Laser Spectroscopy: TDLAS instrumentation and NIR analysis of some organic materials

Near-infrared spectroscopy can be a workhorse technique for materials analysis in industries such as agriculture, pharmaceuticals, chemicals and polymers. A near-infrared spectrum represents combination bands and overtone bands that are harmonics of absorption frequencies in the mid-infrared. Near-infrared absorption includes a combination-band region immediately adjacent to the mid-infrared and three overtone regions. All four near-infrared regions contain "echoes" of the fundamental mid-infrared absorptions. For example, vibrations in the mid-infrared due to the C-H stretches will produce four distinct bands in each of the overtone and combination regions. As the bands become more removed from the fundamental frequencies they become more widely separated from their neighbors, more broadened and are dramatically reduced in intensity. Because near-infrared bands are much less intense, more of the sample can be used to produce a spectra and with near-infrared, sample preparation activities are greatly reduced or eliminated so more of the sample can be utilized. In addition, long path lengths and the ability to sample through glass in the near-infrared allows samples to be measured in common media such as culture tubes, cuvettes and reaction bottles. This is unlike mid-infrared where very small amounts of a sample produce a strong spectrum; thus sample preparation techniques must be employed to limit the amount of the sample that interacts with the beam. In the present work we describe the successful the fabrication and calibration of a linear high resolution linear spectrometer using tunable diode laser and a 36 m path length cell and meuurement of a highly resolved structure of OH group in methanol in the transition region A v =3. We then analyse the NIR spectrum of certain aromatic molecules and study the substituent effects using local mode theory

Studies on rubber compositions as passive acoustic materials in underwater electro acoustic transducer technology-and their aging characteristics

Rubber has become an indispensable material in Ocean technology. Rubber components play critical roles such as sealing, damping, environmental protection, electrical insulation etc. in most under water engineering applications. Technology driven innovations in electro acoustic transducers and other sophisticated end uses have enabled quantum jump in the quality and reliability of rubber components. Under water electro acoustic transducers use rubbers as a critical material in their construction. Work in this field has lead to highly reliable and high performance materials which has enhanced service life of transducers to the extent of 1015 years. Present work concentrates on these materials. Conventional rubbers are inadequate to meet many of the stringent functional of the requirements. There exists large gap of information in the rubber technology of under water rubbers, particularly in the context of under water electro acoustic transducers. Present study is towards filling up the gaps of information in this crucial area. The research work has been in the area of compounding and characterisation of rubbers for use in under water electro acoustic transducers. The study also covers specific material system such as encapsulation material, baffle material, seal material, etc. Life prediction techniques of under water rubbers in general has been established with reference to more than one functional property. This thesis is divided into 6 chapters.

Optical and thermal characterization of dye intercalated montmorillonites and rare earth doped materials

The advent of high optical quality transparent nano—structured glasses, the so-called transparent glass ceramics or vitroceramics disclosed the possibility of producing nano-sized photonic devices based on rare-earth doped up—converters. Transparent glass ceramics have been investigated as hosts for lanthanide ions envisioning the production of materials that are easy to shape and with high performance for photonic applications. Rare earth doped glasses have been extensively studied due to their potential applications in optical devices such as solid state lasers and optical fibers. Various photothermal and optical techniques have been successfully applied for the thermal and optical characterization of these rare earth doped materials. In the present thesis, the effective thermal parameters like thermal diffusivity and thermal effusivity of complex materials for various applications have been investigated using photothermal methods along with their optical characterization utilising the common optical absorption as well as fluorescence spectroscopic techniques. These sensitive optical procedures are also essential for exploiting these materials for further photonic applications.

Preparation of useful raw materials from Refinery sludge and its utilisation in rubber processing

Petroleum, a mixture of organic compounds, comes from underground rock formations ranging in age from ten to several hundred million years. The process by which it is formed and developed is not yet completely known. Studies indicate that petroleum is formed mainly from microscopic-sized marine animals and plants. When these organisms died in water of low oxygen content, they did not decompose. Thus their remains sank to the bottom to be buried under accumulations of sediment. Their conversion to petroleum remains a subject of research even today.

Importance of the embedding environment on the strain within small rings in siliceous materials

The effect of the local environment on the energetic strain within small (SiO)N rings (with N=2,3) in silica materials is investigated via periodic model systems employing density functional calculations. Through comparison of the energies of various nonterminated systems containing small rings in strained and relatively unstrained environments, with alpha quartz, we demonstrate how small ring strain is affected by the nature of the embedding environment. We compare our findings with numerous previously reported calculations, often predicting significantly different small-ring strain energies, leading to a critical assessment of methods of calculating accurate localized ring energies. The results have relevance for estimates of the strain-induced response (e.g., chemical, photo, and radio) of small silica rings, and the propensity for them to form in bulk glasses, thin films, and nanoclusters.

