Granada é um grupo de seis silicatos com a mesma estrutura cristalina e fórmulas químicas semelhantes, diferindo um do outro pelos cátions, dos quais o GROSSULAR de fórmula química Ca IND.3Al IND.2Si IND.30 IND.12 é o segundo mineral mais abundante no Brasil, e talvez o mais colorido das granadas. Foram obtidas duas amostras de Araçuaí - Minas Gerais, denominadas GV e GVI que diferem somente no teor de impurezas, as quais foram pulverizadas e peneiradas para realizar medidas de Termoluminescência (TL) e Ressonância Paramagnética Eletrônica (EPR); e cortadas em lâminas e polidas para as medidas de Absorção Ótica(AO). A análise de fluorescência mostrou a presença de 1,37mol% de Fe IND.20 IND.3 na amostra GV e, 6,2mol% na GVI, 1,03mol% de MnO na GV e 0,26mol% na GVI, 0,66mol% de MgO na GV e 0,72mol% na GVI, que participam como defeitos extrínsecos na amostra. A curva de emissão termoluminescente apresentou um pico intenso em alta temperatura em 470ºC para as amostras naturais. Amostras tratadas termicamente em 600ºC/1h. e irradiadas com diferentes doses gama mostraram picos em 145, 235 e 335ºC em GV e em 145, 200, 250, 335 e 445ºC em GVI, mostrando-se mediante a deconvolução da curva TL que GV está formada de seis picos e GVI de sete picos bastante superpostos. Enquanto que em GV os picos de baixa temperatura crescem mais rápido com a irradiação, é o pico em 340ºC que aumenta rapidamente em GVI mantendo sua individualidade, porém em ambos casos os picos TL crescem sublinearmente após 100Gy de doses gama. Outras diferenças consideráveis entre as amostras GV e GVI foram observadas do comportamento com os diferentes tratamentos térmicos, observando-se o aumento da sensibilidade TL somente em GV enquanto que na amostra GVI, não houve a sensibilização, mas, um comportamento bastante caótico. A irradiação ultra-violeta (UV) produz decaimento na intensidade TL, onde em GV a TL residual diminui com a temperatura do pico e em GVI o comportamento é contrário. Estas diferenças não podem ser explicadas baseados somente na diferença do teor de impurezas das amostras e, possivelmente a estrutura cristalina esteja também envolvida. Os íons de ferro e manganês entram na estrutura do grossular, e o cálculo do campo cristalino mostrou que o Fe POT.3+ pode ocupar o sítio tetraédrico e octaédrico substituindo o AI e Si. Os íons Mn POT.2+ e Fe POT.2+ ocupam posições dodecaédricas substituindo o Ca na estrutura. O espectro de EPR. apresentou sinais em g=4,3 , 6,0 relacionados ao ferro e, o sinal em g=2,004 devido à interação de troca e dipolar de ambos íons Fe POT.3+ e Mn POT.2+. O recozimento das amostras em alta temperatura mostrou que os íons de Fe POT.2+ oxidam-se para Fe POT.3+ e os íons de Mn POT.3+ mudam para Mn POT.2+, respectivamente. Não foi encontrada uma correlação entre os defeitos responsáveis pelos espectros de AO e EPR e os centros que participam na termoluminescência. / Garnet is a group of six silicates with the same crystal structure but with chemical formula differing by their cations. Grossular of chemical formula Ca3AlzSi3012 is the second most abundant garnet in Brazil and probably the most colorful of the garnets. Two samples of grossular, named GV and GVI were obtained of Araçuai-Minas Gerais difIering by impurities content. These samples were pulverized and sieved for termoluminescence (TL) and electron paramagnetic resonance (EPR) measurements. Polished plates of 2.0mm thickness were prepared for optical absorption (AO) measurements. The X-ray fluorescence has revealed several kinds of impurities, being the most important 1,37mol% of Fe203 in GV e, 6,2mol% in GVI, 1,03mol% of MnO in GV and O,26mol% in GVI, O,66mol% of MgO in GV and 0,72mol% in GVI, which might participate as extrinsic defects in the samples. The TL glow curve of natural samples shows a high temperature peak at 470°C that is greater in GVI than in GV. Samples heat treated at 600°C/1h and irradiated with different gamma dose present peaks at 145, 235 and 335°C in GV and, 145 200, 250, 335 and 445°C in GVI. However, the glow curve deconvolution shows that in fact GV is formed by six peaks and GVI by seven peaks overlapped. While, the low temperature peaks increase with the dose in GV, it is the last peak in GVI (340°C) that increases fast keeping its individuality, however a similar sublinear dependence with the irradiation dose was founded for both samples. Other differences between these samples refer to the behavior with the pre-irradiation anneal temperature, namely increase in the TL sensibilities observed only in GV and a caotic behavior in GVI. The UV irradiation produces decay in TL intensity with exposure time. The residual TL diminishes with the peak temperature in GV, being opposite in GVI. The iron and manganese ions can replace some ions in the grossular structure. The crystal field analysis shows that the Fe3+ ions occupy tetrahedral and octahedral sites replacing AI and Si, similarly Ca can be substituited by Fe2+ and Mn2+ in the dodecahedral position. The EPR spectra show signals in g=4.3, g=6.0 related to the iron and g=2.004 signal is due to the dipolar and exchange interactions between M 712+ and Fé+ ions. The high temperature heat treatment of the samples give rise to the change from Fe2+ to Fe3+ by oxidation and from Mn3+ to Mn2+ . No correlation between the defects responsible for the AO and EPR spectra and the TL centers was found.

