Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.

”Studies on Selected conducting polymers for Microwave and Electrical Applications

The electrical properties of polymers make up an inherently interdisciplinary topic, being closely associated, on the one hand, with the mechanical properties of polymers polarization and relaxation) and, on the other hand, with the semi conductive properties (conduction and break down). In addition, unlike conventional technologies, which use these properties in its various applications like antistatic coatings, rechargeable batteries, sensors, electrochromic devices, electrochemical devices etc, microwave technology extract the microwave absorbing ability of electrically conducting polymers. The conducting polymers are widely used in its potential applications like electro magnetic interference shielding, satellite communication links, beam steering radars, frequency selective surfaces etc. Considering the relevance of microwave applications of conducting polymers, the study of microwave properties of conducting polymers stands poised to become a compelling choice for synthetic chemists and condensed - matter physicists, physical chemists and material scientists, electrochemists and polymer scientists. The main aim of the present work is to study the microwave and low frequency properties of various conducting polymers, conducting semi-interpenetrating networks, conducting copolymers and to characterise it. Also this thesis collated the microwave properties of these conducting systems and exposes the various technologically important applications in the industrial, scientific, communication and defence applications.

Investigation of structural, optical and electrical properties and valence band splitting in cu-ln-se compounds

Investigations on thin films that started decades back due to scientific curiosity in the properties of a two-dimensional solid, has developed into a leading research field in recent years due to the ever expanding applications of the thin films in the fann of a variety of active and passive microminiaturized components and devices, solar cells, radiation sowces and detectors, magnetic memory devices, interference filters, refection and antireflection coatings etc. [1]. The recent environment and energy resource concerns have aroused an enonnous interest in the study of materials in thin film form suitable for renewable energy sources such as photovoltaic devices. Recognition of the immense potential applications of the chalcopyrites that can fonn homojunctions or heterojunctions for solar cell fabrication has attracted many researchers to extensive and intense research on them. In this thesis, we have started with studies performed on CuInSe, thin films, a technologically well recognized compound belonging to the l•ill-VI family of semiconductors and have riveted on investigations on the preparation and characterization of compoWlds Culn3Se5. Culn5Seg and CuIn7Se12, an interesting group of compounds related to CuInSe2 called Ordered Vacancy Compounds, having promising applications in photovoltaic devices. A pioneering work attempted on preparing and characterizing the compound Culn7Sel2 is detailed in the chapters on OVC's. Investigation on valence band splitting in avc's have also been attempted for the first time and included as the last chapter in the thesis. Some of the salient features of the chalcopyrite c.ompounds are given in the next section .of this introductory chapter.

An investigation on the preparation and properties of some transparent conducting oxides and lead selenide thin films”

The investigation of physical properties of matter has progressed so much during the last hundred years. Today physics is divided in to a large distinct group of special branches. These branches are distinguished by the particular area studied, method of investigation and so on. An independent and important branch that has developed is the physics ofthin films.Any object in solid or liquid form with one of its dimensions very much smaller than that of the other two may be called a thin film. It is having only one common property, namely, one of their dimensions is very small, though all their physical properties may be different. Thin layers of oil, floating on the surface of water, with their fascinating colours, have attracted men’s curiosity from time immemorial. The earliest application of thin films was the protective coatings in the form of paints. A thin layer of tin has been used from ancient times to protect copper utensils from corrosion. Indium thin films are used in certain applications on account of their good lubricating property. Relay contacts are coated with thin films of rare earth metals in order to prevent burning due to arcing. Hard coatings are also available using diamond like carbon (i-carbon). The basic properties of thin films are of considerable interest because of their potential applications in various fields of science and technology

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.

Evolution of structural and magnetic properties of Co–Fe based metallic glass thin films with thermal annealing

Ultra thin films based on CoFe were prepared from a composite target employing thermal evaporation. The microstructure of the films was modified by thermal annealing. The relationship between microstructure and magnetic properties of the films was investigated using techniques like glancing angle X-ray diffraction (GXRD), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). The GXRD and TEM investigations showed an onset of crystallization of CoFe at around 373 K. The magnetic softness of the films improved with thermal annealing but at higher annealing temperature it is found to be deteriorating. Annealing inducedmodification of surface morphology of the alloy thin filmswas probed by atomic force microscopy (AFM). Surface smoothening was observed with thermal annealing and the observed magnetic properties correlate well with surface modifications induced by thermal annealing

Dezincification of Epoxy Coated Brass in Cochin Estuary, India

Inhibited α brasses are largely immune to dezincification in most water, but the effect of tin and arsenic addition to α/β brasses is not so reliable or predictable in controlling the problem. There have been many cases of dezincification in duplex brasses in both fresh water and seawater. There is no reliable method of inhibiting the dezincification of two-phase brass despite there are some protection methods such as inhibitors, electro deposition and electro polymerization. Organic coatings are effectively used for the protection of metals due to their capacity to act as a physical barrier between the metal surface and corrosive environment. Hence, epoxy coating on brass was applied and effect of this against dezincification in Cochin estuarine water over a period of one year was studied and reported in this paper

