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

Recycling of NR Based Cured Latex Material Reclaimed with 2,2'-Dibenzamidodiphenyldisulphide in a TruckTire Tread Compound

It is observed that reclamation of natural rubber latex based rubber using 2,2'-dibenzamidodiphenvldisulphide as reclaiming agent is an optional methodology for recycling of waste latex rubber (WLR). For progressive replacement of virgin natural rubber by the reclaim, two alternatives curing system were investigated: adjustment or reduction of the curing system with increasing reclaim content, to compensate for the extra amount of curatives brought along by the reclaim. For fixed curing system, as if the reclaim were equivalent to virgin NR. The cure behavior, final crosslink density and distribution, mechanical properties, and dynamic viscoelastic properties of the blends with reclaimed WLR are measured and compared with the virgin compound. The morphology of the blends, sulfur migration, and final distribution are analyzed.The mechanical and dynamic viscoelastic properties deteriorate for both curing systems, but to a lesser extent for fixed curing system compared to adjusted curing system. With the fixed cure system, many properties like tensile strength and compression set do still deteriorate, but tan 6 and Mrrr„/Murxr, representative for the rolling resistance of tires are improved. On the other hand, with the adjusted cure system both mechanical and dynamic properties still deteriorate.

Characterization of Short Nylon-6 Fiber/Acrylonitrile Butadiene Rubber Composite by Thermogravimetry

The thermal degradation of short nylon-6 fiber reinforced acrylonitrile butadiene rubber (NBR) composites with and without epoxy-based bonding agent has been studied by thermogravimetric analysis (TGA). It was found that the onset of degradation shifted from 330.5 to 336.1°C in the presence of short nylon fiber, the optimum fiber loading being 20 phr. The maximum rate of degradation of the composites was lower than that of the unfilled rubber compound, and it decreased with increase in fiber concentration. The presence of epoxy resin-based bonding agent in the virgin elastomer and the composites improved the thermal stability. Results of kinetic studies showed that the degradation of NBR and the short nylon fiber reinforced composites followed first-order kinetics.

Thermal degradation of short polyester fiber polyurethane elastomer composite

The thermal degradation of short polyester fiber reinforced polyurethane composites with and without different bonding agents has been studied by thermogravimetric analysis . It was found that degradation of the polyurethane takes place in two steps and that of the composites takes place in three steps. With the incorporation of 30 phr of fiber in the matrix , the onset of degradation was shifted from 230 to 238 ° C. The presence of bonding agents in the virgin elastomer and the composite gave an improved thermal stability . Results of kinetic studies showed that the degradation of polyurethane and the reinforced composites with and without bonding agents follows first -order reaction kinetics

Studies on the Utilisation of Rubber Reclaim in Elastomers

The thesis describes utilisation of reclaimed rubber, Whole Tyre Reclaim (WTR) produced from bio non- degradable solid pollutant scrap and used tyres. In this study an attempt has made to optimize the substitution of virgin rubber with WTR in both natural and synthetic rubber compounds without seriously compromising the important mechanical properties. The WTR is used as potent source of rubber hydrocarbon and carbon black filler. Apart from natural rubber (NR), Butadiene rubber (BR), Styrene butadiene rubber (SBR), Acrylonitrile butadiene rubber (NBR) and Chloroprene rubber (CR) were selected for study, being the most widely used general purpose and specialty rubbers. The compatibility problem was addressed by functionalisation of WTR with maleic anhydride and by using a coupling agent Si69.The blends were systematically evaluated with respect to various mechanical properties. The thermogravimetric analyses were also carried out to evaluate the thermal stability of the blends.Mechanical properties of the blends were property and matrix dependant. Presence of reinforcing carbon black filler and curatives in the reclaimed rubber improved the mechanical properties with the exception of some of the elastic properties like heat build up, resilience, compression set. When WTR was blended with natural rubber and synthetic rubbers, as the concentration of the low molecular weight, depolymerised WfR was increased above 46-weight percent, the properties deteriorates.When WTR was blended with crystallizing rubbers such as natural rubber and chloroprene rubber, properties like tensile strength, ultimate elongation were decreased in presence of WTR. Where as in the case of blends of WTR with non-crystallizing rubbers reinforcement effect was more prominent.The effect of functionalisation and coupling agent was studied in three matrices having different levels of polarity(NBR, CR and SBR).The grafting of maleic anhydride on to WTR definitely improved the properties of its blends with NBR, CR and SBR, the effect being prominent in Chloroprene rubber.Improvement in properties of these blends could also achieved by using a coupling agent Si69. With this there is apparent plasticizing effect at higher loading of the coupling agent. The optimum concentration of Si69 was 1 phr for improved properties, though the improvements are not as significant as in the case of maleic anhydride grafting.Thermal stability of the blend was increased by using silane-coupling agent.