Materials for Fish Nets-Their Properties, Selection and Preservation

The properties of synthetic fibres vary with thc inherent physical characteristics of the basic raw materials used mode of preparation of yarns and method of construction of twines. Since the synthetic fibres as maufactured from polymers which are synthesized from simple chemical units, the qualities of man-made fibres can he influenced by the process of manufacture and certain modifications can even be introduced at the processing stage to meet any specific requirement to a certain extent. Hence, an elaborate study of the properties of fish not twines produced has been taken up with a view to determining their suitability for various types of fishing gear with particular reference to conditions prevailing in India.

Non-destruct|ve testing of non-metallic materials using microwaves

The motivatitni for" the present work is from .a project sanctioned by TSRO. The work involved the development of a quick and reliable test procedure using microwaves, for tflue inspection of cured propellant samples and a method to monitor the curing conditions of propellant mix undergoing the curing process.Normal testing CHE the propellant samples involvecuttimg a piece from each carton and testing it for their tensile strength. The values are then compared with standard ones and based on this result the sample isaccepted or rejected. The tensile strength is a measure ofdegree of cure of the propellant mix. But this measurementis a destructive procedure as it involves cutting of the sample. Moreover, it does not guarantee against nonuniform curing due to power failure, hot air-line failure,operator error etc. This necessitated the need for the development of a quick and reliable non-destructive test procedure.

Exploring oligo(p-phenylenevinylene) gelators as sensors and stimuli responsive materials

Gelation provides a unique medium, which often induces organization of molecules resulting in the modulation of their optical, morphological and electronic properties thereby opening a new world of fascinating materials with interesting physical properties at nano- meso- and macroscopic levels. Supramolecular gels based on linear π-systems have attracted much attention due to their inherent optical and electronic properties which find application in organic electronics, light harvesting and sensing. They exhibit reversible properties due to the dynamic nature of noncovalent forces. As a result, studies on such soft materials are currently a topic of great interest. Recently, researchers are actively involved in the development of sensors and stimuli-responsive materials based on self-assembled π-systems, which are also called smart materials. The present thesis is divided into four chapters

Non-destructive evaluation of photovoltaic materials and solar cells using Photoluminescence

Photoluminescence (PL) spectroscopy is an optical technique that has emerged successful in the field of semiconductor material and device characterization. This technique is quite a powerful one which gives idea about the defect levels in a material, the band gap of the material, composition as well as material quality. Over the recent years it has received an elevation as a mainstream characterization technique. This thesis is an attempt to characterize each individual layer used in a thin film solar cell with special focus on the electrical properties. This will be highly beneficial from the lab as well as industrial point of view because electrical measurements generally are contact mode measurements which tend to damage the surface. As far as a thin film solar cell is concerned, the constituent layers are the transparent conducting oxide (TCO), absorber layer, buffer layer and top electrode contact. Each layer has a specific role to play and the performance of a solar cell is decided and limited by the quality of each individual layer. Various aspects of PL spectroscopy have been employed for studying compound semiconductor thin films [deposited using chemical spray pyrolysis (CSP)] proposed for solar cell application. This thesis has been structured in to seven chapters

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

“Studies on new base materials for microcellular soles"

The most important part of any footwear is the sole (or sole and heel) which withstands all the hannful external factors such as rouglmess of the ground or road, sharp objects, thorns and stones, heat, dampness and cold during walking. The properties desirable in soling material, therefore, would be 1. lightness 2. resistance to wear and tear for long service life 3. flexibility/softness for wearing comfort 4. thennal insulation Rubber soling surpasses all other soling materials in better performance and lower cost. Because MC sole is soft and very light, and has good abrasion resistance, flex properties and set behaviour it has become very popular all over the world and demand for better quality product is ever increasing. Due to the traditional approach adopted by the footwear industry in foot wear design, the rubber based footwear export surprisingly contributes only a small percentage. The essence of success for any industry lies in the expansion of the export market. Microcellular soles are manufactured for the last three decades without much change in the traditional design and colour pattern. In recent years domestic customers have also started demanding better quality products. In view of the changing taste of the customer and growing competition from other countries, substantial improvement in the export potential will require new base materials for regular or fashion rubber based footwears. The main objective of the present study is to develop new base materials for making MC soles with good quality, viz., light weight, durability and bright colours

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

Development and microwave characterization of selected biocompatible materials and conducting polymers

