”Nonlinear optical properties of polymers containing azomesogens and chiral molecules: theoretical and experimental evaluations."

The present work emphasizes the use of chirality as an efficient tool to synthesize new types of second order nonlinear materials. Second harmonic generation efficiency (SHG) is used as a measure of second order nonlinear response. Nonlinear optical properties of polymers have been studied theoretically and experimentally. Polymers were designed theoretically by ab initio and semiempirical calculations. All the polymeric systems have been synthesized by condensation polymerization. Second harmonic generation efficiency of the synthesized systems has been measured experimentally by Kurtz and Perry powder method

Investigations on Nonlinear and Radiative Properties of Certain Phatonic Materials

Light in its physical and philosophical sense has captured the imagination of human mind right from the dawn of civilization. The invention of lasers in the 60’s caused a renaissance in the field of optics. This intense, monochromatic, highly directional radiation created new frontiers in science and technology. The strong oscillating electric field of laser radiation creates a. polarisation response that is nonlinear in character in the medium through which it passes and the medium acts as a new source of optical field with alternate properties. It was in this context, that the field of optoelectronics which encompasses the generation, modulation, transmission etc. of optical radiation has gained tremendous importance. Organic molecules and polymeric systems have emerged as a class of promising materials of optoelectronics because they offer the flexibility, both at the molecular and bulk levels, to optimize the nonlinearity and other suitable properties for device applications. Organic nonlinear optical media, which yield large third-order nonlinearities, have been widely studied to develop optical devices like high speed switches, optical limiters etc. Transparent polymeric materials have found one of their most promising applicationsin lasers, in which they can be used as active elements with suitable laser dyes doped in it. The solid-matrix dye lasers make possible combination of the advantages of solid state lasers with the possibility of tuning the radiation over a broad spectral range. The polymeric matrices impregnated with organic dyes have not yet widely used because of the low resistance of the polymeric matrices to laser damage, their low dye photostability, and low dye stability over longer time of operation and storage. In this thesis we investigate the nonlinear and radiative properties of certain organic materials and doped polymeric matrix and their possible role in device development

Novel potentiometric sensors for the selective determination of domperidone

The fabrication and electrochemical response characteristics of two novel potentiometric sensors for the selective determination of domperidone (DOM) are described. The two fabricated sensors incorporate DOM–PTA (phosphotungstic acid) ion pair as the electroactive material. The sensors include a PVC membrane sensor and a carbon paste sensor. The sensors showed a linear, stable, and near Nernstian slope of 56.5 and 57.8 mV/decade for PVC membrane and carbon paste sensors, respectively over a relatively wide range of DOM concentration (1.0 9 10-1–1.0 9 10-5 and 1.0 9 10-1–3.55 9 10-6 M). The response time of DOM–PTA membrane sensor was less than 25 s and that in the case of carbon paste sensor was less than 20 s.Auseful pH range of 4–6 was obtained for both types of sensors. A detection limit of 7.36 9 10-5 M was obtained for PVC membrane sensor and 1.0 9 10-6 M was obtained for carbon paste sensor. The proposed sensors showed very good selectivity toDOMin the presence of a large number of other interfering ions. The analytical application of the developed sensors in the determination of the drug in pharmaceutical formulations such as tablets was investigated. The results obtained are in good agreement with the values obtained by the standard method. The sensors were also applied for the determination ofDOMin real samples such as urine by the standard addition method.

Synthesis and Properties of Polyurethanes of Hexamethylene Di-Isocyanate with Multifunctional Chromophores in the Main Chain

Various polyurethanes containing photoactive bis(azo) and bis(o-nitrobenzyl) groups in the main chain were synthesized by polyaddition reactions of diols such as bis(4-hydroxyphenylazo)-2,20-dinitrodiphenylmethane, 4-hydroxy-3-methylphenylazo- 40-hydroxyphenylazo-2,20-dinitrodiphenylmethane and bis(4-hydroxy-3- methylphenylazo)-2,20-dinitrodiphenylmethane with hexamethylene di-isocyanate (HMDI), in dimethyl acetamide (DMAc) in the presence of di-n-butyltin dilaurate (DBTDL) as catalyst. All of them were characterized by IR, UV-vis, 1H NMR and 13C NMR spectra and also by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC).

