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.

Studies on Energy Exchange and Upper Ocean Thermat Structure in Arabian Sea and Heat Transport in Northern Indian Ocean

The thesis focused Studies on Energy Exchange and Upper Ocean Thermal Structure in Arabian Sea and Heat Transport in Northern Indian Ocean. The present thesis is an attempt to understand the upper ocean thermal characteristics at selected areas in the western and eastern Arabian Sea in relation to surface energy exchange and dynamics, on a climatological basis. It is also aimed to examine, the relative importance of different processes in the evolution of SST at the western and eastern Arabian Sea. Short-term variations of energy exchange and upper ocean thermal structure are also investigated. Climatological studies of upper ocean thermal structure and surface energy exchange in the western and eastern parts of Arabian Sea bring out the similarities/differences and the causative factors for the observed features. Annual variation of zonally averaged heat advection in north Indian Ocean shows that maximum export of about 100 W/m2 occurs around 15ON during southwest monsoon season. This is due to large negative heat storage caused by intense upwelling in several parts of northern Indian Ocean. By and large, northern Indian Ocean is an area of heat export

Development of solar air heaters & thermal energy storage system for drying applications in food processing industries

In the present work, the author has designed and developed all types of solar air heaters called porous and nonporous collectors. The developed solar air heaters were subjected to different air mass flow rates in order to standardize the flow per unit area of the collector. Much attention was given to investigate the performance of the solar air heaters fitted with baffles. The output obtained from the experiments on pilot models, helped the installation of solar air heating system for industrial drying applications also. Apart from these, various types of solar dryers, for small and medium scale drying applications, were also built up. The feasibility of ‘latent heat thermal energy storage system’ based on Phase Change Material was also undertaken. The application of solar greenhouse for drying industrial effluent was analyzed in the present study and a solar greenhouse was developed. The effectiveness of Computational Fluid Dynamics (CFD) in the field of solar air heaters was also analyzed. The thesis is divided into eight chapters.

Occurrence and Distribution of a Diatom-Diazotrophic Cyanobacteria Association during a Trichodesmium Bloom in the Southeastern Arabian Sea

Symbiotic diatom-diazotrophic cyanobacteria association (DDA) of Rhizosolenia hebetata and Rhizosolenia formosa with endosymbiotic cyanobacteria Richelia intracellularis was noticed and documented for the first time during a bloom of the cyanobacterium Trichodesmium erythraeum in the oligotrophic shelf waters along Kochi and Mangalore transects, southeastern Arabian Sea (SEAS), during spring intermonsoon (April 2012). Although the host is frequently seen, the symbiont is rarely reported in the Indian EEZ. The presence of nitrogen-fixing symbiotic association of Rhizosolenia-Richelia along with Trichodesmium erythraeum highlights the significance of DDAs on the nutrient and energy budgets of phytoplankton in the oligotrophic environments of the Arabian Sea during spring intermonsoon

Characterisation and Distribution of Amino Acids in the Mangrove Sediments of Kochi

Mangrove swamps are unique inter-tidal wetland ecosystems found in sheltered tropical and subtropical shores.Mangrove sediments can be considered as large reservoirs of amino acids,which exist in several different forms,like free amino acids in the sediment micropores,as amino acids,peptides or proteins bound to clay minerals or as amino acids,peptides or proteins bound to humic colloids.Inorder to assess survival conditions of organisms of mangroves,it is important to understand stability of amino acids in the sediments.The amounts of amino acids present in sediment represent a balance between its synthesis and destruction by microorganisms.Thus amino acid analysis offers more insight into the processes of diagenesis,which changes the nature and characteristics of organic matter deposition and decomposition.

A Study on the Transport and Distribution of Atmospheric Aerosols and its Influence on Regional Meteorological Parameters over the Indian Subcontinent

This doctoral thesis addresses the growing concern about the significant changes in the climatic and weather patterns due to the aerosol loading that have taken place in the Indo Gangetic Plain(IGP)which includes most of the Northern Indian region. The study region comprises of major industrial cities in India (New Delhi, Kanpur, Allahabad, Jamshedpur and Kolkata). Northern and central parts of India are one of the most thickly populated areas in the world and have the most intensely farmed areas. Rapid increase in population and urbanization has resulted in an abrupt increase in aerosol concentrations in recent years. The IGP has a major source of coal; therefore most of the industries including numerous thermal power plants that run on coal are located around this region. They inject copious amount of aerosols into the atmosphere. Moreover, the transport of dust aerosols from arid locations is prevalent during the dry months which increase the aerosol loading in theatmosphere. The topography of the place is also ideal for the congregation of aerosols. It is bounded by the Himalayas in the north, Thar Desert in the west, the Vindhyan range in the south and Brahmaputra ridge in the east. During the non‐monsoon months (October to May) the weather in the location is dry with very little rainfall. Surface winds are weak during most of the time in this dry season. The aerosols that reach the location by means of long distance transport and from regional sources get accumulated under these favourable conditions. The increase in aerosol concentration due to the complex combination of aerosol transport and anthropogenic factors mixed with the contribution from the natural sources alters the optical properties and the life time of clouds in the region. The associated perturbations in radiative balance have a significant impact on the meteorological parameters and this in turn determines the precipitation forming process. Therefore, any change in weather which disturbs the normal hydrological pattern is alarming in the socio‐economic point of view. Hence, the main focus of this work is to determine the variation in transport and distribution of aerosols in the region and to understand the interaction of these aerosols with meteorological parameters and cloud properties.

