Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2019-02-12T15:41:23Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Cristiano Santos Lopes.pdf: 29539894 bytes, checksum: f1c58591825997b77f26dff47e244408 (MD5) / Made available in DSpace on 2019-02-12T15:41:23Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Cristiano Santos Lopes.pdf: 29539894 bytes, checksum: f1c58591825997b77f26dff47e244408 (MD5) Previous issue date: 2018-10-24 / Os nanofluidos plasmônicos tem sido empregados em diversas aplicações nos mais variados campos, como por exemplo, fluidos de arrefecimento, coletores solares e agentes teranósticos. Dentro desta área, o entendimento da difusividade térmica é extremamente importante e as diversas técnicas que existem para a sua determinação podemoferecerresultados divergentes.O usodetécnicasfototérmicasapresentamuma grande sensibilidade para medir vários parâmetros dos nanofluidos. Neste trabalho, nanopartículasesféricasdepratacomtamanhomédiode32nmforamsintetizadaspelo métododeTurkevicherevestidascomosurfactantePolivinilpirrolidona(PVP).Medidas de índice de refração não linear e difusividade térmica de nanofluidos de prata foram realizadas por meio das técnicas de Z-Scan e Lente Térmica. Conseguimos obter uma relação entre o índice de refração com a frequência, e também da difusividade térmica com a concentração de nanopartículas. Estes resultados foram corroborados uma vez que a técnica utilizada neste trabalho foi replicada para a análise da difusidade térmica da água, cujo valor adquirido está de acordo com o valor já conhecido na literatura. / Plasmonic nanofluids have been used in several applications in many different fields, such as cooling fluids, solar collectors and theranostic agents. Related to this area, the understanding of thermal diusivity is extremely important and the various techniques that exist for its determination can offer divergent results. The use of photothermal techniques shows presents a great sensitivity to measure various parameters of nanoflu- ids. In this work, silver spherical nanoparticles with a average diameter of 32 nm were synthesized by the Turkevich method and coated with the surfactant Polyvinylpyrroli- done (PVP). Nonlinear refractive index and thermal diffusivity measurements of silver nanofluids were performed using the Z-Scan and Thermal Lens techniques.We obtained a relation that describe the dependence of the refractive index index of refraction with the frequency and also for of the thermal diffusivity with the nanoparticles concentration. These results were corroborated since the technique used in this work was replicated for the water thermal diffusion analysis, whose obtained value is in agreement with the expected literature value.

>Magister Scientiae - MSc / Recent research shows that the study of optical properties of organic material natural dyes has gained much consideration. The specific functional groups in several natural dyes remain essential for the large nonlinear absorption expressed in terms of nonlinear optical susceptibilities or other mechanism of absorption such as two photon absorption (TPA), reverse saturable absorption (RSA) or intensitydependent refractive index characteristic. In this thesis we highlight the optical limiting responses of selected natural dyes as nonlinear response in the femtosecond regime. This technique refers to the decrease of the transmittance of the material with the increased incident light intensity.Three dyes derived from beetroot, flame flower and mimosa flower dyes were investigated. The results showed a limiting behaviour around 795 mW for the beetroot and the flame dye while there is total transmission in the flame dye sample. The performance of the nonlinearity i.e. the optical limiting is related to the existence of alternating single and double bonds(i.e. C-C and C=C bonds) in the molecules that provides the material with the electron delocalization, but also it is related to the light intensity.Beside nonlinearity study, crystallographic investigation was carried out for more possible applicability of the selected dyes and this concerned only the mimosa and flame flower dye thin film samples since the beetroot thin film was very sensitive to strong irradiation (i.e. immediately destroyed when exposed to light with high intensity). For more stability,dye solutions were encapsulated in gels for further measurements.

