Plasma Polymerised Organic Thin Films-A Study on the Structural, Electrical and Nonlinear Optical Properties for Possible Applications

This proposed thesis is entitled “Plasma Polymerised Organic Thin Films: A study on the Structural, Electrical, and Nonlinear Optical Properties for Possible Applications. Polymers and polymer based materials find enormous applications in the realm of electronics and optoelectronics. They are employed as both active and passive components in making various devices. Enormous research activities are going on in this area for the last three decades or so, and many useful contributions are made quite accidentally. Conducting polymers is such a discovery, and eversince the discovery of conducting polyacetylene, a new branch of science itself has emerged in the form of synthetic metals. Conducting polymers are useful materials for many applications like polymer displays, high density data storage, polymer FETs, polymer LEDs, photo voltaic devices and electrochemical cells. With the emergence of molecular electronics and its potential in finding useful applications, organic thin films are receiving an unusual attention by scientists and engineers alike. This is evident from the vast literature pertaining to this field appearing in various journals. Recently, computer aided design of organic molecules have added further impetus to the ongoing research activities in this area. Polymers, especially, conducting polymers can be prepared both in the bulk and in the thinfilm form. However, many applications necessitate that they are grown in the thin film form either as free standing or on appropriate substrates. As far as their bulk counterparts are concerned, they can be prepared by various polymerisation techniques such as chemical routes and electrochemical means. A survey of the literature reveals that polymers like polyaniline, polypyrrole, polythiophene, have been investigated with a view to studying their structural electrical and optical properties. Among the various alternate techniques employed for the preparation of polymer thin films, the method of plasma polymerisation needs special attention in this context. The technique of plasma polymerisation is an inexpensive method and often requires very less infra structure. This method includes the employment of ac, rf, dc, microwave and pulsed sources. They produce pinhole free homogeneous films on appropriate substrates under controlled conditions. In conventional plasma polymerisation set up, the monomer is fed into an evacuated chamber and an ac/rf/dc/ w/pulsed discharge is created which enables the monomer species to dissociate, leading to the formation of polymer thin films. However, it has been found that the structure and hence the properties exhibited by plasma polymerized thin films are quite different from that of their counterparts produced by other thin film preparation techniques such as electrochemical deposition or spin coating. The properties of these thin films can be tuned only if the interrelationship between the structure and other properties are understood from a fundamental point of view. So very often, a through evaluation of the various properties is a pre-requisite for tailoring the properties of the thin films for applications. It has been found that conjugation is a necessary condition for enhancing the conductivity of polymer thin films. RF technique of plasma polymerisation is an excellent tool to induce conjugation and this modifies the electrical properties too. Both oxidative and reductive doping can be employed to modify the electrical properties of the polymer thin films for various applications. This is where organic thin films based on polymers scored over inorganic thin films, where in large area devices can be fabricated with organic semiconductors which is difficult to achieve by inorganic materials. For such applications, a variety of polymers have been synthesized such as polyaniline, polythiophene, polypyrrole etc. There are newer polymers added to this family every now and then. There are many virgin areas where plasma polymers are yet to make a foray namely low-k dielectrics or as potential nonlinear optical materials such as optical limiters. There are also many materials which are not been prepared by the method of plasma polymerisation. Some of the materials which are not been dealt with are phenyl hydrazine and tea tree oil. The advantage of employing organic extracts like tea tree oil monomers as precursors for making plasma polymers is that there can be value addition to the already existing uses and possibility exists in converting them to electronic grade materials, especially semiconductors and optically active materials for photonic applications. One of the major motivations of this study is to synthesize plasma polymer thin films based on aniline, phenyl hydrazine, pyrrole, tea tree oil and eucalyptus oil by employing both rf and ac plasma polymerisation techniques. This will be carried out with the objective of growing thin films on various substrates such as glass, quartz and indium tin oxide (ITO) coated glass. There are various properties namely structural, electrical, dielectric permittivity, nonlinear optical properties which are to be evaluated to establish the relationship with the structure and the other properties. Special emphasis will be laid in evaluating the optical parameters like refractive index (n), extinction coefficient (k), the real and imaginary components of dielectric constant and the optical transition energies of the polymer thin films from the spectroscopic ellipsometric studies. Apart from evaluating these physical constants, it is also possible to predict whether a material exhibit nonlinear optical properties by ellipsometric investigations. So further studies using open aperture z-scan technique in order to evaluate the nonlinear optical properties of a few selected samples which are potential nonlinear optical materials is another objective of the present study. It will be another endeavour to offer an appropriate explanation for the nonlinear optical properties displayed by these films. Doping of plasma polymers is found to modify both the electrical conductivity and optical properties. Iodine is found to modify the properties of the polymer thin films. However insitu iodine doping is tricky and the film often looses its stability because of the escape of iodine. An appropriate insitu technique of doping will be developed to dope iodine in to the plasma polymerized thin films. Doping of polymer thin films with iodine results in improved and modified optical and electrical properties. However it requires tools like FTIR and UV-Vis-NIR spectroscopy to elucidate the structural and optical modifications imparted to the polymer films. This will be attempted here to establish the role of iodine in the modification of the properties exhibited by the films

