Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Texture, composition and provinance of innershelf sediments between Narakkal and Purakkad, Kerala with special reference to the formation of Mud Banks

The continental shelf of southwest coast of India (Kerala) is broader and . flatter compared to that of the east coast. The unique characteristic feature of the study area (innershelf between Narakkal and Purakkad) is the intermittent appearance of 'mud banks' at certain locations during southwest monsoon. The strong seasonality manifests significant changes in the wind, waves, currents, rainfall, drainage etc., along this area. Peculiar geomorphological variation with high, mid and lowlands in the narrow strip of the hinterland, the geological formations mainly consisting of rocks of metamorphic origin and the humid tropical weathering conditions play significant role in regulating the shelf sedimentation. A complementary pattern of distri bution is observed for clay that shows an abundance in the nearshore. Silt, to a major extent, depicts semblance with clay distribution . Summation of the total asymmetry of grain size distribution are inferred from the variation of skewness and kurtosis.Factor I implies a low energy regime where the transportation and deposition phases are controlled mostly by pelagic suspension process as the factor loadings are dominant on finer phi sizes. The second Factor is inferred to be the result of a high energy regime which gives higher loadings on coarser size fractions. The third Factor which might be a transition phase (medium energy regime) representing the resultant flux of coastal circulation of the re-suspension/deposition and an onshoreoffshore advection by reworking and co-deposition of relict and modern sediments. The spatial variations of the energy regime based on the three end-member factor model exhibits high energy zone in the seaward portion transcending to a low energy one towards the coast.From the combined analysis of granulometry and SEM studies, it is concluded that the sandy patches beyond 20 m depth are of relict nature. They are the resultant responses of beach activity during the lower stand of sea level in the Holocene. Re-crystallisation features on the quartz grains indicate that they were exposed to subaerial weathering process subsequent to thei r deposition

Influence of compounding and process variables on quality of condams made from natural rubber latex

Condoms are widely accepted as a contraceptive for family planning and population control. It is also accepted as the most effective barrier against sexually transmitted diseases, especially AIDS, the incurable disease. But presence of pinholes and low film strength of condoms make it unsuitable for the purpose. Quality improvement of condoms by reducing the pinhole formation and increasing the film strength is thus an essential requirement for population control as well as for preventing the spread of sexually transmitted diseases. Strict implementation of WHO specification of condoms further increases the rejection percentage. This causes higher rejection loss to condom manufacturers because the defects could be identified only at the final stage of processing. If the influence of various factors which cause these defects is known, manufacturers can take remedial measures to reduce the defectives so that rejection loss can be decreased and quality of condoms increased. In the present study, it was proposed to conduct experiments to improve the quality of condoms by reducing the pinhole rejection percentage and increasing the tensile properties, burst volume, and burst pressure. Ageing property improvement also was an important target among other parameters. Until a cure for AIDS is found, a high quality latex condom is the only effective device in the prevention of the spread of HIV, AIDS and STD's. Hence it is all the more necessary to have high quality condoms.

Enhanced UV emission from ZnO nanoflowers synthesized by the hydrothermal process

ZnO nanoflowers were synthesized by the hydrothermal process at an optimized growth temperature of 200 ◦C and a growth/reaction time of 3 h. As-prepared ZnO nanoflowers were characterized by x-ray diffraction, scanning electron microscopy, UV–visible and Raman spectroscopy. X-ray diffraction and Raman studies reveal that the as-synthesized flower-like ZnO nanostructures are highly crystalline with a hexagonal wurtzite phase preferentially oriented along the (1 0 1 1) plane. The average length (234–347 nm) and diameter (77–106 nm) of the nanorods constituting the flower-like structure are estimated using scanning electron microscopy studies. The band gap of ZnO nanoflowers is estimated as 3.23 eV, the lowering of band gap is attributed to the flower-like surface morphology and microstructure of ZnO. Room temperature photoluminescence spectrum shows a strong UV emission peak at 392 nm, with a suppressed visible emission related to the defect states, indicating the defect free formation of ZnO nanoflowers that can be potentially used for UV light-emitting devices. The suppressed Raman bands at 541 and 583 cm−1 related to defect states in ZnO confirms that the ZnO nanoflowers here obtained have a reduced presence of defects

Thermal degradation studies on Edible Oil during Deep Fat Frying Process

Deep fat frying process is one of the widely followed cooking practices throughout the world. Cooking oils serve as a medium for frying food for transferring heat and makes fried food tasty and palatable. Frying process is a most complex process involving numerous physicochemical changes which are complicated to understand. Frying leads to thermal degradation of oil through thermo-oxidation, hydrolysis, and polymerization. Hydrolysis results in formation of free fatty acids whereas oxidation process produces hydroperoxides and small molecular carbonyl compounds. This whole process leads to the formation of polar compounds and degradation of antioxidants that further degrades frying oil. Eventually, through mass transfer process these degradation products accumulate into fried food and reduce the nutritional quality of both oil and food. Thus, the frying process is of research interest calls for detailed systematic study which is chosen for the present study. The primary objective of this study is to understand the mechanism of degradation and characterization ofdegraded products which helps in arriving at the limits for frying oil utilization in terms of number of frying cycles. The mechanistic studies and the knowledge on the degraded products help to understand the way to retard the deterioration of oil for stability and enhancement of frying cycles. The study also explores the formation of the predominant polar compounds and their structural elucidation through mass spectrometry. Oxidation of oil is another important factor that ignites the degradation phenomena. One of the best ways to increase thermal stability of any oil is addition of potent antioxidants. But, most of the natural and synthetic antioxidants are unstable and ineffective at frying temperatures. Therefore, it is necessary to screen alternative antioxidants for their activity in the refined oils which are devoid of any added antioxidants. In this context, this study discussed the efficacy of several natural and synthetic antioxidants to retard the formation of polar compounds and thermooxidation during prolonged frying conditions. Similarly, the advantage of blending of two different oils to improve the thermal stability was explored. The present study brings out the total picture on the type of degradation products formed during frying and the ways of retarding the determination to improve upon the stability of the oil and enhancement of frying cycles.