Studies on short Nylon-6 fiber - elastomer composites with epoxy resin as bonding agent

The thesis describes the development and evaluation of epoxy resin as interfacial bonding agent for short Nylon-6 fiber elastomer composites. Epoxy resin is well known for its adhesive property. The potential use of it as interfacial bonding agent in short fiber composite is not explored yet. Three rubbers viz., acrylonitrile butadiene rubber (NBR), Neoprene rubber (CR) and styrene butadiene rubber (SBR) were selected and different fiber loading were tried. The resin concentration was optimized for each fiber loading with respect to cure characteristics and mechanical properties. Rheological characteristics and thermal degradation of the composites containing different fiber loading and different resin concentrations were studied in detail to find the effect of epoxy resin bonding system. The mechanical properties were studied in detail. The short Nylon -6 fiber improved most of the mechanical properties of all the three rubbers. Tensile strength showed a dip at 10 phr fiber loading in the case of CR while it was continuously increased with fiber loading in the case of NBR and SBR. All the composites showed anisotropy in mechanical properties. The epoxy resin is an effective bonding agent for short Nylon -6 fiber reinforced NBR and CR composites. Epoxy resin improved tensile strength, abrasion resistance and modulus of these composites. SEM studies confirmed the improved bonding of fiber and matrix in the presence of epoxy bonding agent. Epoxy resin was not effective as bonding agent in the case of short Nylon fiber- SBR composite. From the rheological studies of the composites with and without bonding agent it was observed that all the composite exhibited pseudoplasticity, which decreased with temperature. At higher shear rates all the mixes showed plug flow. SEM pictures showed that maximum orientation of fibers occured at a shear rate, just before the onset of plug flow. The presence of fiber reduced the temperature sensitivity of the flow at a given shear rate. Die swell was reduced in the presence of fiber. Shear viscosity of the composite was increased in the presence of resin. Die swell was increased in the presence of epoxy resin for composites at all shear rates. The thermal degradation of NBR and SBR composites with and without bonding agent followed single step degradation pattern. Thermal stability of the composites was improved in the presence of bonding agent. The degradation of virgin elastomer and the composites followed first order kinetics.

Development of Polymer Cement Composites

Research in the field of polymer modified cement has been carried out for the last 70 years or more. Polymers are mostly used to enhance durability and sustainability of cement concrete and in combination with classical construction materials a synergistic effect is obtained. In this work different polymers were added to Portland cement in various proportions and the mechanical and chemical resistance properties of the resultant composites when exposed to chemical environments were studied. Microstructural studies were also carried out to investigate the morphology of the composite and analyse the nature of interactions taking place between the cement and polymer phases. Though most polymers did not improve the compressive strength of the cement paste, it was found that they enhanced the resistance of the virgin cement paste to external chemical environments. The polymers seal the pores in the cement matrix and bridge the microcracks within the composite. Some of the polymers underwent chemical interactions with the cement paste thereby interfering in the hydration of cement. Polymers also decreased the leachability of water soluble components of virgin cement resulting in composites having improved durability. An attempt to correlate the structure of the polymers with the properties of the resultant composites is also presented.

Economics of Ornamental Fisheries in Kerala

Comprehensive studies integrating production, consumption and marketing of ornamental fishes were never conducted in the past in Kerala and this study is an attempt to highlight the dynamics in a systematic manner by making a primary empirical study. The advantages of such an approach are many. First, the study entails detailed empirical data under a given time frame on various inter linked economic activities in ornamental fisheries sector. Second, the study tries to improve upon the previous discipline-bound studies by adopting an integrated approach. As Kerala has diverse ecological and climatic conditions, case studies on various ornamental fish production systems help identifying suitable culture practice for selected environmental conditions. One of the major conclusions of this study as explained in the concluding chapter is that although Kerala is blessed with favourable geographic and climatic conditions needed for developing ornamental fishery, diverse local conditions and requirements contain adopting modern methods of enterprise development.Consumer studies conducted would help to identify the demand of ornamental fishes and the factors leading to it. Market studies would help in understanding the forces behind domestic market, which is very promising, but neglected. Viability studies throw light on the economic performance of both the production systems and the trading units of ornamental fishes. Despite the economic significance of ornamental fisheries industry, its development has been constrained due to various bio-technical, cultural, socio-economic, organisational and above all, institutional and policy failures. The outcome of the study would identify constraints facing the industry and institutional arrangements for development.