Orientador: Keizo Yukimitu / Banca: Antonio Medina Neto / Banca: Elso Drigo Filho / Resumo: Neste trabalho foram estudadas as propriedades ópticas de vidros teluretos do sistema (20-x)Li2O-80TeO2-xTiO2 com x = 0, 5, 10 e 15 mol%. Foram preparadas amostras para cada uma das composições através do convencional método de "meltquenting". Medimos, para cada amostra, o espectro de infravermelho e o espectro na faixa do ultravioleta-visível. Também obtemos os valores de índice de refração de cada amostra para diversos comprimentos de onda na faixa do visível. Para tanto, utilizamos um interferômetro de Michelson-Morley modificado. Medidas de densidade foram feitas utilizando-se o convencional método de Arquimedes. Por fim, foram feitas medidas do coeficiente térmico do caminho óptico através da interferometria. A análise estrutural foi feita através do espectro de infravermelho. Pode-se observar a tendência à formação de pirâmides trigonais em substituição às bipirâmides (encontradas no TeO2 cristalino) quando aumentamos a porcentagem de óxido de lítio. Uma análise qualitativa da absorção na faixa de interesse em comunicações ópticas (~1500 nm) foi feita através do espectro de infravermelho próximo, mostrando que nesta faixa temos a predominância do espalhamento Rayleigh, com o coeficiente de absorção proporcional a λ-4. Usando os dados da espectroscopia na faixa ultravioleta-visível foi possível observar a mudança das freqüências de corte para cada composição e ainda calcular a energia de gap e a energia de cauda de Urbach. Através do modelo clássico de osciladores harmônicos forçados de Wemple, os resultados de índice de refração foram interpretados. Buscou-se ainda relacionar as mudanças observadas para os valores medidos para cada composição com possíveis mudanças estruturais. Concluímos, usando as considerações de Wemple, que o aumento... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work had been studied tellurite glasses's the optic properties of the system (20-x) Li2O-80TeO2-xTiO2 with x = 0, 5, 10 and 15 mol%. Samples for each one of the compositions through the conventional method of melt-quenting had been prepared. We measure, for each sample, the infra-red ray specter and the specter in the band of the ultraviolet-visible one. Also we get the values of refractive index of each sample for diverse wave lengths in the visible band. For in such a way, we use a modified interferometer of Michelson-Morley. Measures of density had been made using the conventional method of Archimedes. Finally, they had been made measured of the thermal coefficient of the optic way through the interferometry. The structural analysis was made through the infra-red ray specter. The trend to the formation of trigonais pyramids in substitution to the bipyramids can be observed (found in the crystalline TeO2) when increases the lithium oxide percentage. A qualitative analysis of the absorption in the band of interest in optic communications (~1500 nm) was made through the infra-red ray specter, showing that in this band we have the predominance of the Rayleigh scattering, with the coefficient of absorption proportional to λ-4. Using the data of the spectroscopy in the ultraviolet-visible band to each composition was possible to observe the change of the cut-off frequencies and still to calculate the energy of gap and the energy of Urbach. Through the classic model of forced harmonic oscillators of Wemple, the results of refractive index had been interpreted. We still searched to relate the changes observed for the values measured for each composition with possible structural changes. We conclude, using the considerations of Wemple, that the increase for the values of... (Complete abstract click electronic access below) / Mestre

Orientador: Keizo Yukimitu / Resumo: Com a crescente populacional a demanda pelos polímeros aumentou significativamente, levando assim a pesquisas cientificas visando adequar materiais as nossas necessidades. O PMMA ou acrílico é muito utilizado em nosso cotidiano, sendo um material muito versátil com aplicabilidade em diversos setores. O intuito deste trabalho foi realizar a produção de um filme de acrílico [Poli(metil-metacrilato)] isento de bolhas e transparente, a qual tivesse uma repetibilidade. Foi realizada a dopagem com terras raras, sendo o Óxido de Érbio e o Óxido de Itérbio escolhidos como dopantes em diferentes concentrações de gramas/mol por gramas/mol (0 % referência, 5 %, 10%, 15% e 20 %). Logo após foi feita a caracterização dos filmes, determinando o índice de refração das amostras utilizando o Interferomêtro de Michelson com laser He-Ne (vermelho) de comprimento de onda de 632,8 nm. Notamos que o índice de refração do PMMA na amostra de referência aumentou gradativamente com as dopagens, o laser diodo na cor verde de comprimento de onda de 532 nm também foi utilizado e os resultados demostraram comportamentos similares. A Espectroscopia no Infravermelho por Transformada de Fourier (FTIR) foi realizada, observando o aparecimento de picos característicos dos elementos dopantes nas amostras e que esses picos aumentavam conforme a concentração de dopagem aumentava. A Difração de Raios-X (DRX) nos mostrou a incidência picos de cristalinidade referentes aos elementos dopantes em contraste com o espec... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: With the growing population demand for polymers has increased significantly, leading to scientific research aimed at adapting materials to our needs. PMMA or acrylic is widely used in our daily lives, being a very versatile material with applicability in several sectors. The purpose of this work was to produce an acrylic film [Poly (methyl-methacrylate)] which had a repeatability. Rare earth doping was performed, with Erbium Oxide and Ytterbium Oxide chosen as dopants in different concentrations of grams / mole per gram / mole (0% reference, 5%, 10%, 15% and 20%). After the characterization of the films, determining the refractive index of the samples using the Michelson Interferometer with He-Ne (red) laser of wavelength of 632.8 nm, we noticed that the refractive index of the PMMA in the sample of reference period increased gradually with doping, the green diode laser wavelength of 532 nm was also used and the results demonstrated similar behaviors. Fourier Transform Infrared Spectroscopy (FTIR) was performed, observing the appearance of characteristic peaks of the dopant elements in the samples and that these peaks increased as the doping concentration increased. X-ray Diffraction (XRD) showed us the incidence of crystallinity peaks relative to the dopant elements in contrast to the normal PMMA spectrum demonstrating the insertion of the rare earths into the matrix structure. / Mestre