Biodegradability Studies on LDPE-Starch Blends using Amylase-Producing Vibrios

Low-density polyethylene, (LDPE) was mixed with two grades of tapioca starch–lowgrade and high-grade. Various compositions were prepared and mechanical and thermal studies performed. The biodegradability of these samples was checked using a culture medium containing Vibrios (an amylase-producing bacteria), which was isolated from a marine benthic environment. The soil burial test and reprocessability of these samples were checked. The studies on biodegradability show that these blends are partially biodegradable. These low-density polyethylene-starch blends are reprocessable without sacrificing much of their mechanical properties

Influence Of Additives On The Drain Down Characteristics Of Stone Matrix Asphalt Mixtures

In Kerala highways, where traditional dense graded mixtures are used for the surface courses, major distress is due to moisture induced damages. Development of stabilized Stone Matrix Asphalt (SMA) mixtures for improved pavement performance has been the focus of research all over the world for the past few decades. Many successful attempts are made to stabilize SMA mixtures with synthetic fibres and polymers. India, being an agricultural economy produces fairly huge quantity of natural fibres such as coconut, sisal, banana, sugar cane, jute etc.. Now- a -days the disposal of waste plastics is a major concern for an eco- friendly sustainable environment. This paper focuses on the influence of additives like coir, sisal, banana fibres (natural fibres), waste plastics (waste material) and polypropylene (polymer) on the drain down characteristics of SMA mixtures. A preliminary investigation is conducted to characterize the materials used in this study. Drain down sensitivity tests are conducted to study the bleeding phenomena and drain down of SMA mixtures. Based on the drain down characteristics of the various stabilized mixtures it is inferred that the optimum fibre content is 0.3% by weight of mixture for all fibre mixtures irrespective of the type of fibre. For waste plastics and polypropylene stabilized SMA mixtures, the optimum additive contents are respectively 7% and 5% by weight of mixture. Due to the absorptive nature of fibres, fibre stabilizers are found to be more effective in reducing the drain down of the SMA mixture. The drain values for the waste plastics mix is within the required specification range. The coir fibre additive is the best among the fibres investigated. Sisal and banana fibre mixtures showed almost the same characteristics on stabilization.

Processability And Magnetic Properties Of Rubber Ferrite Composites Containing Barium Ferrite

Rubber ferrite composites (RFC) are magnetic polymer composites and have a variety of applications as flexible magnets, pressure=photo sensors, and microwave absorbers. The mouldability into complex shapes is one of the advantages of these magnetic elastomers. They have the potential of replacing the conventional ceramic materials, due to theire flexible nature. In the present study, the incorporation of pre-characterized hexagonal ferrites, namely barium ferrite (BaFe12O19), into natural rubber matrix is carried out according to a suitable recipe for various loadings of the filler. The processability of these compounds was determined by evaluating the cure characteristics: scorch time, cure time, and minimum and maximum torque. It has been found that the addition of magnetic fillers does not affect the processability of the composites, whereas the physical properties are modified. The magnetic properties of these composites containing various loadings of the magnetic filler were also investigated. The magnetic properties of RFC can be controlled by the addition of appropriate amount of the ferrite filler.

Cure Kinetics and Sorption Characteristics of Neoprene-Based Rubber Ferrite Composites

Rubber ferrite composites were prepared by incorporating nickel ferrite in a neoprene rubber matrix. Kinetics of the cure reaction were determined from the rheometric torque values and found to follow first-order kinetics. Analysis of the swelling behavior of the rubber ferrite composites in toluene elucidates the mechanism of solvent penetration and sorption characteristics, and reveals the extent of the physical interaction of the ferrite particles with the neoprene rubber matrix. Mechanical properties of rubber ferrite composites were determined, which support the reinforcing nature of nickel ferrite to the neoprene rubber matrix. These results show that magnetic composites with the required processing safety can be prepared economically by incorporating higher amounts of nickel ferrite in the neoprene rubber matrix

