Investigations on some amino acid based single crystals for nonlinear optical applications and amino acid capped nanocrystals

Organic crystals possess extremely large optical nonlinearity compared to inorganic crystals. Also organic compounds have the amenability for synthesis and scope for introducing desirable characteristics by inclusions. A wide variety of organic materials having electron donor and acceptor groups, generate high order of nonlinearity. In the present work, a new nonlinear optical crystal, L-citrulline oxalate (LCO) based on the aminoacid L-citrulline was grown using slow evaporation technique. Structural characterization was carried out by single crystal XRD. It crystallizes in the noncentrosymmetric, orthorhombic structure with space group P21 P21 P21. Functional groups present in the sample were identified by Fourier transform infra red (FTIR) and FT-Raman spectral analysis. On studying the FTIR and Raman spectra of the precursors L-citrulline and oxalic acid, used for growing L-citrulline oxalate crystal, it is found that the significant peaks of the precursors are present in the spectra of the L-citrulline oxalate crystal . This observation along with the presence of NH3 + group in the spectra of L-citrulline oxalate, confirms the formation of the charge transfer complex

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.

Methylene Blue Doped Polymers: efficient Media for Optical Recording

Polymer materials find application in optical storage technology, namely in the development of high information density and fast access type memories. A new polymer blend of methylene blue sensitized polyvinyl alcohol (PVA) and polyacrylic acid (PAA) in methanol is prepared and characterized and its comparison with methylene blue sensitized PVA in methanol and complexed methylene blue sensitized polyvinyl chloride (CMBPVC) is presented. The optical absorption spectra of the thin films of these polymers showed a strong and broad absorption region at 670-650 nm, matching the wavelength of the laser used. A very slow recovery of the dye on irradiation was observed when a 7:3 blend of polyvinyl alcohol/polyacrylic acid at a pHof 3.8 and a sensitizer concentration of 4.67 10 5 g/ml were used. A diffraction efficiency of up to 20% was observed for the MBPVA/alcohol system and an energetic sensitivity of 2000 mJ/cm2 was obtained in the photosensitive films with a spatial frequency of 588 lines/mm.

Methylene Blue Doped Polymers:Efficient Media for Optical Recording

Polymer materials find application in optical storage technology, namely in the development of high information density and fast access type memories. A new polymer blend of methylene blue sensitized polyvinyl alcohol (PVA) and polyacrylic acid (PAA) in methanol is prepared and characterized and its comparison with methylene blue sensitized PVA in methanol and complexed methylene blue sensitized polyvinyl chloride (CMBPVC) is presented. The optical absorption spectra of the thin films of these polymers showed a strong and broad absorption region at 670-650 nm, matching the wavelength of the laser used. A very slow recovery of the dye on irradiation was observed when a 7:3 blend of polyvinyl alcohol/polyacrylic acid at a pHof 3.8 and a sensitizer concentration of 4.67 10 5 g/ml were used. A diffraction efficiency of up to 20% was observed for the MBPVA/alcohol system and an energetic sensitivity of 2000 mJ/cm2 was obtained in the photosensitive films with a spatial frequency of 588 lines/mm.

Development of Elastomeric Hybrid Composite Based on Synthesised Manosilica and Short Nylon Fiber