No description available.

Understanding the fundamental physics in light absorption and perfect light absorption is vital for device applications in detector, sensor, solar energy harvesting and imaging. In this research study, a large area fabrication of Al-doped ZnO/Al2O3/graphene/Al2O3/gold/silicon device was enabled by a spin-processable hydrophilic mono-layer graphene oxide. In contrast to the optical properties of noble metals, which cannot be tuned or changed, the permittivity of transparent metal oxides, such as Al-doped ZnO and indium tin oxide, are tunable. Their optical properties can be adjusted via doping or tuned electrically through carrier accumulation and depletion, providing great advantages for designing tunable photonic devices or realizing perfect absorption. A significant shift of Raman frequency up to 360 cm-1 was observed from graphene in the fabricated device reported in this work. The absorption from the device was tunable with a negative voltage applied on the Al-doped ZnO side. The generated absorption change was sustainable when the voltage was off and erasable when a positive voltage was applied. The reflection change was explained by the Fermi level change in graphene. The sustainability of tuned optical property in graphene can lead to a design of device with less power consumption.

The development of nanoscale heterostructure photocatalysts for the effective, direct utilization of visible light (400-750 nm, ~44% of solar spectrum) to drive important chemical conversions is a prime research area in the field of photocatalysis. Particles at nanoscale dimensions have a large surface area-to-volume ratio, expose a high number of active surface sites, and exhibit unique electronic properties (different from bulk) that are beneficial for improving the overall catalytic activity. However, the advantages of size reduction are often overshadowed by the low optical absorption (as absorption power  size3) and colloidal instability (extensive aggregation) of particles at the nanoscale. In this dissertation, we demonstrate a strategy to improve the colloidal stability and enhance the optical absorption of nano-sized semiconductor and metal nanoparticles (NPs) that exhibit weak visible light absorption. The colloidal, free-standing NPs are placed on transparent, dielectric silica nanospheres (SiOx NSs) that act as optical antenna supports, forming SiOx/NP composite nanostructures. The spherical morphology of SiOx enables scattering resonances (Fabry Perot or Whispering Gallery Modes) which enhances the local electric field on or near the surface of the NS. The NPs placed on the surface of SiOx NS interact with the locally enhanced electric field and exhibit improved optical absorption. By varying the size of the SiOx NS, the resonance wavelengths and the intensity of the local electric field enhancement can be tuned, offering the ability of such structures to effectively utilize a wide range of energies in the visible region. Composite nanostructures comprised of various classes of nanomaterials such as metal-doped semiconductor, plasmonic, and non-plasmonic metal NPs were investigated to perform the desirable solar-to-chemical transformations. First, we employed SiOx-loaded silver-doped silver chloride (SiOx/AgCl(Ag)) photocatalyst to investigate the role of metal-induced gap states in AgCl, a wide bandgap semiconductor. SiOx/AgCl(Ag) exhibit high catalytic performance and photostability after 10 cycles of the probe reaction, methylene blue (MB) degradation under visible light irradiation. The results indicate that the visible light absorption due to metal-induced gap states can be further improved by employing the SiOx NSs as supports that act as optical nanoantenna. We then studied the influence of NP size on the catalytic activity to understand the effect of size in promoting the generation and transfer of hot electrons to surface adsorbates. Our findings indicate that upon employing Ag NPs of different particle size (<10 nm and >10 nm) and normalizing for the optical absorption and moles of surface Ag atoms, the efficient generation and transfer of photoexcited hot electrons is favored in the small-sized Ag NPs (size <10 nm) than bigger Ag NPs. Next, we investigated the selective partial hydrogenation of nitroarene to N-aryl hydroxylamine using SiOx-loaded platinum (SiOx/Pt) photocatalysts. We found that change in the surface electronic structure of the small Pt NPs (size <5 nm) due to light illumination and surface modification (by adding suitable organic ligands), minimize the adsorption of the electron-rich hydroxylamine molecules and minimize their complete conversion to aniline, resulting in high N-hydroxylamine selectivity. Overall, our work shows that well-controlled composite nanostructures comprising of active catalyst loaded on dielectric SiOx NS supports that act as optical nanoantenna are a promising class of photocatalysts for driving photon-to-chemical transformations with high activity and product selectivity. / Chemistry