Studies on Energy Requirement and Conservation in Selected Fish Harvesting Systems

Present work deals with the studies on energy requirement and convervation in selected fish harvesting systems.Modem fishing is one of the most energy intensive methods of food production. Fossil fuels used for motorised and mechanised fishing are nonrenewable and limited. Most of the environmental problems that confront mankind today are connected to the use of energy in one way or another. Code of Conduct for Responsible Fisheries (FAO, 1995) highlights the need for efficient use of energy in the fisheries sector. Information on energy requirement in different fish harvesting systems, based on the principles of energy analysis, is entirely lacking in respect of Indian fisheries. Such an analysis will provide an unbiased decision making support for maximising the yield per unit of non-renewable energy use, from different fishery resource systems, by rational deployment of harvesting systems. In the present study, results of investigations conducted during 1997-2000 on energy requirement in selected fish harvesting systems and approaches to energy conservation in fishing, are presented along with a detailed description of the fish harvesting systems and their operation. The content of the thesis is organised into 8 Chapters.

Studies on prevulcanization of rubber latex with special reference to influence of storage and after treatments on properties of films

Systematic investigations on prevulcanization of NR latex with special reference to the influence of storage of latex and after-treatments of films, have been carried out. The other aspects studied include the effect of temperature on sulphur prevulcanization, the extent of crosslinking, tensile properties, stress relaxation characteristics, water absorption and leaching characteristics of prevulcanizcd latex films

Bionomics, Resource Characteristics And Distribution Of The Threatened Freshwater Fishes Of Kerala

The previous faunistic studies were concentrated.on the taxonomical and zoogeo— graphical aspects. These studies contributed to many new additions to the fish fauna of Kerala meanwhile many species described earlier are reported missing in recent years. Many fish species were collected only once or twice by scientists. Detailed information on distribution, habitat, feeding habits, reproduction, population size, etc. are available only with regard to a very few fish species. A meaningful assessment on the biodiversity status of the majority of freshwater fishes cannot be done for want of sufficient data base and therefore, no suitable conservation and management programmes are forthcoming for the protection and preservation of the unique fish germplasm resources of Kerala. The present study was conceptualised and undertaken mostly aiming at bridging these gaps by generating an authentic data base on the distribution, resource characteristics and bionomics of the threatened fishes inhabiting the rivers of Kerala. Osteobrama bakeri (Day) is an endemic fish having a very highly restricted and fragmented distribution in Periyar, Chalakudy, Kabini, Kallada and Meenachil rivers of Kerala. This belongs to vulnerable category and is locally known as Mullanpaval which is valued as food fish. Besides, due to its vibrant and attractive colouration and easiness for domestication, it has great potential for being propagated as an ornamental fish. Hitherto, no information is available on the bionomics and resource characteristics of this species. Studies on detailed life history traits are indispensable for fishery management, development of captive breeding technique and implementation of various conservation programmes. In the present study, a pioneer attempt is also made to investigate the life history traits, resource characteristics, proximate composition, etc. of O.baken'.

Studies On The Electrical Properties Of Some Crystalline Organic Compounds And Conducting Polymers

Solid electrolytes for applications like chemical sensing, energy storage, and conversion have been actively investigated and developed since the early sixties. Although of immense potential, solid state protonic conductors have been ignored in comparison with the great interest that has been shown to other ionic conductors like lithium and silver ion conductors. The non-availability of good, stable protonic conductors could be partly the reason for this situation. Although organic solids are better known for their electrical insulating character, ionic conductors of organic origin constitute a recent addition to the class of ionic conductors. However, detailed studies (N1 such conductors are scarce. Also the last decade has witnessed an unprecedented boom in research on organic "conducting polymers". These newly devised materials show conductivity spanning from insulator to metallic regimes, which can be manipulated by appropriate chemical treatment. They find applications in devices ranging from rechargeable batteries to "smart windows". This thesis mainly deals with the synthesis and investigations on the electrical properties of (i) certain organbc protonic conductors derived from ethylenediamine and (ii) substituted polyanilines

Prevalence and distribution of Salmonella serotypes in marketed broiler chickens and processing environment in Coimbatore City of southern India

Broiler chicken is gaining popularity among the consumers of India. Since poultry is recognised as a leading food vehicle for Salmonella contamination, the prevalence and distribution of Salmonella serotypes in broiler chickens and processing environments of retail outlets has been studied. In the present study 214 samples of broiler chicken and 311 environmental samples from cage were analysed for the presence of Salmonella. Of the various body parts of live chicken analysed prevalence varied from 1.4% in cloacca to 6.9% in crop region. Environmental samples from the cage showed higher prevalence of Salmonella ranging from0 to 16.67%. Apart from Salmonella enteritidis, which was the predominant Salmonella serotype in the chickens as well as in the environmental samples, other serotypes such as S. bareilly, S. cerro, S. mbandaka and S. moladewere also encountered. The results of the research calls for strict hygiene standards for retail broiler chicken processing outlets