Nanoscale silica was synthesized by precipitation method using sodium silicate and dilute hydrochloric acid under controlled conditions. The synthesized silica was characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), BET adsorption and X-Ray Diffraction (XRD). The particle size of silica was calculated to be 13 nm from the XRD results and the surface area was found to be 295 m2/g by BET method. The performance of this synthesized nanosilica as a reinforcing filler in natural rubber (NR) compound was investigated. The commercial silica was used as the reference material. Nanosilica was found to be effective reinforcing filler in natural rubber compound. Filler-matrix interaction was better for nanosilica than the commercial silica. The synthesized nanosilica was used in place of conventional silica in HRH (hexamethylene tetramine, resorcinol and silica) bonding system for natural rubber and styrene butadiene rubber / Nylon 6 short fiber composites. The efficiency of HRH bonding system based on nanosilica was better. Nanosilica was also used as reinforcing filler in rubber / Nylon 6 short fiber hybrid composite. The cure, mechanical, ageing, thermal and dynamic mechanical properties of nanosilica / Nylon 6 short fiber / elastomeric hybrid composites were studied in detail. The matrices used were natural rubber (NR), nitrile rubber (NBR), styrene butadiene rubber (SBR) and chloroprene rubber (CR). Fiber loading was varied from 0 to 30 parts per hundred rubber (phr) and silica loading was varied from 0 to 9 phr. Hexa:Resorcinol:Silica (HRH) ratio was maintained as 2:2:1. HRH loading was adjusted to 16% of the fiber loading. Minimum torque, maximum torque and cure time increased with silica loading. Cure rate increased with fiber loading and decreased with silica content. The hybrid composites showed improved mechanical properties in the presence of nanosilica. Tensile strength showed a dip at 10 phr fiber loading in the case of NR and CR while it continuously increased with fiber loading in the case of NBR and SBR. The nanosilica improved the tensile strength, modulus and tear strength better than the conventional silica. Abrasion resistance and hardness were also better for the nanosilica composites. Resilience and compression set were adversely affected. Hybrid composites showed anisotropy in mechanical properties. Retention in ageing improved with fiber loading and was better for nanosilica-filled hybrid composites. The nanosilica also improved the thermal stability of the hybrid composite better than the commercial silica. All the composites underwent two-step thermal degradation. Kinetic studies showed that the degradation of all the elastomeric composites followed a first-order reaction. Dynamic mechanical analysis revealed that storage modulus (E’) and loss modulus (E”) increased with nanosiica content, fiber loading and frequency for all the composites, independent of the matrix. The highest rate of increase was registered for NBR rubber.

Development of Photorefractive Polymers: Evaluation of Photoconducting and Electro-optic Properties

This Thesis discussed molecules suitable for photorefractive effect. Out of the molecules studied, only one system was used to make photorefractive polymers system. Other molecules, especially, the electro-optic polymer, Poly(3-methacrloyl-1-(4'-nitro-4-azo-1'-phenyl)phenylalanine-co- methyl methacrylate) can be subjected to more detailed studies to explore the possibilities of using them for electro-optic applications. Though not included in the thesis, the efficient photoconductor, Poly(6-tert-butyl-3- phenyl-3,4-dihydro-2H-1,3-benzoxazine) sensitized with C60, which was described in Chapter 3 showed a low magnitude photovoltaic effect. This hints at the possibility of using this system for organic solar cells also. The thesis presented the initial observation of photorefractive effect in a polybenzoxazine based polymer system. A detailed analysis of the effect of C60, ECZ and DR1 can be carried out to check for the possibility of a high efficiency photorefractive system.

Sorptional Behaviour of Metals on the Sediments and Humic acid of Mangrove Ecosystem

Humic substances are complex polymeric structures.No other polymers with such a wide range of properties are so widely distributed in nature.But still their moleculer structures are unknown. A structural knowledge is essential in determining their reactivity with metals.In the present work structural elucidation of humic acids from three different mangrove ecosystems of Cochin area is done with the available data from functional group analysis and various spectroscopic methods.13C NMR spectra of the solid samples with CPMAS,IR and SEM are very promising in revealing the complex structures of these polymeric substances.Sorptional studies on the sediment and humic acid of mangrove ecosystem reveals that the major portion of the organic matter is not extractable with Sodium hydroxide and humic acid only a small portion of the total organic matter. Humic acid is a good complexing agent and scavenger. Due to the nonextractable nature of the organic matter present with the sediment left after alkali extraction it is a better scavenger.

Studies on Conducting Polymers and Conductive Elastomer Composites

The primary aim of this work has been to develop conductive silicone and nitrile rubbers, which are extensively used for making conductive pads in telephone sets, calculators and other applications. Another objective of the work has been to synthesise and characterize novel conducting polymers based on glyoxal and paraphenylenediamine- poly(p-phenylenediazomethine. Conducting polymer matrices were developed from polymer blends such as poly(pphenylenediazomethine), polyethylene, PVC and silica and their properties were studied.

Characterisation of the acid-base properties of pillared montmorillonites

Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed reactions.