A study on mitigating the effect of sulphates in lime stabilised Cochin marine clays

Soft clays known for their high compressibility, low stiffness and low shear strength are always associated with large settlement. In place soil treatment using calcium-based stabilizers like lime and cement is a feasible solution to readdress strength deficiencies and problematic shrink/swell behaviour of unstable subgrade soils. Out of these, lime has been proved unambiguously as the most effective and economical stabilising agent for marine clays. Lime stabilisation creates long-term chemical changes in unstable clay soils to create strong, but flexible, permanent structural layers in foundations and other pavement systems. Even though calcium-based stabilizers can improve engineering properties of soft clays, problems can arise when they are used in soils rich in sulphates. It is possible for marine clays to be enriched with sulphates, either by nature or due to the discharge of nearby industrial wastes containing sulphates. The presence of sulphates is reported to adversely affect the cation exchange and pozzolanic reactions of cement and lime treated soil systems. The anions of sulphates may combine with the available calcium and alumina, and form insoluble ettringite in the soil system. Literature on sulphate attack in lime treated marine clays reports that formation of ettringite in lime-sodium sulphate-clay system is capable of adversely affecting the engineering behavior of marine clays. Only very few studies have been conducted on soft marine clays found along the coastal belt of Kerala and that too, is limited to Cochin marine clays. The studies conducted also have the limitation that the strength behaviour of lime stabilised clay was investigated only for one year. Practically no data pertaining to long term adverse effects likely to be brought about by sulphates on the strength and compressibility characteristics of Cochin marine clays is available. The overriding goal of this investigation was thus to examine the effectiveness of lime stabilisation in Cochin marine clays under varying sulphate contents. The study aims to reveal the changes brought about by varying sulphate contents on both physical and engineering properties of these clays stabilised by lime and the results for various curing periods up to two years is presented in this thesis. Quite often the load causing an unacceptable settlement may be less than the load required to cause shear failure and therefore attempt has been made in this research to highlight sulphate induced changes in both the compressibility and strength characteristics of lime treated Cochin marine clays. The study also aimed at comparing the available IS methods for sulphate quantification and has attempted to determine the threshold level of sulphate likely make these clays vulnerable by lime stabilisation. Clays used in this study were obtained from two different sites in Kochi and contained sulphate in two different concentrations viz., 0.5% and 0.1%. Two different lime percentages were tried out, 3% and 6%. Sulphate content was varied from 1% to 4% by addition of reagent grade sodium sulphate. The long term influence of naturally present sulphate is also investigated. X-ray diffraction studies and SEM studies have been undertaken to understand how the soil-lime reactions are affected in the presence of sodium sulphate. Natural sulphate content of 0.1% did not seem to have influenced normal soil lime reactions but 0.5% sulphate could induce significant changes adversely in both compressibility and strength behaviour of lime treated clays after long duration. Compressibility is seen to increase drastically with increasing sulphate content suggesting formation of ettringite on curing for longer periods. Increase in compression index and decrease in bond strength with curing period underlined the adverse effects induced in lime treated marine clays by the presence of sulphates. Presence of sulphate in concentrations ranging from 0.5 % to 4% is capable of adversely affecting the strength of lime treated marine clays. Considerable decrease is observed with increasing concentrations of sulphate. Ettringite formation due to domination of sodium ions in the system was confirmed in mineralogical studies made. Barium chloride and barium hydroxide is capable of bringing about beneficial changes both in compressibility and strength characteristics of lime treated Cochin marine clays in the presence of varying concentrations of sulphate and is strongly influenced by curing time. Clay containing sodium sulphate has increased strength values when either of barium compounds was used with lime ascompared with specimens treated with lime only. Barium hydroxide is observed to remarkably increase the strength as compared to barium chloride,when used in conjunction with lime to counteract the effect of sulphate.