Influence of Selected Dietary Micronutrient Elements on Growth and Biochemistry of Farmed Prawns

From the present study, it is clear that all the three metals, selenium, molybdenum and cobalt have significant effect on the antioxidant status of the shrimps. Selenium and molybdenum were observed to induce peroxidative damage at elevated levels. But at the same level, cobalt did not show such an effect. Selenium was found to be growth promoting at lower levels of dietary supplementation. Even though low levels of dietary selenium had a protective effect against the lipid peroxidation, the present study indicates that high levels of dietary selenium could promote lipid peroxidation. The selenium-dependent antioxidant enzyme, GPx behaved differently in muscle and hepatopancreas. A high concentration of selenium was required for the active expression of the enzyme in the muscle, where as in hepatopancreas maximum activity was observed at lower selenium concentration. Selenium supplementation had a positive effect on GSH concentration. The other antioxidant enzymes such as GST, SOD and CAT showed enhanced activity at higher concentration of selenium. Molybdenum supplementation significantly reduced the free radical scavenger enzymes SOD and CAT. This resulted in enhanced lipid peroxidation in tissues. The activity of antioxidant enzyme GPx and the concentration of the substrate for the enzyme, GSH also were lower at elevated levels of molybdenum supplementation. In addition to this amino acids and fatty acids were also altered in molybdenum supplemented groups. In trace amounts, dietary molybdenum exerts a beneficial effect on the growth and also in the activities of the enzymes XO and SO. At the same time it also indicates a possibility of oxidative damage as a result of the peroxidation caused by the activities of the enzymes SO and XO at elevated concentrations of molybdenum is also indicated. The absorption of various trace elements was also altered by molybdenum supplementation.Among the three metals studied, cobalt was the least toxic one at the administered levels. But this metal has a significant effect on the lipid content, amino acid composition, cholesterol levels and phospholipid levels. Increased growth was also observed as a result of cobalt supplementation in shrimps. The antioxidant system of the animal was activated by dietary cobalt. Tissue levels of the trace metals were also found to be altered in cobalt supplemented groups of shrimps.These studies, thus shows that influence of dietary trace metals calls for more detailed studies in farmed shrimp. They may hold the key to growth and even disease resistance in shrimp. But this still remains as a virgin field which demands more attention, especially in view of the increasing importance of shrimp farming.

Current status and biodiversity modification in the coastal wetland ecosystems of India with objectives for its sustainable management

The South West (S.W.) coast of India is blessed with a series of wetland systems popularly referred to as backwaters covering a total area of 46128.94 ha. These backwaters are internationally renowned for their aesthetic and scientific values including being a repository for several species fish and shell fishes. This is more significant in that three wetlands (Vembanad, Sasthamcotta and Ashtamudi) have recently been designated as Ramsar sites of international importance. Thirty major backwaters forming the crux of the coastal wetlands form an abode for over 200 resident or migratory fish and shellfish species. The fishing activities in these water bodies provide the livelihood to about 200,000 fishers and also provide full-time employment to over 50,000 fishermen. This paper describes the changes on the environmental and biodiversity status of selected wetlands, during 1994-2005 period. The pH was generally near neutral to alkaline in range. The salinity values indicated mixohaline condition ranging from 5.20-32.38 ppt. in the 12 wetlands. The productivity values were generally low in most of the wetlands during the study, where the gross production varied from 0.22 gC/m3/day in Kadinamkulam to 1.10 gC/m3/day in the Kayamkulam. The diversity of plankton and benthos was more during the pre-monsoon compared to the monsoon and post-monsoon periods in most of the wetlands. The diversity of plankton and benthos was more during the pre-monsoon compared to the monsoon and post-monsoon periods in most of the wetlands. The average fish yield per ha. varied from 246 kg. in Valapattanam to 2747.3 kg. in Azhikode wetland. Retting of coconut husk in most of the wetlands led to acidic pH conditions with anoxia resulting in the production of high amounts of sulphide, coupled with high carbon dioxide values leading to drastic reduction in the incidence and abundance of plankton, benthic fauna and the fishery resources. The major fish species recorded from the investigation were Etroplus suratensis, E. maculatus, Channa marulius, Labeo dussumieri, Puntius sp. Lutianus argentimaculatus, Mystus sp., Tachysurus sp. and Hemiramphus sp. The majority of these backwaters are highly stressed, especially during the pre monsoon period when the retting activity is at its peak. The study has clearly reflected that a more restrained and cautious approach is needed to manage and preserve the unique backwater ecosystems of South-west India