Studies on Soft Bycatch Reduction Devices for Selective Trawling

Trawling, though an efficient method of fishing, is known to be one of the most non-selective methods of fish capture. The bulk of the wild caught penaeid shrimps landed in India are caught by trawling.In addition to shrimps, the trawler fleet also catches considerable amount of non-shrimp resources. The term bycatch means that portion of the catch other than target species caught while fishing, which are either retained or discarded. Bycatch discards is a serious problem leading to the depletion of the resources and negative impacts on biodiversity. In order to minimize this problem, trawling has to be made more selective by incorporating Bycatch Reduction Devices (BRDs). There are several advantages in using BRDs in shrimp trawling. BRDs reduce the negative impacts of shrimp trawling on marine community. Fishers could benefit economically from higher catch value due to improved catch quality, shorter sorting time, lower fuel costs, and longer tow duration. Adoption of BRDs by fishers would forestall criticism by conservation groups against trawling.

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

Studies on the Bioactive Natural Antioxidants From Oilseeds

Antioxidants are substances that when present at low concentrations compared to that of an oxidisable substrate significantly delays or inhibits oxidation of that substrate in food products or in living systems. Antioxidants are either endogenous to the body or derived from the diet. Several types of synthetic antioxidants like BHT, BHA, TBHQ etc. are also used in the food industry. However, findings and subsequent publicity has fostered significant consumer resistance to the use of synthetic food additives as antioxidants, colourants etc. and therefore food industry is in search of potential natural antioxidants from edible sources.The major dietary sources of antioxidant phytochemicals are cereals, legumes, fruits, vegetables, oilseeds, beverages, spices and herbs. In the present study, we have focused on rice bran and its byproducts. Rice is one of the oldest of food crops and has been a staple food in India from very ancient times. It is also the staple food for about 60% of the world's population. Rice bran is a byproduct of the rice milling industry and is a potential commercial source of a healthy edible oil viz. rice bran oil and a variety of bio-active phytochemicals.Defatted rice bran (DRB), a byproduct of rice bran oil extraction, is also a good source of insoluble dietary fiber, protein, phytic acid, inosito I, vitamin B and a variety of other phytochemicals. Though the antioxidant potential of DRB has been demonstrated, it still remained a relatively unexplored source material, which demanded further investigation especially with regard to its detailed phytochemical profile leading to practical application. The focus of the present investigation therefore has been on DRB primarily to establish its phytochemical status and feasibility of using it as a source of bio-active phytochemicals and natural antioxidants leading to value addition of DRB otherwise used as cattle feed. To gain a better understanding of the value of rice bran as a source of phytochemicals, five popular rice varieties of the region viz. PTB 50, PTB 39, PTB 38, JA Y A, and MO 10 and a wild variety (oryza nivara) that is mainly used for medicinal applications in traditional ayurvedic system were characterized along with commercial samples of rice bran. The present study also explains the feasibility of a process for the extraction, enrichment, and isolation of antioxidant compounds from DRB. The antioxidant potential of the extracts were evaluated both in bulk oils and in food relevant model emulsions, using standard in vitro models. Radical scavenging effects, indicative of possible biological effects, were also evaluated.

