A comparative study on aniline alkylation activity using methanol and dimethyl carbonate as the alkylating agents over Zn–Co–Fe ternary spinel systems

The catalyst compositions of the Zn1−xCOxFe2O4 (x= 0, 0.2, 0.5, 0.8 and 1.0) spiel series possessing ‘x’ values, x less than or equal to 0.5, are unique for selective N-monomethylation of aniline using methanol as the alkylating agent. Since dimethyl carbonate (DMC) is another potential non-toxic alkylating agent, alkylation of aniline was investigated over various Zn–Co ferrites using DMC as the alkylating agent. The merits and demerits of the two alkylating agents are compared. Catalytic activity followed a similar trend with respect to the composition of the ferrospinel systems. DMC is active at comparatively low temperature, where methanol shows only mild activity. However, on the selectivity basis, DMC as an alkylating agent could not compete with methanol, since the former gave appreciable amounts of N,N-dimethylaniline (NNDMA) even at low temperature where methanol gave nearly 99% N-methylaniline (NMA) selectivity. As in the case of methanol, DMC also did not give any C-alkylated products.

Propagation of Microwaves in the Troposphere with Potential Application to GPS based Navigation and Meteorology with emphasis on Indian region

Global Positioning System (GPS), with its high integrity, continuous availability and reliability, revolutionized the navigation system based on radio ranging. With four or more GPS satellites in view, a GPS receiver can find its location anywhere over the globe with accuracy of few meters. High accuracy - within centimeters, or even millimeters is achievable by correcting the GPS signal with external augmentation system. The use of satellite for critical application like navigation has become a reality through the development of these augmentation systems (like W AAS, SDCM, and EGNOS, etc.) with a primary objective of providing essential integrity information needed for navigation service in their respective regions. Apart from these, many countries have initiated developing space-based regional augmentation systems like GAGAN and IRNSS of India, MSAS and QZSS of Japan, COMPASS of China, etc. In future, these regional systems will operate simultaneously and emerge as a Global Navigation Satellite System or GNSS to support a broad range of activities in the global navigation sector.Among different types of error sources in the GPS precise positioning, the propagation delay due to the atmospheric refraction is a limiting factor on the achievable accuracy using this system. The WADGPS, aimed for accurate positioning over a large area though broadcasts different errors involved in GPS ranging including ionosphere and troposphere errors, due to the large temporal and spatial variations in different atmospheric parameters especially in lower atmosphere (troposphere), the use of these broadcasted tropospheric corrections are not sufficiently accurate. This necessitated the estimation of tropospheric error based on realistic values of tropospheric refractivity. Presently available methodologies for the estimation of tropospheric delay are mostly based on the atmospheric data and GPS measurements from the mid-latitude regions, where the atmospheric conditions are significantly different from that over the tropics. No such attempts were made over the tropics. In a practical approach when the measured atmospheric parameters are not available analytical models evolved using data from mid-latitudes for this purpose alone can be used. The major drawback of these existing models is that it neglects the seasonal variation of the atmospheric parameters at stations near the equator. At tropics the model underestimates the delay in quite a few occasions. In this context, the present study is afirst and major step towards the development of models for tropospheric delay over the Indian region which is a prime requisite for future space based navigation program (GAGAN and IRNSS). Apart from the models based on the measured surface parameters, a region specific model which does not require any measured atmospheric parameter as input, but depends on latitude and day of the year was developed for the tropical region with emphasis on Indian sector.Large variability of atmospheric water vapor content in short spatial and/or temporal scales makes its measurement rather involved and expensive. A local network of GPS receivers is an effective tool for water vapor remote sensing over the land. This recently developed technique proves to be an effective tool for measuring PW. The potential of using GPS to estimate water vapor in the atmosphere at all-weather condition and with high temporal resolution is attempted. This will be useful for retrieving columnar water vapor from ground based GPS data. A good network of GPS could be a major source of water vapor information for Numerical Weather Prediction models and could act as surrogate to the data gap in microwave remote sensing for water vapor over land.

Design and Development of Fiber Grating Based Chemical and Bio-Sensors

International School of Photonics

New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

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.

Predicted impact of the sea-level rise at VellareColeroon estuarine region of Tamil Nadu coast in India: Mainstreaming adaptation as a coastal zone management option

Low-lying coastal areas are more vulnerable to the impacts of climate change as they are highly prone for inundation to SLR (Sea-Level Rise). This study presents an appraisal of the impacts of SLR on the coastal natural resources and its dependent social communities in the low-lying area of VellareColeroon estuarine region of the Tamil Nadu coast, India. Digital Elevation Model (DEM) derived from SRTM 90M (Shuttle Radar Topographic Mission) data, along with GIS (Geographic Information System) techniques are used to identify an area of inundation in the study site. The vulnerability of coastal areas in Vellar-Coleroon estuarine region of Tamil Nadu coast to inundation was calculated based on the projected SLR scenarios of 0.5 m and 1 m. The results demonstrated that about 1570 ha of the LULC (Land use and Land cover) of the study area would be permanently inundated to 0.5 m and 2407 ha for 1 m SLR and has also resulted in the loss of three major coastal natural resources like coastal agriculture, mangroves and aquaculture. It has been identified that six hamlets of the social communities who depend on these resources are at high-risk and vulnerable to 0.5 m SLR and 12 hamlets for 1 m SLR. From the study, it has been emphasized that mainstreaming adaptation options to SLR should be embedded within a coastal zone management and planning effort, which includes all coastal natural resources (ecosystem-based adaptation), and its dependent social communities (community-based adaptation) involved through capacity building