Photothermal and photoacoustic investigations on certain polymers and semi conducting materials

Material synthesizing and characterization has been one of the major areas of scientific research for the past few decades. Various techniques have been suggested for the preparation and characterization of thin films and bulk samples according to the industrial and scientific applications. Material characterization implies the determination of the electrical, magnetic, optical or thermal properties of the material under study. Though it is possible to study all these properties of a material, we concentrate on the thermal and optical properties of certain polymers. The thermal properties are detennined using photothermal beam deflection technique and the optical properties are obtained from various spectroscopic analyses. In addition, thermal properties of a class of semiconducting compounds, copper delafossites, arc determined by photoacoustic technique.Photothermal technique is one of the most powerful tools for non-destructive characterization of materials. This forms a broad class of technique, which includes laser calorimetry, pyroelectric technique, photoacollstics, photothermal radiometric technique, photothermal beam deflection technique etc. However, the choice of a suitable technique depends upon the nature of sample and its environment, purpose of measurement, nature of light source used etc. The polynler samples under the present investigation are thermally thin and optically transparent at the excitation (pump beam) wavelength. Photothermal beam deflection technique is advantageous in that it can be used for the detennination of thermal diffusivity of samples irrespective of them being thermally thick or thennally thin and optically opaque or optically transparent. Hence of all the abovementioned techniques, photothemlal beam deflection technique is employed for the successful determination of thermal diffusivity of these polymer samples. However, the semi conducting samples studied are themlally thick and optically opaque and therefore, a much simpler photoacoustic technique is used for the thermal characterization.The production of polymer thin film samples has gained considerable attention for the past few years. Different techniques like plasma polymerization, electron bombardment, ultra violet irradiation and thermal evaporation can be used for the preparation of polymer thin films from their respective monomers. Among these, plasma polymerization or glow discharge polymerization has been widely lIsed for polymer thin fi Im preparation. At the earlier stages of the discovery, the plasma polymerization technique was not treated as a standard method for preparation of polymers. This method gained importance only when they were used to make special coatings on metals and began to be recognized as a technique for synthesizing polymers. Thc well-recognized concept of conventional polymerization is based on molecular processcs by which thc size of the molecule increases and rearrangemcnt of atoms within a molecule seldom occurs. However, polymer formation in plasma is recognized as an atomic process in contrast to the above molecular process. These films are pinhole free, highly branched and cross linked, heat resistant, exceptionally dielectric etc. The optical properties like the direct and indirect bandgaps, refractive indices etc of certain plasma polymerized thin films prepared are determined from the UV -VIS-NIR absorption and transmission spectra. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer. The thermal diffusivity has been measured using the photothermal beam deflection technique as stated earlier. This technique measures the refractive index gradient established in the sample surface and in the adjacent coupling medium, by passing another optical beam (probe beam) through this region and hence the name probe beam deflection. The deflection is detected using a position sensitive detector and its output is fed to a lock-in-amplifIer from which the amplitude and phase of the deflection can be directly obtained. The amplitude and phase of the deflection signal is suitably analyzed for determining the thermal diffusivity.Another class of compounds under the present investigation is copper delafossites. These samples in the form of pellets are thermally thick and optically opaque. Thermal diffusivity of such semiconductors is investigated using the photoacoustic technique, which measures the pressure change using an elcctret microphone. The output of the microphone is fed to a lock-in-amplificr to obtain the amplitude and phase from which the thermal properties are obtained. The variation in thermal diffusivity with composition is studied.

An optical fibre based evanescent wave sensor to monitor the deposition rate of thin films

A novel fibre optic sensor for the in situ measurement of the rate of deposition of thin films has been developed. Evanescent wave in the uncladded portion of a multimode fibre is utilised for this sensor development. In the present paper we demonstrate how this sensor is useful for the monitoring of the deposition rate of polypyrrole thin films, deposited by an AC plasma polymerisation method. This technique is simple, accurate and highly sensitive compared with existing techniques.

Development of thermoplastic conducting polymer composites based on polyaniline and polythiophenes for microwave and electrical applications

The microwave and electrical applications of some important conducting polymers are analyzed in this investigation.One of the major drawbacks of conducting polymers is their poor processability,and a solution to overcome this is sought in this investigation.Conducting polymer thermoplastic composites were prepared by the insitu polymerization method to improve the extent of miscibility probably to a semi IPN level.The attractive features of the conducting composite developed are excellent processability,good microwave and electrical conductivity,good microwave absorption,load sensitivity and satisfactory mechanical properties.The composite shows typical frequency selective microwave absorption and refelection behaviors.