11 resultados para Photothermal spectroscopy of liquids

em Cochin University of Science


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We have performed thermal diffusion measurements of nanofluid containing gold and rhodamine 6G dye in various ratios. At certain concentrations, gold is nearly four times more efficient than water in dissipating small temperature fluctuations in a medium, and therefore it will find applications as heat transfer fluids. We have employed dual-beam mode-matched thermal lens technique for the present investigation. It is a sensitive technique in measuring photothermal parameters because of the use of a lowpower, stabilized laser source as the probe. We also present the results of fluorescence measurements of the dye in the nanogold environment.

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In this article we present size dependent spectroscopic observations of nanocolloids of ZnO. ZnO is reported to show two emission bands, an ultraviolet (UV) emission band and another in the green region. Apart from the known band gap 380 nm and impurity 530 nm emissions, we have found some peculiar features in the fluorescence spectra that are consistent with the nanoparticle size distribution. Results show that additional emissions at 420 and 490 nm are developed with particle size. The origin of the visible band emission is discussed. The mechanism of the luminescence suggests that UV luminescence of ZnO colloid is related to the transition from conduction band edge to valence band, and visible luminescence is caused by the transition from deep donor level to valence band due to oxygen vacancies and by the transition from conduction band to deep acceptor level due to impurities and defect states. A correlation analysis between the particle size and spectroscopic observations is also discussed.

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A novel cavity perturbation technique using coaxial cavity resonators for the measurement of complex permittivity of liquids is presented. The method employs two types of resonators (Resonator I and Resonator II). Resonator I operates in the frequency range 600 MHz-7 GHz and resonator II operates in the frequency range 4 GHz-14 GHz. The introduction of the capillary tube filled with the sample liquid into the coaxial resonator causes shifts in the resonance frequency and loaded Q-factor of the resonator. The shifts in the resonance frequency and loaded Q-factor are used to determine the real and imaginary parts of the complex permittivity of the sample liquid, respectively. Using this technique, the dielectric parameters of water and nitrobenzene are measured. The results are compared with those obtained using other standard methods. The sources of errors are analyzed.

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Photothermal effect refers to heating of a sample due to the absorption of electromagnetic radiation. Photothermal (PT) heat generation which is an example of energy conversion has in general three kinds of applications. 1. PT material probing 2. PT material processing and 3. PT material destruction. The temperatures involved increases from 1-. 3. Of the above three, PT material probing is the most important in making significant contribution to the field of science and technology. Photothermal material characterization relies on high sensitivity detection techniques to monitor the effects caused by PT material heating of a sample. Photothermal method is a powerful high sensitivity non-contact tool used for non-destructive thermal characterization of materials. The high sensitivity of the photothermal methods has led to its application for analysis of low absorbance samples. Laser calorimetry, photothermal radiometry, pyroelectric technique, photoacoustic technique, photothermal beam deflection technique, etc. come under the broad class ofphotothermal techniques. However the choice of a suitable technique depends upon the nature of the sample, purpose of measurement, nature of light source used, etc. The present investigations are done on polymer thin films employing photothermal beam deflection technique, for the successful determination of their thermal diffusivity. Here the sample is excited by a He-Ne laser (A = 6328...\ ) which acts as the pump beam. Due to the refractive index gradient established in the sample surface and in the adjacent coupling medium, another optical beam called probe beam (diode laser, A= 6500A ) when passed through this region experiences a deflection and 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 signal is suitably analysed for determining the thermal diffusivity.The production of polymer thin film samples has gained considerable attention for the past few years. Plasma polymerization is an inexpensive tool for fabricating organic thin films. It refers to formation of polymeric materials under the influence of plasma, which is generated by some kind of electric discharge. Here plasma of the monomer vapour is generated by employing radio frequency (MHz) techniques. Plasma polymerization technique results in homogeneous, highly adhesive, thermally stable, pinhole free, dielectric, highly branched and cross-linked polymer films. The possible linkage in the formation of the polymers is suggested by comparing the FTIR spectra of the monomer and the polymer.Near IR overtone investigations on some organic molecules using local mode model are also done. Higher vibrational overtones often provide spectral simplification and greater resolution of peaks corresponding to nonequivalent X-H bonds where X is typically C, N or O. Vibrational overtone spectroscopy of molecules containing X-H oscillators is now a well established tool for molecular investigations. Conformational and steric differences between bonds and structural inequivalence ofCH bonds (methyl, aryl, acetylenic, etc.) are resolvable in the higher overtone spectra. The local mode model in which the X-H oscillators are considered to be loosely coupled anharmonic oscillators has been widely used for the interpretation of overtone spectra. If we are exciting a single local oscillator from the vibrational ground state to the vibrational state v, then the transition energy of the local mode overtone is given by .:lE a......v = A v + B v2 • A plot of .:lE / v versus v will yield A, the local mode frequency as the intercept and B, the local mode diagonal anharmonicity as the slope. Here A - B gives the mechanical frequency XI of the oscillator and B = X2 is the anharmonicity of the bond. The local mode parameters XI and X2 vary for non-equivalent X-H bonds and are sensitive to the inter and intra molecular environment of the X-H oscillator.