Studies on the use of Nanokaolin, MWCNT and Graphene in NBR and SBR

The current research investigates the possibility of using unmodified and modified nanokaolin, multiwalled carbon nanotube (MWCNT) and graphene as fillers to impart enhancement in mechanical, thermal, and electrical properties to the elastomers. Taking advantage of latex blending method, nanoclay, MWCNT and graphene dispersions, prepared by ultra sound sonication are dispersed in polymer latices. The improvement in material properties indicated better interaction between filler and the polymer.MWCNT and graphene imparted electrical conductivity with simultaneous improvement in mechanical properties. Layered silicates prepared by microwave method also significantly improve the mechanical properties of the nanocomposites. The thesis entitled ‘Studies on the use of Nanokaolin, MWCNT and Graphene in NBR and SBR’ consists of ten chapters. The first chapter is a concise introduction of nanocomposites, nanofillers, elastomeric matrices and applications of polymer nanocomposites. The state-of-art research in elastomer based nanocomposites is also presented. At the end of this chapter the main objectives of the work are mentioned. Chapter 2 outlines the specifications of various materials used, details of experimental techniques employed for preparing and characterizing nanocomposites. Chapter3 includes characterization of the nanofillers, optimsation of cure time of latex based composites and the methods used for the preparation of latex based and dry rubber based nanocomposites. Chapter4 presents the reinforcing effect of the nanofillers in XNBR latex and the characterization of the nanocomposites. Chapter5 comprises the effect of nanofillers on the properties of SBR latex and their characterization Chapter 6 deals with the study of cure characteristics, mechanical and thermal properties and the characterization of NBR based nanocomposites. Chapter7 is the microwave studies of MWCNT and graphene filled elastomeric nanocomposites. Chapter 8 gives details of the preparation of layered silicates, their characterization and use in different elastomeric matrices. Chapter 9 is the study of mechanical properties of nanoclay incorporated nitrile gloves .Chapter 10 presents the summary and conclusions of the investigation.

VUV-Laserablation von Spinnenseide

Spinnenseide gehört zu den stabilsten bekannten Polymerverbindungen. Spinnfäden können bis auf das Dreifache ihrer ursprünglichen Länge gedehnt werden, bevor sie reißen, und dabei mit rund 160 MJ/m³ mehr als dreimal soviel Energie absorbieren wie die stärkste synthetisch hergestellte Faser Kevlar (50 MJ/m³). Dabei weisen Spinnfäden mit 2 bis 5 Mikrometer nur ein Zehntel des Durchmessers eines menschlichen Haares auf. Das präzise, berührungslose Bearbeiten von Spinnenseide ist für verschiedene technische Anwendungen interessant, insbesondere wenn dabei ihre außergewöhnlichen Eigenschaften erhalten bleiben. Könnten die von Natur aus dünnen Seidenfäden gezielt in ihrem Durchmesser verringert werden, so wären sie unter anderem in der Mikroelektronik einzusetzen. Hier könnten sie als Trägermaterial für eine dünne, elektrisch leitfähige Schicht fungieren. Man erhielte Nanodrähte, die auch in mechanisch besonders belasteten Mikroelektronikbauteilen (MEMS) Verwendung finden könnten. In dieser Arbeit wird die Verwendung der laserinduzierten Ablation zur gezielten Bearbeitung von Haltefäden der Schwarzen Witwe (Latrodectus hesperus) beschrieben. Eingesetzt wurde ein VUV-Excimerlaser vom Typ LPF 205 (Lambda-Physik, Göttingen) mit einer Wellenlänge von 157 nm und einer Pulsdauer von 18 ns. Eine berührungslose Laserbearbeitung bei 157 nm erlaubt einen effizienten und präzisen Abtrag von Material durch Ablation aufgrund der geringen optischen Eindringtiefe von unter 100 nm oberhalb einer Schwellenfluenz (Energie/Fläche) von Φth=29 mJ/cm², ohne dabei das umgebende Material thermisch zu beeinträchtigen. Parallel zur Ablation setzt allerdings eine wellenförmige Oberflächenstrukturierung auf der Faseroberfläche ein, wodurch die mechanische Belastbarkeit der Faser entscheidend geschwächt wird. Die Ursache hierfür liegt im Abbau materialbedingter Spannungsfelder („stress release“) innerhalb einer durch das Laserlicht induzierten dünnen Schmelzschicht. Im Rahmen dieser Arbeit ist es nun gelungen, diese Strukturen durch einen anschließenden Glättungsprozeß zu entfernen. Dabei wird auf der bestrahlten Oberfläche mittels Laserlichts eine glatte Ablation erzielt. Mit feinerer Abstufung dieser Prozeßschritte konnte der Durchmesser des verwendeten Spinnenseidefadens zum Teil um 70 Prozent bis auf ca. 750 nm verringert werden. Durch Zugfestigkeitsexperimente wurde belegt, daß die mechanischen Eigenschaften der so bearbeiteten Spinnenseide weitgehend erhalten bleiben. Die im Rahmen dieser Arbeit angewandte Methode erlaubt somit eine präzise Laserablation von Spinnenseide und ähnlichen hochabsorbierenden Materialien, ohne deren Kernsubstanz in ihrer Beschaffenheit zu verändern.