A great deal of attention has been paid to brown carbon aerosol in the troposphere because it can both scatter and absorb solar radiation, thus affecting the Earth’s climate. However, knowledge of the optical and chemical properties of brown carbon aerosol is still limited. In this thesis, we have investigated different aspects of the optical and physicochemical properties of various brown carbon aerosol samples of potential atmospheric importance. First, reactions involving the di-carbonyl species methylglyoxal (MG) have been previously suggested as an important pathway for the production of secondary organic aerosol (SOA) in the atmosphere. Reaction in an aqueous inorganic salt solution, such as ammonium sulfate (AS), leads to the formation of light-absorbing brown carbon (BrC) product. In this thesis work, we employed a variety of experimental approaches to investigate the optical and physicochemical properties of BrC aerosol generated from this AS-MG reaction (BrC (AS/MG)). Optical properties of the dried BrC (AS/MG) aerosol particles were studied by Fourier transform infrared (FTIR) extinction spectroscopy in the mid-infrared region, cavity ring-down spectroscopy (CRDS) at 403 nm in the visible, and by measuring the light scattering phase function and polarization profiles at two different visible wavelengths, 532 and 402 nm. In addition, we used UV−vis spectroscopy to measure the mass absorption coefficient (MAC) of the solution-phase reaction products. The different optical properties were measured as a function of reaction time for a period of up to 22 days. The UV-vis absorption spectra showed a clear increase in measured MAC in the visible and near UV as the solution aged. However, analysis of the light scattering data showed no significant differences between AS and BrC aerosol in the derived refractive indices at either 532 or 402 nm, even for the longest reaction times. The FTIR extinction spectra was modeled in a Mie theory simulation to derive the complex refractive index in the mid-IR range (7000-800 cm−1); the results showed no significant changes in either the real or the imaginary parts of the refractive indices for BrC (AS/MG) aerosol particles when compared to unreacted AS aerosol. From the CRDS extinction data, the optical constants for BrC (AS/MG) particles at 403 nm were also determined through a Mie theory based analysis. The retrieved real index of refraction at 403 nm is n = 1.551 ± 0.005, with an imaginary index value of k = 0.000 ± 0.002; these values do not appear to change significantly with aging time over the course of 22 days and are not markedly different from the AS aerosol values. The small imaginary index value suggests that BrC (AS/MG) aerosol formed from this pathway may not significantly contribute to warming. In addition, CRDS measurements of the BrC (AS/MG) aerosol extinction at 403 nm as a function of particle size show a significant deviation from Mie theory simulations for particles with diameters of ≳500 nm, probably as a result of non-spherical particle shape effects. We also employed atomic force microscopy (AFM)-based IR spectroscopy to investigate the morphology and chemical composition of single SOA particles. AFM analysis of the particle morphology shows that a significant fraction of BrC (AS/MG) particles with diameters of ≳500 nm are non-spherical in shape, consistent with our observed breakdown in the applicability of Mie theory for larger particles. In addition to these measurements, we have characterized additional physicochemical properties of the BrC (AS/MG) aerosol particles including hygroscopic growth using a tandem-differential mobility analyzer. Compared to AS, BrC aerosol particles are found to have lower deliquescence relative humidity (DRH), efflorescence relative humidity (ERH), and hygroscopic growth at the same relative humidity values. Second, we investigated the optical properties of the water soluble products of limonene BrC generated from ozonolysis of d-limonene with further aging by AS. Optical constants for the dried limonene BrC aerosol product were measured at 403 nm by CRDS over the course of 9 days of aging. While the fresh limonene BrC aerosol showed a significant non-zero absorption index, the aged samples showed absorption index values consistent with zero. This result was somewhat unexpected because UV-vis absorption spectra of the bulk reaction solution showed a continued increase in absorption as the solution aged. One possible explanation for this result is that there could be an increase in the fraction of volatile chromophores as the solution ages, that are then removed in the aerosol drying process. Third, we investigated optical properties and chemical compositions of several humic substance (HS) reference samples including humic acid (HA) and fulvic acid (FA) standards by CRDS, UV-vis spectroscopy, elemental analysis, and 13C NMR spectroscopy. Measurements of the optical properties of HS is important in atmospheric science, because it is thought that HS samples have similar optical properties to organic materials, such as HUmic-Like Substances (HULIS), that exist in clouds, fogs, rainwater, and atmospheric aerosol. The humic acid aerosol samples generally showed higher absorption index values than the fulvic acid aerosol samples. We also found a correlation between the absorption index and chemical composition, with the value for k generally increasing with both increasing carbon-to-oxygen atomic ratio and sample aromaticity. In addition, we compared our measured optical constants for the HS aerosol samples with results from previous studies of field collected HULIS. The absorption index values for the fulvic acid aerosol samples give a better match than the humic acid samples when compared to the results from the field collected samples. Overall, these studies provide new details of the optical and physicochemical properties of a class of brown carbon organic aerosol which may have important implications for atmospheric chemistry and climate.