The 20th century witnessed the extensive use of microwaves in industrial, scientific and medical fields. The major hindrance to many developments in the ISM field is the lack of knowledge about the effect of microwaves on materials used in various applications. The study of the interaction of microwaves with materials demanded the knowledge of the dielectric properties of these materials. However, the dielectric properties of many of these materials are still unknown or less studied. This thesis is an effort to shed light into the dielectric properties of some materials which are used in medical, scientific and industrial fields. Microwave phantoms are those materials used in microwave simulation applications. Effort has been taken to develop and characterize low cost, eco-friendly phantoms from Biomaterials and Bioceramics. The interaction of microwaves with living tissues paved way to the development of materials for electromagnetic shielding. Materials with good conductivity/absorption properties could be used for EMI shielding applications. Conducting polymer materials are developed and characterized in this context. The materials which are developed and analyzed in this thesis are Biomaterials, Bioceramics and Conducting polymers. The use of materials of biological origin in scientific and medical applications provides an eco-friendly pathway. The microwave characterization of the materials were done using cavity material perturbation method. Low cost and ecofriendly biomaterial films were developed from Arrowroot and Chitosan. The developed films could be used in applications such as microwave phantom material, capsule material in pharmaceutical applications, trans-dermal patch material and eco-friendly Band-Aids. Bioceramics with better bioresorption and biocompatibility were synthesized. Bioceramics such as Hydroxyapatite, Beta tricalcium phosphate and Biphasic Calcium Phosphate were studied. The prepared bioceramics could be used as phantom material representing Collagen, Bone marrow, Human abdominal wall fat and Human chest fat. Conducting polymers- based on Polyaniline, are developed and characterized. The developed materials can be used in electromagnetic shielding applications such as in anechoic chambers, transmission cables etc

Development of selected electro-active polymer-ceramic nanocomposites as pyroelectric thermal/infrared detector materials

The present work emphasises on the synthesis and characterization of electro-active polymer-ceramic nanocomposites which can be used for pyroelectric thermal/infrared detection applications. Two sets of samples belong to polymer-microcrystalline composites have also been investigated in the work. The polymers used in the work have been commercially available ones, but the nanoceramics have been synthesized following simple chemical routes and aqueous organic gel routes. After characterizing the nanoceramics for their structure by powder XRD, they have been dispersed in liquid polymer and sonicated for uniform dispersion. The viscous mixture so formed was cast in the form of films for experimentation. Samples with volume fraction of the ceramic phase varied from 0 to 0.25 have been prepared. Solution growth was followed to prepare microcrystalline samples for the polymer-microcrystalline composites. The physical properties that determine the pyroelectric sensitivity of a material are dielectric constant, dielectric loss, pyroelectric coefficient, thermal conductivity and specific heat capacity. These parameters have been determined for all the samples and compositions reported in this work.The pyroelectric figures of merit for all the samples were determined. The pyroelectric figures of merit that determine the pyroelectric sensitivity of a material are current sensitivity, voltage responsivity and detectivity. All these have been determined for each set of samples and reported in the thesis. In order to assess the flexibility and mouldability of the composites we have measured the Shore hardness of each of the composites by indentation technique and compared with the pyroelectric figures of merit. Some important factors considered during the material fabrication stages were maximum flexibility and maximum figures of merit for pyroelectric thermal/IR detection applications. In order to achieve these goals, all the samples are synthesized as composites of polymers and nano/microcrystalline particles and are prepared in the form of freestanding films. The selected polymer matrices and particle inclusions possess good pyroelectric coefficients, low thermal and dielectric properties, so that good pyroelectric figures of merit could be achieved. The salient features of the work include the particle size of the selected ceramic materials. Since they are in nanometer size it was possible to achieve high flexibility and moldability with high figures of merit for even low volume fractions of inclusions of the prepared nanocrystalline composites. In the case of microcrystalline TGS and DTGS, their composites in PU matrix protect them from fragility and humidity susceptibility and made them for environmental friendly applications.

Investigations on TiO2 Based Nanocomposites as Potential Photonic Materials

This Study overviews the basics of TiO2with respect to its structure, properties and applications. A brief account of its structural, electronic and optical properties is provided. Various emerging technological applications utilising TiO2 is also discussed.Till now, exceptionally large number of fundamental studies and application-oriented research and developments has been carried out by many researchers worldwide in TiO2 with its low-dimensional nanomaterial form due to its various novel properties. These nanostructured materials have shown many favourable properties for potential applications, including pollutant photocatalytic decomposition, photovoltaic cells, sensors and so on. This thesis aims to make an in-depth investigation on different linear and nonlinear optical and structural characteristics of different phases of TiO2. Correspondingly, extensive challenges to synthesise different high quality TiO2 nanostructure derivatives such as nanotubes, nanospheres, nanoflowers etc. are continuing. Here, different nanostructures of anatase TiO2 were synthesised and analysed. Morphologically different nanostructures were found to have different impact on their physical and electronic properties such as varied surface area, dissimilar quantum confinement and hence diverged suitability for different applications. In view of the advantages of TiO2, it can act as an excellent matrix for nanoparticle composite films. These composite films may lead to several advantageous functional optical characteristics. Detailed investigations of these kinds of nanocomposites were also performed, only to find that these nanocomposites showed higher adeptness than their parent material. Fine tuning of these parameters helps researchers to achieve high proficiency in their respective applications. These innumerable opportunities aims to encompass the new progress in studies related to TiO2 for an efficient utilization in photo-catalytic or photo-voltaic applications under visible light, accentuate the future trends of TiO2-research in the environment as well as energy related fields serving promising applications benefitting the mankind. The last section of the thesis discusses the applicability of analysed nanomaterials for dye sensitised solar cells followed by future suggestions.