Chemical gas sensors based on functionalized self-actuated piezo-resistive cantilevers

Der Schwerpunkt dieser Arbeit liegt in der Anwendung funktionalisierter Mikrocantilever mit integrierter bimorpher Aktuation und piezo-resistiver Detektion als chemische Gassensoren für den schnellen, tragbaren und preisgünstigen Nachweis verschiedener flüchtiger Substanzen. Besondere Beachtung erfährt die Verbesserung der Cantilever-Arbeitsleistung durch den Betrieb in speziellen Modi. Weiterer Schwerpunkt liegt in der Untersuchung von spezifischen Sorptionswechselwirkungen und Anwendung von innovativen Funktionsschichten, die bedeutend auf die Sensorselektivität wirken.

Amphiphile Verbindungen der 14. Gruppe - Synthese, Eigenschaften und Anwendungen von Organosilanolen

Im Rahmen dieser Dissertation wurde an der Darstellung stabiler, amphiphiler Silantriole gearbeitet. Es ist gelungen eine kontinuierliche Reihe sukzessive um CH2-Einheiten verlängerter Silantriole des Typs H3C(CH2)nC(CH3)2Si(OH)3 (n = 1-5) durch eine vierstufige Synthesesequenz ausgehend von n-Alkylbromiden herzustellen und zum Teil röntgenographisch zu untersuchen. Ihre oberflächenaktiven Eigenschaften in wässrigen Lösungen konnten erstmals mittels Oberflächenspannungsmessungen belegt werden. Durch gezielte Kondensationsreaktionen mit Trifluoressigsäure wurden ausgehend von den oben beschriebenen Silantriolen selektiv die entsprechenden Disiloxan-Tetrole erhalten und ebenfalls zum Teil durch Röntgenstrukturanalysen charakterisiert. Als weitere Kondensationsprodukte der Silantriole konnten die ersten Octasilsesquioxane mit tertiären Kohlenstoff-Substituenten durch Umsetzungen mit n-Bu4NF selektiv und in hohen Ausbeuten erhalten und ebenfalls röntgenographisch identifiziert werden. Es wurde an der Darstellung Aryl-substituierter Silantriole RSi(OH)3 (R = Mesityl-, Xylyl- und Tetramethyl-phenyl-) gearbeitet. Diese zeichnen sich jedoch durch ihre hohe Instabilität in Lösung und im Festkörper aus und konnten zum Teil nur zusammen mit ihren primären Kondensationsprodukten erhalten werden. Darüber hinaus wurden stabile Silandiole des Typs R(t-Bu)Si(OH)2 (R = n-Butyl und n-Pentyl) sowie das (o-CF3C6H4)2Si(OH)2 in hohen Ausbeuten und selektiv synthetisiert. Die Festkörpereigenschaften des (o-CF3C6H4)2Si(OH)2 sowie seiner Vorstufe (o-CF3C6H4)2SiCl2 konnten durch Kristallstrukturanalysen genauer untersucht werden. In der Arbeit wurden die ersten Anwendungen von Silanolen als Silan-Kupplungsreagenzien bei der Oberflächenmodifizierung von Glas beschrieben. Im Gegensatz zu gängigen säureassistierten Beschichtungen zeichnen sich diese Silanol-Beschichtungen durch eine deutlich höhere Hydrophobizität aus. Dies konnte durch Kontaktwinkel- und Zeta-Potential-Messungen bestätigt werden. Durch Röntgenreflektivitäts- und Sarfus-Messungen ist die Ausbildung von Monolagen im Falle von t-BuSi(OH)3-beschichteten Oberflächen plausibel. Die Oberflächenmorphologie der Silantriol-Beschichtungen wurde mittels AFM-Messungen untersucht. Die Si(OH)3-Funktion konnte in der vorliegenden Arbeit als ein neues Pharmakophor etabliert werden. Die Silantriole CySi(OH)3, TerSi(OH)3 und CH3CH2C(CH3)2Si(OH)3 (Cy = Cyclohexyl, Ter = Terphenyl) sind in der Lage das Enzym Acetylcholinesterase reversibel zu hemmen. Dabei zeigt das CySi(OH)3 mit 45 % relativ zur Kontrolle die höchste Inhibition.

Cooled Infrared Dichroic Beamsplitters and Filters for the MIRI Spectrometer and Imager (5-29µm)

The spectral design and fabrication of cooled (7K) mid-infrared dichroic beamsplitters and bandpass filter coatings for the MIRI spectrometer and imager are described. Design methods to achieve the spectral performance and coating materials are discussed.