Mineral dust aerosols play an important role in atmospheric chemistry through photolysis and heterogeneous uptake. Both mechanisms strongly depend on the size and composition of mineral dust. Because of the complex nature of dust, chemistry modeling commonly relies on simplified assumptions about the properties of dust particles relevant to physiochemical processes. The goal of this thesis is to investigate the impact of size-resolved composition of dust aerosols on atmospheric photochemistry. The relative importance of dust characteristics in photolysis and heterogeneous loss and the relative roles of the two mechanisms on atmospheric photochemistry are investigated. A new block of spectral aerosol optical properties was developed and incorporated into the tropospheric ultraviolet and visible radiation transfer code in order to calculate spectral actinic fluxes and photolysis rates, J-values. The Fuchs-Sutugin approximation was employed to compute mass transfer from gas to dust mineral species and heterogeneous loss rate, kloss,j. The J-values and kloss,j were incorporated into a one-dimensional photochemistry model to simulate the diurnal cycle of a vertical profile of photochemical species. Several cases of dust loading were considered in the clean and polluted marine environments. A size-resolved mineralogical composition was constructed by selecting a range of the mass fraction of the three main mineral species such as iron oxide-containing clay minerals, carbonate-containing species, and quartz. This work demonstrates that differences in microphysical and chemical properties of mineral dust lead to the important changes in spectral optical properties, J-values, and kloss,j. It also shows that non-linear relationships of photochemical species with two mechanisms result in various changes in the photochemical oxidant fields and that the most important factor controlling the photochemistry field is the dust size distribution, followed by the amount of mineral species with high uptake coefficients and the amount of iron oxide-clay aggregates. This work demonstrates that accounting for regional differences in microphysical and chemical properties of mineral dust will improve the assessment of the impact of mineral dust on tropospheric photochemistry. In addition, it suggests that the size and composition of mineral dust will lead to a deeper understanding of the impact of mineral dust on the global climate system.

Τα τελευταία χρόνια, οι μη επεμβατικές μέθοδοι διάγνωσης αλλά και θεραπείας κερδίζουν συνεχώς έδαφος έναντι των παραδοσιακών επεμβατικών μεθόδων. Σκοπός της διπλωματικής αυτής εργασίας είναι η μελέτη της μετάδοσης του φωτός μέσα στο ανθρώπινο δέρμα και κυρίως η μελέτη της απορρόφησης που υφίσταται από αυτό, με σκοπό την μέτρηση βιολογικών συντελεστών, όπως οι συγκεντρώσεις κάποιων ουσιών στον οργανισμό, ο υπολογισμός των οποίων μπορεί να οδηγήσει σε χρήσιμα διαγνωστικά συμπεράσματα. Επίσης, αναλύεται η μέθοδος της παλμικής οξυμετρίας, που χρησιμοποιείται ευρύτατα για την παρακολούθηση του αρτηριακού κορεσμού οξυγόνου και του καρδιακού παλμού. Μετρώντας την απορρόφηση του φωτός σε δύο διαφορετικά μήκη κύματος, ένα στο ερυθρό (660 nm) και ένα στο εγγύς υπέρυθρο (940 nm), και απομονώνοντας το μεταβαλλόμενο μέρος αυτής, που οφείλεται στις διακυμάνσεις στον όγκο του αρτηριακού αίματος, μπορούμε να υπολογίσουμε με τη χρήση του νόμου των Beer-Lambert τον κορεσμό του αίματος σε οξυγόνο μέσω του υπολογισμού των συγκεντρώσεων του σε μειωμένη αιμογλοβίνη και σε οξυαιμογλοβίνη. Τέλος, περιγράφεται η υλοποίηση της μεθόδου και ο σχεδιασμός ενός παλμικού οξυμέτρου ενός chip με τη χρήση του μικροεπεξεργαστή MSP430. / Over recent years, non-invasive methods of diagnosis and treatment are gaining ground against the traditional invasive methods. In this thesis, an integrated review of the transfer of optical radiation into human skin and primarily light absorption through human skin is presented, aiming at measuring biological information, such as concentrations of certain substances in the human body, whose calculation can lead to useful diagnostic conclusions. The method of Pulse Oximetry, which is widely used for monitoring arterial oxygen saturation and heart rate of a patient, is also presented. By measuring the absorption of light at two different wavelengths, one red (660 nm) and one near-infrared (940 nm), and isolating its AC component, which is a result of the variations in the volume of arterial blood, we can calculate the oxygen saturation using the Beer-Lambert law, by estimating the concentrations of oxyhemoglobin and reduced hemoglobin. Moreover, the implementation of a single chip portable pulse oximeter using the ultra low power capability of the MSP430 is demonstrated.