Nitrogen rich glasses in the systems Ca-Si-O-N, Sr-Si-O-N and AE-Ca-Si-O-N (AE = Mg, Sr and Ba) have been prepared using a novel glass-synthesis route. The limits of the glass forming regions in the Ca and Sr systems and substitution limits in the AE-Ca-Si-O-N systems have been determined and physical properties of the glasses measured. Transparent glasses were obtained for a few specific compositions in the Ca-Si-O-N and Mg-Ca-Si-O-N systems. All other glasses were found to be translucent gray to opaque black, with the coloration of the glasses depending on the modifier. Small inclusions of Ca/Sr silicides and, in much smaller amounts, elemental Si are believed to be responsible for their poor transparency. A large glass forming region was found for the Ca-Si-O-N system, with glasses retaining up to 58 e/o N and 42 e/o Ca. In comparison, a more narrow glass forming region was found for the corresponding Sr system, with glasses retaining up to 45 e/o N and 39 e/o Sr. The glass formation was found to depend on reaction kinetics and precursors used. A strong exothermic reaction was observed at temperatures 650–1000oC, providing improved conditions for reaction kinetics upon further heating. Physical property measurements for the Ca and Sr glasses showed that glass transition and crystallization temperatures, viscosity, hardness, Young’s modulus and shear modulus depend strongly on the nitrogen content and that these properties increase approximately linearly with increasing nitrogen content. Glass density and refractive index are also dependent on the modifier element and content, in particular for the Sr glasses. Glasses AE-Ca-Si-O-N, with approximately constant (Ca/AE): Si:O:N ratios, showed that mixed modifier glass properties, such as density, molar volume, glass transition temperature, hardness, refractive index can be related to the effective cation field strength of the modifiers.

The field of inverse problems is an area in applied mathematics that is of great importance in several scientific and industrial applications. Since an inverse problem is typically founded on non-linear and ill-posed models it is a very difficult problem to solve. To find a regularized solution it is crucial to have a priori information about the solution. Therefore, general theories are not sufficient considering new applications. In this thesis we consider the inverse problem to determine the beam bending stiffness from measurements of the transverse dynamic displacement. Of special interest is to localize parts with reduced bending stiffness. Driven by requirements in the wood-industry it is not enough considering time-efficient algorithms, the models must also be adapted to manage extremely short calculation times. For the developing of efficient methods inverse problems based on the fourth order Euler-Bernoulli beam equation and the second order string equation are studied. Important results are the transformation of a nonlinear regularization problem to a linear one and a convex procedure for finding parts with reduced bending stiffness.

