 S/cm. Influence of fillers on the dielectric constant and conductivity of the new ionic thermoplastic elastomer has been studied. The ionomer I nylon compound shows the highest microwave conductivity. Use of the 26.5 ZnS-RISGNR ionomer as a compatibilizer for obtaining the technologically compatible blends from the immiscible SBR/NBR system has been verified. The heat fugitive ionic cross-linked natural rubber may be, therefore, useful as an alternative to vulcanized rubber and thermoplastic elastomer

Studies on some supported transition metal complex and metal oxide catalysts for oxidation reactions

Zeolite encapsulated transition metal complexes have received wide attention as an effective heterogenized system that combines the tremendous activity of the metal complexes and the attractive features of the zeolite structure. Zeolite encapsulated complexes offer a bright future for attempts to replace homogeneous systems retaining its catalytic activity and minimizing the technical problems. especially for the partial oxidation of organic compounds. Studies on some zeolite encapsulated transition metal complexes are presented in this thesis. The ligands selected are technically important in a bio-mimetic or structural perspective. Attempts have been made in this study to investigate the composition, structure and stability of encapsulated complexes using available techniques. The catalytic activity of encapsulated complexes was evaluated for the oxidation of some organic compounds. The recycling ability of the catalyst as a result of the encapsulation was also studied.Our studies on Cu-Cr/Al2O3, a typical metal oxide catalyst. illustrate the use of design techniques to modify the properties of such conventional catalysts. The catalytic activity of this catalyst for the oxidation of carbon monoxide was measured. The effect of additives like Ce02 or Ti02 on the activity and stability of this system was also investigated. The additive is potent to improve the activity and stability ofthe catalyst so as to be more effective in commercial usage.

Optical properties of phthalocyanine molecules in cyano acrylate polymer matrix

Optical absorption and emission spectral studies of various phthalocyanine molecules, viz., LaPc, NdPc, SmPc, EuPc, CuPc and ZnPc in a polymer matrix of cyano acrylate are reported for the first time. All the absorption spectra show an intense B band (Soret) in the UV region followed by a weaker Q band in the visible region. The positions of the Q and B bands are found to have dependence on the metallic substitution. Values of the important spectral parameters, viz., molar extinction coefficient (ϵ), oscillator strength (f), radiative transition rate and decay time of the excited singlet state are also presented and compared with other solid matrices. The recorded fluorescence spectrum shows two broad emission bands in the case of NdPc, whereas for ZnPc only a very weak band is observed. The absence of emission bands for the other metallated phthalocyanines is attributed to increased spin orbit interaction and intersystem crossing.

Studies on Simple and Encapsulated Transition Metal Complexes of Schiff Bases Derived from Diaminonaphthalene

Schiff base complexes of transition metal ions have played a significant role in coordination chemistry.In the present study we have synthesized some new Mn(II),Co(II) and Cu(II) complexes of Schiff bases derived from 1,8-diaminonaphthalene.Even though we could not isolate theses Schiff bases (as they readily cyclise to form the perimidine compounds),we were able to characterize unequivacally the complexes synthesized from these compounds as complexes of Schiff Bases. We Synthesized three perimidine derivatives ,2-(quinoxalin-2-yl)-2,3-dihydro-1H-perimidine,2-(2,3-dihydro-1H-perimidin-2-yl)-6-methoxyphenol and 4-(2,3-dihyro-1H-perimidin-2-yl)-2-methoxyphenol by the condensation of 1,8-diaminonaphthalene with quinoxaline-2-carboxaldehyde,2- hydroxy-3-methoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde respectively.Theses compounds were used as precursor ligands for the preparation of Schiff base complexes.The complexes were characterized by using elemental analysis ,conductance and magnetic susceptibility measuremets ,infrared and UV-Visible spectroscopy ,thermogravimetric analysis and EPR spectroscopy .We also encapsulated the complexes in zeolite Y matrix and these encapsulated complexes were also characterized. We have also tried theses complexes as catalysts in the oxidation of cyclohexanol and decomposition of hydrogen peroxide.

An Error-Localization, Validation and Optimization Tool for Embedded Code Augmentation: an Architecture Oriented Approach