Determination of the laser-induced damage threshold of bulk polymer samples at 1.06 mu m using the pulsed photothermal deflection technique

A pulsed Nd-YAG laser beam is used to produce a transient refractive index gradient in air adjoining the plane surface of the sample material. This refractive index gradient is probed by a continuous He-Ne laser beam propagating parallel to the sample surface. The observed deflection signals produced by the probe beam exhibit drastic variations when the pump laser energy density crosses the damage threshold for the sample. The measurements are used to estimate the damage threshold for a few polymer samples. The present values are found to be in good agreement with those determined by other methods.

Measurement of laser ablation threshold on doped BiSrCaCuO high temperature superconductors by the pulsed photothermal deflection technique

Laser‐induced damage and ablation thresholds of bulk superconducting samples of Bi2(SrCa)xCu3Oy(x=2, 2.2, 2.6, 2.8, 3) and Bi1.6 (Pb)xSr2Ca2Cu3 Oy (x=0, 0.1, 0.2, 0.3, 0.4) for irradiation with a 1.06 μm beam from a Nd‐YAG laser have been determined as a function of x by the pulsed photothermal deflection technique. The threshold values of power density for ablation as well as damage are found to increase with increasing values of x in both systems while in the Pb‐doped system the threshold values decrease above a specific value of x, coinciding with the point at which the Tc also begins to fall.  

Damage threshold determination of bulk polymer samples using pulsed photothermal deflection technique

Photothermal deflection technique was used for determining the laser damage threshold of polymer samples of teflon (PTFE) and nylon. The experiment was conducted using a Q-switched Nd-YAG laser operating at its fundamental wavelength (1-06μm, pulse width 10 nS FWHM) as irradiation source and a He-Ne laser as the probe beam, along with a position sensitive detector. The damage threshold values determined by photothermal deflection method were in good agreement with those determined by other methods.

Realization of a Scanning Photoacoustic Technique: Thermal properties of Bulk and Film Samples

Among the large number of photothcrmal techniques available, photoacoustics assumes a very significant place because of its essential simplicity and the variety of applications it finds in science and technology. The photoacoustic (PA) effect is the generation of an acoustic signal when a sample, kept inside an enclosed volume, is irradiated by an intensity modulated beam of radiation. The radiation absorbed by the sample is converted into thermal waves by nonradiative de-excitation processes. The propagating thermal waves cause a corresponding expansion and contraction of the gas medium surrounding the sample, which in tum can be detected as sound waves by a sensitive microphone. These sound waves have the same frequency as the initial modulation frequency of light. Lock-in detection method enables one to have a sufficiently high signal to noise ratio for the detected signal. The PA signal amplitude depends on the optical absorption coefficient of the sample and its thermal properties. The PA signal phase is a function of the thermal diffusivity of the sample.Measurement of the PA amplitude and phase enables one to get valuable information about the thermal and optical properties of the sample. Since the PA signal depends on the optical and thennal properties of the sample, their variation will get reflected in the PA signal. Therefore, if the PA signal is collected from various points on a sample surface it will give a profile of the variations in the optical/thennal properties across the sample surface. Since the optical and thermal properties are affected by the presence of defects, interfaces, change of material etc. these will get reflected in the PA signal. By varying the modulation frequency, we can get information about the subsurface features also. This is the basic principle of PA imaging or PA depth profiling. It is a quickly expanding field with potential applications in thin film technology, chemical engineering, biology, medical diagnosis etc. Since it is a non-destructive method, PA imaging has added advantages over some of the other imaging techniques. A major part of the work presented in this thesis is concemed with the development of a PA imaging setup that can be used to detect the presence of surface and subsmface defects in solid samples.Determination of thermal transport properties such as thermal diffusivity, effusivity, conductivity and heat capacity of materials is another application of photothennal effect. There are various methods, depending on the nature of the sample, to determine these properties. However, there are only a few methods developed to determine all these properties simultaneously. Even though a few techniques to determine the above thermal properties individually for a coating can be found in literature, no technique is available for the simultaneous measurement of these parameters for a coating. We have developed a scanning photoacoustic technique that can be used to determine all the above thermal transport properties simultaneously in the case of opaque coatings such as paints. Another work that we have presented in this thesis is the determination of thermal effusivity of many bulk solids by a scanning photoacoustic technique. This is one of the very few methods developed to determine thermal effiisivity directly.