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Photothermal spectroscopy is a group of high sensitivity methods used to measure optical absorption and thermal characteristics of a sample.The basis of photothermal spectroscopy is a photo-induced change in the thermal state of the sample.Light energy absorbed and not lost by subsequent emission results in sample heating.This heating results in a temperature change as well as changes in thermodynamic parameters of the sample which are related to temperature.Measurements of the temperature,pressure,or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic methods.This is a more direct measure of optical absorption than optical transmission based spectroscopies.Sample heating is a direct consequence of optical absorption and so photothermal spectroscopy signals are directly dependent on light absorption.Scattering and reflection losses do not produce photothermal signals.Subsequently,photothermal spectroscopy more accurately measures optical absorption in scattering solutions,in solids,and at interfaces.This aspect makes it particularly attractive for application to surface and solid absorption studies,and studies in scattering media.

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Vibrational overtone spectroscopy of X-H (X=C,N,O) containing molecules is an area of recent interest. The spectroscopic studies of higher vibrational levels yield valuable informations, regarding,the molecular structure, intra- and inter-molecular interactions, radiationless transitions, intra-molecular vibrational relaxations, multiphoton excitations and chemical reactivities, which cannot be z obtained by other spectroscopic methods. This thesis presents the results of experimental investigations on the overtone spectra of some organic compounds in the liquid phase for the characterization of CH bonds. The spectra in the fifth overtone region (1fiV=6) are recorded using a dual beam thermal lens setup and the lower overtones (.AV=2-5) are recorded spectrophotometrically.The thesis is presented in six chapters.

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The spectral and nonlinear optical characteristics of nano ZnO and its composites are investigated. The fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength and there is a red shift in emission peak with excitation wavelength. Apart from the observation of the reported ultra violet and green emissions, our results reveal that additional blue emissions at 420 nm and 490 nm are developed with increasing particle size. Systematic studies on nano ZnO have indicated the presence of luminescence due to excitonic emissions when excited with 255 nm as well as significant contribution from surface defect states when excited with 325 nm. In the weak confinement regime, the third-order optical susceptibility χ(3) increases with increasing particle size (R) and annealing temperature (T) and a R2 and T2.5 dependence of χ(3) is obtained for nano ZnO. ZnO nanocolloids exhibit induced absorption whereas the self assembled films of ZnO exhibit saturable absorption due to saturation of linear absorption of ZnO defect states and electronic effects. ZnO nanocomposites exhibit negative nonlinear index of refraction which can be attributed to two photon absorption followed by weak free carrier absorption. The increase of the third-order nonlinearity in the composites can be attributed to the enhancement of exciton oscillator strength. The nonlinear response of ZnO nanocomposites is wavelength dependent and switching from induced absorption to saturable absorption has been observed at resonant wavelengths. Such a change-over is related to the interplay of plasmon/exciton band bleach and optical limiting mechanisms. This study is important in identifying the spectral range and the composition over which the nonlinear material acts as an optical limiter. ZnO based nanocomposites are potential materials for enhanced and tunable light emission and for the development of nonlinear optical devices with a relatively small optical limiting threshold.