Biofilmbildung bei Pflanzen-assoziierten Bakterien der Gattung Methylobacterium und molekulargenetisch-physiologische Charakterisierung eines neuen Marchantia-Isolats (Mtb. sp. JT1)

Bakterien existieren bevorzugt in Biofilmen. Das Zusammenleben in diesen Gemeinschaften bietet den einzelnen Mikroben einen wirksamen Schutz und ermöglicht die Ausbildung langfristiger, synergistischer Wechselwirkungen, die mit multizellulären Systemen verglichen werden können. Biofilme bestehen aus Mikrooganismen-Populationen, die sich an Grenzflächen ansammeln und typischerweise von einer Matrix aus extrazellulären polymeren Substanzen umgeben sind. Auch auf Pflanzen-Oberflächen bilden viele Bakterien Biofilme, um ihre Überlebenswahrscheinlichkeit zu erhöhen. In dieser Arbeit wurde die Biofilmbildung bei Pflanzen-assoziierten Bakterien der Gattung Methylobacterium (Mtb.) untersucht, wobei molekular- und mikrobiologische sowie mikroskopische Techniken eingesetzt wurden. Es zeigte sich, dass alle untersuchten Vertreter der Gattung Methylobacterium in unterschiedlichem Ausmaß Biofilme bilden. Die Ausprägung ist dabei Taxon (bzw. Isolat)-spezifisch und vor allem von der Stickstoff-Verfügbarkeit abhängig. Jedoch spielen auch andere Umweltfaktoren, wie die Versorgung der Zellen mit Phosphat und die Zelldichte, bei der Ausbildung der überzellulären Einheiten eine wichtige Rolle. Die Matrix der Biofilme wird meist durch ein fibrilläres Netzwerk gebildet. Dabei handelt es sich um Heteropolysaccharide, die von den Bakterien synthetisiert und sezerniert werden. Einige Isolate bilden zusätzlich zahlreiche Fimbrien (Auswüchse), durch die sie an andere Zellen oder Oberflächen binden können. Im zweiten Teil dieser Arbeit wurden mehrere neue Methylobacterium-Isolate physiologisch und molekulargenetisch charakterisiert (Nährstoffverwertung, DNA-Sequenzen verschiedener Gene, phylogenetische Analysen usw.). Im Vordergrund stand hierbei der von einer urtümlichen Landpflanze, dem Lebermoos (Marchantia polymorpha), isolierte Stamm Mtb. sp. JT1. Dabei zeigten sich deutliche Unterschiede in der Morphologie und Physiologie des Bakterienstamms JT1 und dem nahe verwandten Stamm 5b.2.20 zu den bereits beschriebenen Taxa der Gattung, so dass eine Spezies-Neubeschreibung erforderlich war. Als Artname wurde aufgrund der außergewöhnlichen Oberflächenstrukturen Mtb. fimbriae sp. nov. eingeführt. Auch andere Methylobakterien (unter anderem Isolat Mtb. sp. F3.2, isoliert vom Laubmoos Funaria hygrometrica) stellen wahrscheinlich Vertreter einer neue Spezies dar (Artname Mtb. funariae sp. nov.). Jedoch zeigen Mtb. fimbriae und Mtb. funariae nur geringe physiologische und morphologische Unterschiede und konnten auf Grundlage umfassender DNA-DNA-Hybridisierungs-Studien nicht eindeutig voneinander abgegrenzt werden.