The purpose of this thesis is to describe the development of an anatomically based, young adult eye model, which includes a crystalline lens with a gradient refractive index (GRIN). This model will then be used to investigate the effect of laser refractive surgery. The first step in this process involved developing a symmetrical eye model that was found to be a better predictor of empirical longitudinal spherical aberration than any previous model. Myopia was simulated by either a purely axial or refractive technique. While these models were found to be good predictors of the spherical aberration measured in young adults, they did not predict the total amount of high-order aberrations. The techniques used to simulate a single type of myopia caused the myopic models to become anatomically inaccurate. To improve the eye models a biconic surface was used to quantify the anterior corneal shape as a function of myopia. A method to describe the refractive error and biconic shape parameters in Jackson Cross Cylinder terms was implemented to determine correlations. Results indicate that a biconic accurately models the average shape of the anterior corneal surface as a function of myopia. Adopting the biconic model for the anterior corneal surface and adding average misalignments of the ocular components transformed the models from symmetrical to asymmetrical. Refractive error was now simulated by the anatomically accurate changes in both the anterior corneal shape and axial length. The asymmetrical aberrations resulted from the misalignment of the ocular components and provided a good prediction of average empirical aberrations but underestimated the aberrations of individual subjects. Photorefractive keratectomy, a form of laser refractive surgery, was simulated by theoretically calculated and by empirically measured changes in the shape of the anterior corneal surface. Applying the change in anterior corneal shape to the asymmetrical models was used to develop postoperative models. Changes in corneal shape and model aberrations attributed to theoretical calculations do not match empirical observations. The prediction of increased high-order aberrations in postoperative models based on empirically measured changes in the anterior corneal topography was similar to clinical results. Average anatomically based, GRIN eye models have been developed that accurately predict the average aberrations of emmetropic and myopic young adults. These models underestimate the asymmetrical and total high-order aberrations that have been measured in individual subjects but are still useful for investigating the average effects of procedures like refractive surgery.

Plasmonic nanoparticles support surface plasmon resonances that are sensitive to the environment. Factors contributing to the refractive index sensitivity are explored systematically through simulation, theory, and experiment. Particles small with respect to the wavelength of light and with size parameters much less than 1 have optical properties accurately predicted by quasi-electrostatic theory while particles with larger size parameters necessitate electrodynamics. A theory is developed that captures the effects of geometry on the refractive index sensitivity with a single factor, plasmon band location, and, although based on electrostatic theory, well predicts the sensitivity of particles whose properties are beyond the electrostatic limit. This theory is validated by high quality simulations for compact particles with shape parameters approaching 1 and, therefore, electrodynamic in nature, as well as higher aspect ratio particles that are electrostatic. Experimentally observed optical spectra for nanorods immobilized on glass and subjected to changes in n of the medium are used to calculate the sensitivity of the particles, found to be well matched by a variation on the homogeneous plasmon band theory. The separate electrostatic and electrodynamic components of plasmon band width, are explored and the overall width is found to affect the observability of the aforementioned sensitivity similarly within each particle class. The extent of the sensing volume around a spherical particle is explored and found to vary with particle size for small particles. Through simulation of oriented dielectric layers, it is shown particles are most sensitive to material located in regions of highest field enhancement. Variations on seed-mediated growth of gold nanorods results in spectra exhibiting a middle peak, intermediate to the generally accepted longitudinal and transverse modes. Simulated optical properties and calculated field enhancement illustrates the correlation between geometry and optical properties and allows for identification of the middle peak. / Dissertation

The impact of swirl (i.e., flow with axial and azimuthal velocity components) on the turbulent flow in a pipe is studied using two-component laser-Doppler velocimetry (LDV). There are practical motivations for the flow geometry. For example, previous studies demonstrate that introducing swirl in the tube bank of a paper machine headbox can significantly increase mixing, and hence increase fiber dispersion and orientation isotropy in the finished paper product. The flow characteristics in a pipe downstream of a single straight tapered fin, a single fin with 180??ist but otherwise identical geometry, and four twisted fins were therefore studied at a pipe-based Reynolds number of 80,000. Radial profiles of the mean and rms fluctuations of the streamwise and azimuthal velocity components are measured; results for the straight and twisted single fin are compared to determine the effects of fin geometry and swirl on the turbulent wake downstream of the fin. From a practical viewpoint, it is also desirable to have adjustable swirl, where swirl can either be turned on or off depending upon the type of paper product being produced. The next generation swirler concept consists of fins fabricated from two-way shape memory alloys. Using the two-way memory effect, the fins will be in their straight configuration when cold and twisted configuration (hence acting as a swirler) when hot. This study is the initial phase in developing new active control mechanisms, known as the Vortigen concept, for increasing productivity, and hence reducing wasted raw material and energy, in the pulp and paper industry.