Construction waste management in India

The management of construction waste is important today. The scarcity in the availability of aggregate for the production of concrete is one of the important problems facing by the construction industry. Appropriate use of the construction waste is a solution to the fast degradation of virgin raw materials in the construction industry. This paper enlightens the importance of reduce, reuse and recycle (3R) concept for managing the construction waste in India

Design, Development and Realization of Quadratic Volterra Filters for Selected Applications

The basic concepts of digital signal processing are taught to the students in engineering and science. The focus of the course is on linear, time invariant systems. The question as to what happens when the system is governed by a quadratic or cubic equation remains unanswered in the vast majority of literature on signal processing. Light has been shed on this problem when John V Mathews and Giovanni L Sicuranza published the book Polynomial Signal Processing. This book opened up an unseen vista of polynomial systems for signal and image processing. The book presented the theory and implementations of both adaptive and non-adaptive FIR and IIR quadratic systems which offer improved performance than conventional linear systems. The theory of quadratic systems presents a pristine and virgin area of research that offers computationally intensive work. Once the area of research is selected, the next issue is the choice of the software tool to carry out the work. Conventional languages like C and C++ are easily eliminated as they are not interpreted and lack good quality plotting libraries. MATLAB is proved to be very slow and so do SCILAB and Octave. The search for a language for scientific computing that was as fast as C, but with a good quality plotting library, ended up in Python, a distant relative of LISP. It proved to be ideal for scientific computing. An account of the use of Python, its scientific computing package scipy and the plotting library pylab is given in the appendix Initially, work is focused on designing predictors that exploit the polynomial nonlinearities inherent in speech generation mechanisms. Soon, the work got diverted into medical image processing which offered more potential to exploit by the use of quadratic methods. The major focus in this area is on quadratic edge detection methods for retinal images and fingerprints as well as de-noising raw MRI signals

Sustainable Building Materials in Kerala – An Overview

Kerala, God’s own country is blessed with immense natural resources. It’s high time that the state’s natural resources being utilized effectively. While sustainable development is the need of the hour, we have to take lead in initiating activities that would minimize the exploitation of our natural resources resulting in their effective utilization. This paper narrates an overview of innovative building materials especially using natural fibres available in Kerala and discusses the feasibility of utilising such fibres in the context of sustainable building materials in Kerala. The paper also discusses how these materials can be effectively utilized to reduce the huge investment in the construction industry

Rice husk ash – A valuable reinforcement for high density polyethylene

This paper presents the results of a study on the use of rice husk ash (RHA) for property modification of high density polyethylene (HDPE). Rice husk is a waste product of the rice processing industry. It is used widely as a fuel which results in large quantities of RHA. Here, the characterization of RHA has been done with the help of X-ray diffraction (XRD), Inductively Coupled Plasma Atomic Emission Spectroscopy (ICPAES), light scattering based particle size analysis, Fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscope (SEM). Most reports suggest that RHA when blended directly with polymers without polar groups does not improve the properties of the polymer substantially. In this study RHA is blended with HDPE in the presence of a compatibilizer. The compatibilized HDPE-RHA blend has a tensile strength about 18% higher than that of virgin HDPE. The elongation-at-break is also higher for the compatibilized blend. TGA studies reveal that uncompatibilized as well as compatibilized HDPERHA composites have excellent thermal stability. The results prove that RHA is a valuable reinforcing material for HDPE and the environmental pollution arising from RHA can be eliminated in a profitable way by this technique.

Utilization of waste expanded polystyrene: Blends with silica-filled natural rubber

Expanded polystyrene (EPS) constitutes a considerable part of thermoplastic waste in the environment in terms of volume. In this study, this waste material has been utilized for blending with silica-reinforced natural rubber (NR). The NR/EPS (35/5) blends were prepared by melt mixing in a Brabender Plasticorder. Since NR and EPS are incompatible and immiscible a method has been devised to improve compatibility. For this, EPS and NR were initially grafted with maleic anhydride (MA) using dicumyl peroxide (DCP) to give a graft copolymer. Grafting was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy. This grafted blend was subsequently blended with more of NR during mill compounding. Morphological studies using Scanning Electron Microscopy (SEM) showed better dispersion of EPS in the compatibilized blend compared to the noncompatibilized blend. By this technique, the tensile strength, elongation at break, modulus, tear strength, compression set and hardness of the blend were found to be either at par with or better than that of virgin silica filled NR compound. It is also noted that the thermal properties of the blends are equivalent with that of virgin NR. The study establishes the potential of this method for utilising waste EPS