Effects of activated charcoal and quebracho tannins on the turnover of goat manure in irrigated organic agriculture of the subtropics

Agriculture in semi-arid and arid regions is constantly gaining importance for the security of the nutrition of humankind because of the rapid population growth. At the same time, especially these regions are more and more endangered by soil degradation, limited resources and extreme climatic conditions. One way to retain soil fertility under these conditions in the long run is to increase the soil organic matter. Thus, a two-year field experiment was conducted to test the efficiency of activated charcoal and quebracho tannin extract as stabilizers of soil organic matter on a sandy soil low in nutrients in Northern Oman. Both activated charcoal and quebracho tannin extract were either fed to goats and after defecation applied to the soil or directly applied to the soil in combination with dried goat manure. Regardless of the application method, both additives reduced decomposition of soil-applied organic matter and thus stabilized and increased soil organic carbon. The nutrient release from goat manure was altered by the application of activated charcoal and quebracho tannin extract as well, however, nutrient release was not always slowed down. While activated charcoal fed to goats, was more effective in stabilising soil organic matter and in reducing nutrient release than mixing it, for quebracho tannin extract the opposite was the case. Moreover, the efficiency of the additives was influenced by the cultivated crop (sweet corn and radish), leading to unexplained interactions. The reduced nutrient release caused by the stabilization of the organic matter might be the reason for the reduced yields for sweet corn caused by the application of manure amended with activated charcoal and quebracho tannin extract. Radish, on the other hand, was only inhibited by the presence of quebracho tannin extract but not by activated charcoal. This might be caused by a possible allelopathic effect of tannins on crops. To understand the mechanisms behind the changes in manure, in the soil, in the mineralisation and the plant development and to resolve detrimental effects, further research as recommended in this dissertation is necessary. Particularly in developing countries poor in resources and capital, feeding charcoal or tannins to animals and using their faeces as manure may be promising to increase soil fertility, sequester carbon and reduce nutrient losses, when yield reductions can be resolved.

Plasma polymerization of C[subscript 4]F[subscript 8] thin film on high aspect ratio silicon molds

High aspect ratio polymeric micro-patterns are ubiquitous in many fields ranging from sensors, actuators, optics, fluidics and medical. Second generation PDMS molds are replicated against first generation silicon molds created by deep reactive ion etching. In order to ensure successful demolding, the silicon molds are coated with a thin layer of C[subscript 4]F[subscript 8] plasma polymer to reduce the adhesion force. Peel force and demolding status are used to determine if delamination is successful. Response surface method is employed to provide insights on how changes in coil power, passivating time and gas flow conditions affect plasma polymerization of C[subscript 4]F[subscript 8].

UV Embossed Plastic Chip for Protein Separation and Identification

This report demonstrates a UV-embossed polymeric chip for protein separation and identification by Capillary Isoelectric Focusing (CIEF) and Matrix Assisted Laser Desportion/Ionization Mass Spectrometry (MALDI-MS). The polymeric chip has been fabricated by UV-embossing technique with high throughput; the issues in the fabrication have been addressed. In order to achieve high sensitivity of mass detection, five different types of UV curable polymer have been used as sample support to perform protein ionization in Mass Spectrometry (MS); the best results is compared to PMMA, which was the commonly used plastic chip for biomolecular separation. Experimental results show that signal from polyester is 12 times better than that of PMMA in terms of detection sensitivity. Finally, polyester chip is utilized to carry out CIEF to separate proteins, followed by MS identification.