Possibility of waveguide formation on organic nonlinear crystal methyl para-hydroxy benzoate using high energy ion irradiation

Organic nonlinear optical single crystals of Methyl para-Hydroxy Benzoate (MHB) have been grown using gel-solution technique. These crystals are cut along z-axis and are bombarded with Ag14+ ions of energy 100 MeV. The results show an increase in refractive index at the ion irradiated region. The dielectric constant of the irradiated crystal is increased more than 15 times compared to that of a nonirradiated crystal. The result of these changes and comparative study of second harmonic generation (SHG) efficiency before and after irradiation is discussed.

Growth and characterisation of certain organic crystals

The thesis presents the results of the investigations on the crystallisation ‘behaviour, detect structure end electrical properties of certain organic crystals---phthslic snhydride end potsssiun scid phthalate Hollow crystals of phthalic snhydride were grown from vapour. the norpholog of these hollow crystals were studied in detail and s. mechanism for their growth has been proposed. A closed crystal—vapour system was used to study the basal plane growth of the whiskers and the sequential growth, observed, confirmed the mechanism suggested for hollow crystals. The dendritic crystals of phthslic enhydride were grown, both iron the melt and solution. The observed morphologies of these dendrites ere described. Bpherulites of phthalic anhydride have been grown by the artificial initiation of nucleation, from melt and solution. The variation of the substructure oi’ these spherulites with the growth tenperature wee investigated. The spherulitic filll having ribbon substructure were etched to reveal dislocations. A mechanism for the formation of the observed etch pattern has been suggested. the slip occurring in these ribbons were studied and the results are presented

Two new fluorescent heterocyclic perimidines: first syntheses, crystal structure and spectral characterization

An efficient one-pot synthesis of two new heterocyclic perimidines 4-(2,3-dihydro-1H-perimidin-2-yl)-2-methoxyphenol and 2-(quinoxalin-2-yl)-2,3-dihydro-1H-perimidine in good yields is presented. This methodology provides a simple, straightforward synthetic route to these interesting classes of heterocycles. Crystal structure, solvatochromism and antibacterial activity of these organic compounds are discussed.

Elastic constant measurements of super ionic LiKSO4:Na single crystals

Elastic properties of sodium doped Lithium potassium sulphate, LiK0.9Na0.1SO4, crystal has been studied by ultrasonic Pulse Echo Overlap [PEO] technique and are reported for the first time. The controversy regarding the type of crystal found while growth is performed at 35 °C with equimolar fraction of Li2SO4H2O, K2SO4 and Na2SO4 has been resolved by studying the elastic properties. The importance of this crystal is that it exhibits pyroelectric, ferroelectric and electro optic properties. It is simultaneously ferroelastic and superionic. The elastic properties of LiK0.9Na0.1SO4 crystal are well studied by measuring ultrasonic velocity in the crystal in certain specified crystallographic directions and evaluating the elastic stiffness constants, compliance constants and Poisson’s ratios. The anisotropy in the elastic properties of the crystal are well explained by the pictorial representation of the surface plots of phase velocity, slowness and linear compressibility in a-b and a-c planes.

Biochemical Effects of Anionic, Cationic and Non Ionic Surfactants on a Tropical Teleost Oreochromis Mossambicus(Peters) and a Marine Cyanobacterium Synechocystis Salina Wislouch

The present work is a base line attempt to investigate and assess the toxicities of three surfactants viz. anionic sodium dodecyl sulfate (SDS), non ionic Triton X-1OO (TX-IOO) and cationic cetyl trimethyl ammonium bromide (CTAB). These compounds represent simple members of the often neglected group of aquatic pollutants i.e. the anionic alkyl sulfates, non ionics and the cationics. These compounds are widely used In plastic industry, pesticide/herbicide formulations, detergents, oil spill dispersants, molluscicides etc. The test organisms selected for the present study are the cyanobacterium Synechocystis salina Wislouch representing a primary producer in the marine environment and a fresh water adapted euryhaline teleost Oreochromis mossambicus (peters) at the consumer level of the ecological pyramid. The fish species, though not indigenous to our country, is now found ubiquitously in fresh water systems and estuaries. Also it is highly resistant to pollutants and has been suggested as an indicator of pollution in tropical region .

Thermal lens spectrum of organic dyes using optical parametric oscillator

The wavelength dependence of thermal lens signal from organic dyes are studied using dual beam thermal lens technique. It is found that the profile of thermal lens spectrum widely differ from the conventional absorption spectrum in the case of rhodamine B unlike in the case of crystal violet. This is explained on the basis of varying contribution of nonradiative relaxations from the excited vibronic levels.

Thermal lens spectrum of organic dyes using optical parametric oscillator

The wavelength dependence of thermal lens signal from organic dyes are studied using dual beam thermal lens technique. It is found that the profile of thermal lens spectrum widely differ from the conventional absorption spectrum in the case of rhodamine B unlike in the case of crystal violet. This is explained on the basis of varying contribution of nonradiative relaxations from the excited vibronic levels.

Studies On The Electrical Properties Of Some Crystalline Organic Compounds And Conducting Polymers

Solid electrolytes for applications like chemical sensing, energy storage, and conversion have been actively investigated and developed since the early sixties. Although of immense potential, solid state protonic conductors have been ignored in comparison with the great interest that has been shown to other ionic conductors like lithium and silver ion conductors. The non-availability of good, stable protonic conductors could be partly the reason for this situation. Although organic solids are better known for their electrical insulating character, ionic conductors of organic origin constitute a recent addition to the class of ionic conductors. However, detailed studies (N1 such conductors are scarce. Also the last decade has witnessed an unprecedented boom in research on organic "conducting polymers". These newly devised materials show conductivity spanning from insulator to metallic regimes, which can be manipulated by appropriate chemical treatment. They find applications in devices ranging from rechargeable batteries to "smart windows". This thesis mainly deals with the synthesis and investigations on the electrical properties of (i) certain organbc protonic conductors derived from ethylenediamine and (ii) substituted polyanilines

Raman spectra of KTP crystal in an in situ electric field

Raman spectra of the KTP single crystal are recorded in electric fields (dc and ac) applied along the polar axis c. Spectra with the laser beam focused near the cathode end, anode end and the centre of the crystal are recorded. The cathode end of the crystal develops a spot ‘grey track’ where the laser beam is focused after a lapse of 5 h from the application of a dc electric field of 38 V/cm. The spectra recorded at the cathode end after the application of field show variations in intensity of bands. A new band appears at 177 cm21. Changes in band intensities are explained on the basis of changes in polarizability of the crystal due to the movement of K1 ions along the polar axis. K1 ions accumulate at the cathode end, where the ‘Grey track’ formation occurs. The intensity enhancement observed for almost all bands in the ac field is attributed to the improvement of crystalline quality.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.