Global Value Chain Linkages of Manufacturing Export Firms: A Study of The Kannur Home Textile Industry

The literature on the involvement of developing countries in trade has focused on the effects of different aspects of globalization on firms, regions and countries. The study attempts to examine how an export based industry, locallyembedded and originated on the basis of regional strengths has been inserted into the global trade framework. Though the unit of analysis is the manufacturing export firm in the region of Kannur, it represents the entire home textile export industry from the state of Kerala, as close to 90% of fabric exports in home furnishing material, textiles for upholstery and decoration and stitched or fused, and branded made ups are from the region. From a global perspective, how developing countries face newer trade restrictions and overcome non quota barriers by firm and region specific activities within a value chain framework is a major research area, which has already contributions from the Ludhiana woolen cluster (Tewari,1999 ) and the Tirupur cluster in India (Cawthorne, 1995). The study contributes to the value chain literature by examining the governance and upgrading as well as how firms benefit from linkages. India has a number of export oriented agglomerations or regions where firms have been serving export markets for many years. In many cases it is no longer the supply side policy actions that determine how they are able to penetrate new markets or expand existing market share. Based on this study it becomes possible to understand how the global value chain operates in these different industries to examine whether there is a danger of immiserisation of growth or low road growth

Value orientation of professional students in kerala

The present study is on value orientation of professional students•and as such the theoretical value is inherent and implied. Variation on this value is likely to be limited among the subjects. The relevance of the present study is with particular reference, to management as a profession. In organisational settings motivation plays an important role. According to McClelland's theory of needs, achievement, power, and affiliation are the three important needs that help in understanding motivation. Achieve~ent need may be defined as the drive to excel, to achieve in relation to a set of standards, and to strive to succeed. Some people have a compelling drive to succeed. They have a desire to do something better or more efficiently than it has been done before. McClelland found that high achievers differentiate themselves from others by their desire to do things . better. Considering this fact, 'achievement' is included as one of the values for the study

Attribute reduction and missing value imputing with ANN: prediction of learning disabilities

Learning disability (LD) is a neurological condition that affects a child’s brain and impairs his ability to carry out one or many specific tasks. LD affects about 10% of children enrolled in schools. There is no cure for learning disabilities and they are lifelong. The problems of children with specific learning disabilities have been a cause of concern to parents and teachers for some time. Just as there are many different types of LDs, there are a variety of tests that may be done to pinpoint the problem The information gained from an evaluation is crucial for finding out how the parents and the school authorities can provide the best possible learning environment for child. This paper proposes a new approach in artificial neural network (ANN) for identifying LD in children at early stages so as to solve the problems faced by them and to get the benefits to the students, their parents and school authorities. In this study, we propose a closest fit algorithm data preprocessing with ANN classification to handle missing attribute values. This algorithm imputes the missing values in the preprocessing stage. Ignoring of missing attribute values is a common trend in all classifying algorithms. But, in this paper, we use an algorithm in a systematic approach for classification, which gives a satisfactory result in the prediction of LD. It acts as a tool for predicting the LD accurately, and good information of the child is made available to the concerned