Embedded systems are usually designed for a single or a specified set of tasks. This specificity means the system design as well as its hardware/software development can be highly optimized. Embedded software must meet the requirements such as high reliability operation on resource-constrained platforms, real time constraints and rapid development. This necessitates the adoption of static machine codes analysis tools running on a host machine for the validation and optimization of embedded system codes, which can help meet all of these goals. This could significantly augment the software quality and is still a challenging field.Embedded systems are usually designed for a single or a specified set of tasks. This specificity means the system design as well as its hardware/software development can be highly optimized. Embedded software must meet the requirements such as high reliability operation on resource-constrained platforms, real time constraints and rapid development. This necessitates the adoption of static machine codes analysis tools running on a host machine for the validation and optimization of embedded system codes, which can help meet all of these goals. This could significantly augment the software quality and is still a challenging field.Embedded systems are usually designed for a single or a specified set of tasks. This specificity means the system design as well as its hardware/software development can be highly optimized. Embedded software must meet the requirements such as high reliability operation on resource-constrained platforms, real time constraints and rapid development. This necessitates the adoption of static machine codes analysis tools running on a host machine for the validation and optimization of embedded system codes, which can help meet all of these goals. This could significantly augment the software quality and is still a challenging field.Embedded systems are usually designed for a single or a specified set of tasks. This specificity means the system design as well as its hardware/software development can be highly optimized. Embedded software must meet the requirements such as high reliability operation on resource-constrained platforms, real time constraints and rapid development. This necessitates the adoption of static machine codes analysis tools running on a host machine for the validation and optimization of embedded system codes, which can help meet all of these goals. This could significantly augment the software quality and is still a challenging field.This dissertation contributes to an architecture oriented code validation, error localization and optimization technique assisting the embedded system designer in software debugging, to make it more effective at early detection of software bugs that are otherwise hard to detect, using the static analysis of machine codes. The focus of this work is to develop methods that automatically localize faults as well as optimize the code and thus improve the debugging process as well as quality of the code.Validation is done with the help of rules of inferences formulated for the target processor. The rules govern the occurrence of illegitimate/out of place instructions and code sequences for executing the computational and integrated peripheral functions. The stipulated rules are encoded in propositional logic formulae and their compliance is tested individually in all possible execution paths of the application programs. An incorrect sequence of machine code pattern is identified using slicing techniques on the control flow graph generated from the machine code.An algorithm to assist the compiler to eliminate the redundant bank switching codes and decide on optimum data allocation to banked memory resulting in minimum number of bank switching codes in embedded system software is proposed. A relation matrix and a state transition diagram formed for the active memory bank state transition corresponding to each bank selection instruction is used for the detection of redundant codes. Instances of code redundancy based on the stipulated rules for the target processor are identified.This validation and optimization tool can be integrated to the system development environment. It is a novel approach independent of compiler/assembler, applicable to a wide range of processors once appropriate rules are formulated. Program states are identified mainly with machine code pattern, which drastically reduces the state space creation contributing to an improved state-of-the-art model checking. Though the technique described is general, the implementation is architecture oriented, and hence the feasibility study is conducted on PIC16F87X microcontrollers. The proposed tool will be very useful in steering novices towards correct use of difficult microcontroller features in developing embedded systems.

Analysis of System Signals Based on Cross Recurrence Method for System Dynamics Characterization

Natural systems are inherently non linear. Recurrent behaviours are typical of natural systems. Recurrence is a fundamental property of non linear dynamical systems which can be exploited to characterize the system behaviour effectively. Cross recurrence based analysis of sensor signals from non linear dynamical system is presented in this thesis. The mutual dependency among relatively independent components of a system is referred as coupling. The analysis is done for a mechanically coupled system specifically designed for conducting experiment. Further, cross recurrence method is extended to the actual machining process in a lathe to characterize the chatter during turning. The result is verified by permutation entropy method. Conventional linear methods or models are incapable of capturing the critical and strange behaviours associated with the dynamical process. Hence any effective feature extraction methodologies should invariably gather information thorough nonlinear time series analysis. The sensor signals from the dynamical system normally contain noise and non stationarity. In an effort to get over these two issues to the maximum possible extent, this work adopts the cross recurrence quantification analysis (CRQA) methodology since it is found to be robust against noise and stationarity in the signals. The study reveals that the CRQA is capable of characterizing even weak coupling among system signals. It also divulges the dependence of certain CRQA variables like percent determinism, percent recurrence and entropy to chatter unambiguously. The surrogate data test shows that the results obtained by CRQA are the true properties of the temporal evolution of the dynamics and contain a degree of deterministic structure. The results are verified using permutation entropy (PE) to detect the onset of chatter from the time series. The present study ascertains that this CRP based methodology is capable of recognizing the transition from regular cutting to the chatter cutting irrespective of the machining parameters or work piece material. The results establish this methodology to be feasible for detection of chatter in metal cutting operation in a lathe.

An evaluation of Primary health care system in Kerala

The thesis entitled An Evaluation of Primary Health Care System in Kerala. The present study is intended to examine the working of primary health care system and its impact on the health status of people. The hypothesis tested in the thesis includes, a. The changes in the health profile require reallocation of resources of primary health care system, b. Rate of utilization depends on the quality of services provided by primary health centers, and c. There is a significant decline in the operational efficiency of the primary health care system. The major elements of primary health care stated in the report of AlmaAta International Conference on Primary Health Care (WHO, 1994)” is studied on the basis of the classification of the elements in to three: Preventive, Promotive, and Curative measures. Preventive measures include Maternal and Child Health Care including family Planning. Provision of water and sanitation is reviewed under promotive measures. Curative measures are studied using the disease profile of the study area. Collection of primary data was done through a sample survey, using pre-tested interview schedule of households of the study area. Multi stage random sampling design was used for selecting the sample. The design of the present study is both descriptive and analytical in nature. As far as the analytical tools are concerned, growth index, percentages, ratios, rates, time series analysis, analysis of variance, chi square test, Z test were used for analyzing the data. Present study revealed that no one in these areas was covered under any type of health insurance. Conclusion states that considering the present changes in the health profile, traditional pattern of resource allocation should be altered to meet the urgent health care needs of the people. Preventive and promotive measures like health education for giving awareness among people to change health habits, diet pattern, life style etc. are to be developed. Proper diagnosis and treatment of the disease at the beginning of the stage itself may help to cure majority of disease. For that, Public health policy must ensure the primary health care as enunciated at Alma- Ata international Conference. At the same time Public health is not to be treated as the sole responsibility of the government. Active community participation is an essential means to attain the goals.