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Vibrational overtone spectroscopy of molecules containing X-H oscillators (X = C, N, O...) has become an effective tool for the study of molecular structure, dynamics, inter and intramolecular interactions, conformational aspects and substituent effects in aliphatic and aromatic compounds. In the present work, the author studied the NIR overtone spectra of some liquid phase organic compounds. The analysis of the CH, NH and OH overtones yielded important structural information about these systems. In an attempt to get information on electronic energy levels, we studied the pulsed Nd:YAG laser induced fluorescence spectra of certain organic compounds. The pulsed laser Raman spectra of some organic compounds are also studied. The novel high resolution technique of near infrared tunable diode laser absorption spectroscopy (TDLAS) is used to record the rotational structure of the second OH overtone spectrum of 2-propanol. The spectral features corresponding to the different molecular conformations could be identified from the high resolution spectrum. The whole work described in this thesis is divided into five chapters.

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FT-IR spectrum of quinoline-2-carbaldehyde benzoyl hydrazone (HQb H2O) was recorded and analyzed. The synthesis and crystal structure data are also described. The vibrational wavenumbers were examined theoretically using the Gaussian03 package of programs using HF/6-31G(d) and B3LYP/6-31G(d) levels of theory. The data obtained from vibrational wavenumber calculations are used to assign vibrational bands obtained in infrared spectroscopy of the studied molecule. The first hyperpolarizability, infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non-linear optics. The geometrical parameters of the title compound obtained from XRD studies are in agreement with the calculated values. The changes in the CAN bond lengths suggest an extended p-electron delocalization over quinoline and hydrazone moieties which is responsible for the non-linearity of the molecule

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One of the interesting consequences of Einstein's General Theory of Relativity is the black hole solutions. Until the observation made by Hawking in 1970s, it was believed that black holes are perfectly black. The General Theory of Relativity says that black holes are objects which absorb both matter and radiation crossing the event horizon. The event horizon is a surface through which even light is not able to escape. It acts as a one sided membrane that allows the passage of particles only in one direction i.e. towards the center of black holes. All the particles that are absorbed by black hole increases the mass of the black hole and thus the size of event horizon also increases. Hawking showed in 1970s that when applying quantum mechanical laws to black holes they are not perfectly black but they can emit radiation. Thus the black hole can have temperature known as Hawking temperature. In the thesis we have studied some aspects of black holes in f(R) theory of gravity and Einstein's General Theory of Relativity. The scattering of scalar field in this background space time studied in the first chapter shows that the extended black hole will scatter scalar waves and have a scattering cross section and applying tunneling mechanism we have obtained the Hawking temperature of this black hole. In the following chapter we have investigated the quasinormal properties of the extended black hole. We have studied the electromagnetic and scalar perturbations in this space-time and find that the black hole frequencies are complex and show exponential damping indicating the black hole is stable against the perturbations. In the present study we show that not only the black holes exist in modified gravities but also they have similar properties of black hole space times in General Theory of Relativity. 2 + 1 black holes or three dimensional black holes are simplified examples of more complicated four dimensional black holes. Thus these models of black holes are known as toy models of black holes in four dimensional black holes in General theory of Relativity. We have studied some properties of these types of black holes in Einstein model (General Theory of Relativity). A three dimensional black hole known as MSW is taken for our study. The thermodynamics and spectroscopy of MSW black hole are studied and obtained the area spectrum which is equispaced and different thermo dynamical properties are studied. The Dirac perturbation of this three dimensional black hole is studied and the resulting quasinormal spectrum of this three dimensional black hole is obtained. The different quasinormal frequencies are tabulated in tables and these values show an exponential damping of oscillations indicating the black hole is stable against the mass less Dirac perturbation. In General Theory of Relativity almost all solutions contain singularities. The cosmological solution and different black hole solutions of Einstein's field equation contain singularities. The regular black hole solutions are those which are solutions of Einstein's equation and have no singularity at the origin. These solutions possess event horizon but have no central singularity. Such a solution was first put forward by Bardeen. Hayward proposed a similar regular black hole solution. We have studied the thermodynamics and spectroscopy of Hay-ward regular black holes. We have also obtained the different thermodynamic properties and the area spectrum. The area spectrum is a function of the horizon radius. The entropy-heat capacity curve has a discontinuity at some value of entropy showing a phase transition.

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Materials and equipment which fail to achieve the design requirements or projected life due to undetected defects may require expensive repair or early replacement. Such defects may also be the cause of unsafe conditions or catastrophic unexpected failure, and will lead to loss of revenue due to plant shutdown. Non-Destructive Evaluation (NDE) / Non Destructive Testing (NDT) is used for the examination of materials and components without changing or destroying their usefulness. NDT can be applied to each stage of a system’s construction, to monitor the integrity of the system or structure throughout its life.