On the optical and electrical properties of rf and a.c. plasma polymerized aniline thin films

Polyaniline is a widely studied conducting polymer and is a useful material in its bulk and thin film form for many applications, because of its excellent optical and electrical properties. Pristine and iodine doped polyaniline thin films were prepared by a.c. and rf plasma polymerization techniques separately for the comparison of their optical and electrical properties. Doping of iodine was effected in situ. The structural properties of these films were evaluated by FTIR spectroscopy and the optical band gap was estimated from UV-vis-NIR measurements. Comparative studies on the structural, optical and electrical properties of a.c. and rf polymerization are presented here. It has been found that the optical band gap of the polyaniline thin films prepared by rf and a.c. plasma polymerization techniques differ considerably and the band gap is further reduced by in situ doping of iodine. The electrical conductivity measurements on these films show a higher value of electrical conductivity in the case of rf plasma polymerized thin films when compared to the a.c. plasma polymerized films. Also, it is found that the iodine doping enhanced conductivity of the polymer thin films considerably. The results are compared and correlated and have been explained with respect to the different structures adopted under these two preparation techniques

Impact of Product Quality, Service Quality and Contextual Experience on Customer Perceived Value and Future Buying Intentions

Recognizing that high satisfaction leads to high customer loyalty, companies today are aiming for total customer satisfaction. This article explains relative impact of product quality, service quality and contextual experience on customer perceived value and intention to shop in the future. The data has been collected using a questionnaire from 205 customers of a national retailer chain. The relative importance of product quality, service quality and contextual experience on customer perceived value and thus on customer preference and future intentions was measured using multiple regression. Also, the contribution of perceived value to preference and thus on future buying intention was also measured. Structural Equation Model (SEM) using Amos 4 was used to find the overall fitness of the model. It was found that product quality, service quality and contextual experience have a major influence on customer perceived value

Studies on fish waste management practices in Aroor Seafood Industrial Belt, Kerala and conversion of seafood waste into a liquid plant growth supplement

This study was materialized to analyze the management issues regarding the seafood processing waste generated including its impact on the coastal community in one of the important seafood hubs of India Aroor Seafood Industrial Belt Alappuzha District Kerala The area has witnessed serious pollution issues related to seafood waste and seldom has any action been implemented by either the polluters or the preventers Further this study is also intended to suggest a low cost eco friendly method for utilizing the bulk quantity of seafood solid waste generated in the area for the promotion of organic farming The high nutritional value of seafood enables the subsequent offal to be considered as an excellent source for plant nutrition The liquid silage accepted worldwide as the cheapest and practical solution for rendering fish waste in bulk for production of livestock feed is adopted in this study to develop foliar fertilizer formulations from various seafood waste The effect of seafood foliar sprays is demonstrated by field studies on two plant varieties such as Okra and Amaranthus

Spray pyrolysed In2S3 thin films: A potential electron selective layer for large area inverted bulk-heterojunction polymer solar cells

In this paper, we report the results of investigations on the potential of spray pyrolysis technique in depositing electron selective layer over larger area for the fabrication of inverted bulk-heterojunction polymer solar cells. The electron selective layer (In2S3) was deposited using spray pyrolysis technique and the linear heterojunction device thus fabricated exhibited good uniformity in photovoltaic properties throughout the area of the device. An MEH-PPV:PCBM inverted bulk-heterojunction device with In2S3 electron selective layer (active area of 3.25 3.25 cm2) was also fabricated and tested under indoor and outdoor conditions. Fromthe indoor measurements employing a tungsten halogen lamp (50mW/cm2 illumination), an opencircuit voltage of 0.41V and a short-circuit current of 5.6mA were obtained. On the other hand, the outdoor measurements under direct sunlight (74mW/cm2) yielded an open-circuit voltage of 0.46V and a short-circuit current of 9.37mA