Characteristics of silica-rich pedofeatures in a buried paleosol

Whitish and whitish-light brown milky-like textural pedofeatures and impregnations were found in the voids and the matrix of buried paleosols older than 2.7 million years in a site in Sardinia, Italy. The pedofeatures were described and analysed using micromorphology, X-ray diffraction and microprobe techniques, and their spatial distribution correlated with field evidence. The suite of analyses showed that the main components of the pedofeatures were more or less ordered silica phases. As well as forming a matrix cement, these pedofeatures also occurred as coatings and infillings in pores. Significant amounts of alumina and, less, Mg, Ca and Fe were also present in the pedofeatures, possibly in the form of silicate coatings and inclusions/impurities, or alumino-silicates of the adjacent soil matrix. A number of hypotheses are drawn on the possible mechanisms of formation of these silica-rich pedofeatures, including the possibility of prolonged weathering of volcanic materials and the resulting formation of colloids and more or less ordered silica phases, with successive dehydration and progressive ordering of phases during the at least 2.5 million years. (C) 2003 Elsevier B.V. All rights reserved.

The solubility of gypsum in calcareous soils

Three gypsiferous-calcareous soils from the Al-Hassa Oasis in Saudi Arabia were examined to determine the conditions under which dissolution of gypsum could be hindered by the formation of coatings of calcite during leaching. Batch extraction with water of a sandy clay loam, a sandy clay and a sandy loam containing 40, 26 and 5% gypsum and 14, 12 and 13% calcite respectively was followed by chemical analysis of the extracts, SEM examination and XRD and EDX microprobe analysis. Extraction in closed centrifuge tubes for I h or 5 h showed that initially gypsum dissolved to give solutions near to equilibrium but then in the sandy clay loam, between one quarter and one third of the gypsum could not dissolve. In the sandy clay about one fifth of the gypsum could not dissolve with none remaining in the sandy loam. All the extracts were close to equilibrium with calcite. SEM and EDX examination showed that coatings of calcite had formed on the gypsum particles. The sandy clay loam was also extracted using an open system in which either air or air +1% CO2 was bubbled through the suspensions for 1 h with stirring. The gypsum dissolved more rapidly and all of the gypsum dissolved. Thus, where the rate of dissolution of gypsum was rapid, calcite did not manage to cover the gypsum surfaces probably because the surface was being continuously removed. Slower leaching conditions in the field are likely to be conducive to the formation of coatings and less dissolution of gypsum. (c) 2006 Elsevier B.V. All rights reserved.

Dust production and the release of iron oxides resulting from the aeolian abrasion of natural dune sands

Global dust trajectories indicate that significant quantities of aeolian-transported iron oxides originate in contemporary dryland areas. One potential source is the iron-rich clay coatings that characterize many sand-sized particles in desert dunefields. This paper uses laboratory experiments to determine the rate at which these coatings can be removed from dune sands by aeolian abrasion. The coatings impart a red colour to the grains to which previous researchers have assigned variable geomorphological significance. The quantities or iron removed during a 120 hour abrasion experiment are small (99 mg kg(-1)) and difficult to detect by eye; however, high resolution spectroscopy clearly indicates that ferric oxides are released during abrasion and the reflectance of the particles alters. One of the products of aeolian abrasion is fine particles (<10 mum diameter) with the potential for long distance transport. Copyright (C) 2004 John Wiley Sons, Ltd.

Weathering microenvironments on feldspar surfaces: implications for understanding fluid-mineral reactions in soils

The mechanisms by which coatings develop on weathered grain surfaces, and their potential impact on rates of fluid-mineral interaction, have been investigated by examining feldspars from a 1.1 ky old soil in the Glen Feshie chronosequence, Scottish highlands. Using the focused ion beam technique, electron-transparent, foils for characterization by transmission electron microscopy were cut from selected parts of grain surfaces. Some parts were bare whereas others had accumulations, a few micrometres thick, of Weathering products, often mixed with mineral and microbial debris. Feldspar exposed at bare grain surfaces is crystalline throughout and so there is no evidence for the presence of the amorphous 'leached layers' that typically form in acid-dissolution experiments and have been described from some natural Weathering contexts. The weathering products comprise sub-mu m thick crystallites of an Fe-K aluminosilicate, probably smectite, that have grown within an amorphous and probably organic-rich matrix. There is also evidence for crystallization of clays having been mediated by fungal hyphae. Coatings formed within Glen Feshie soils after similar to 1.1 ky are insufficiently continuous or impermeable to slow rates Of fluid-feldspar reactions, but provide valuable insights into the complex Weathering microenvironments oil debris and microbe-covered mineral surfaces.