Tese(mestrado) - Universidade Federal Do Rio Grande, Programa de Pós-graduação em Oceanografia Biológica, Instituto de Oceanografia, 2013. / Submitted by Cristiane Gomides (cristiane_gomides@hotmail.com) on 2013-11-18T12:52:36Z No. of bitstreams: 1 AMABILE.pdf: 5765676 bytes, checksum: a4926b187c0614bc4d913a29b23870ab (MD5) / Approved for entry into archive by Angelica Miranda (angelicacdm@gmail.com) on 2013-11-18T19:07:50Z (GMT) No. of bitstreams: 1 AMABILE.pdf: 5765676 bytes, checksum: a4926b187c0614bc4d913a29b23870ab (MD5) / Made available in DSpace on 2013-11-18T19:07:50Z (GMT). No. of bitstreams: 1 AMABILE.pdf: 5765676 bytes, checksum: a4926b187c0614bc4d913a29b23870ab (MD5) Previous issue date: 2013 / Imagens de satélite da cor do oceano detectam intensas florações do fitoplâncton durante primavera e verão ao longo da quebra de plataforma Argentina, mas são escassas as medidas ópticas in situ na região. O objetivo geral desta tese foi investigar a variabilidade das propriedades ópticas das florações do fitoplâncton na quebra de plataforma Argentina e arredores. Entre 2006 e 2009, seis cruzeiros foram conduzidos com diversas medidas biológicas e físicas, incluindo medicões bio-ópticas, dentre as quais algumas inéditas na região. As seguintes medidas foram consideradas: coeficientes spectrais de absorção da luz pelo material particulado, que inclui o fitoplâncton e detritos; coeficiente de atenuação da luz pelo material particulado a 660nm; irradiância descendente e radiância ascendente da luz com alta resolução espectral, a partir das quais se obtém os coeficientes da atenuação difusa e a reflectância do sensoriamento remoto in situ; reflectância do sensoriamento remoto medida por satélite; concentração de clorofila-a total e fracionada por classes de tamanho do fitoplâncton estimada pelo método fluorimétrico; concentrações de clorofila-a e pigmentos acessórios do fitoplâncton, obtidas por HPLC; abundância taxonômica relativa do fitoplâncton estimada por CHEMTAX; e fator de tamanho celular do fitoplâncton estimado pelos espectros de absorção da luz pelo fitoplâncton. Grande variabilidade foi observada nos coeficientes de absorção, atenuação (e espalhamento) e atenuação difusa da luz para uma dada concentração de clorofila-a e vice-versa. Grande parte dessa variabilidade pôde ser explicada por variações no tamanho celular do fitoplâncton e, portanto, ao efeito “pacote”. A variabilidade nos espectros de reflectância do sensoriamento remoto (propriedade óptica aparente) medidos in situ revelou o fitoplâncton como componente dominante nas propriedades ópticas das florações na região. Porém, a variabilidade nos coeficientes específicos (i.e., normalizados por clorofila-a) de absorção e espalhamento (propriedades ópticas inerentes), devido a variações no tamanho celular do fitoplâncton, influenciou o desempenho de modelos bio-ópticos para estimar concentração de clorofila-a por satélite. As principais situações de composição taxonômica do fitoplâncton que ocorrem durante as florações na região (dominância por diatomáceas, haptofíceas, e com contribuições destes grupos e de outros, sem dominância) foram refletidas de forma coerente nos comportamentos espectrais de absorção da luz pelo fitoplâncton, indicando o potencial em discriminar as assembleias das florações na região através de dados ópticos. Particularmente, a identificação de dominância de diatomáceas e haptofíceas, a partir de um comprimento de onda, e também pelo fator de tamanho celular do fitoplâncton, que pode ser estimado por satélite, indica o potencial em identificar a dominância de tais grupos taxonômicos por sensoriamento remoto na região. / Satellite images usually detect intense phytoplankton blooms during spring and summer along the Argentina shelf break. Because in situ optical measurements are scarce in the region, six cruises were conducted from 2006 to 2009 to measure several physical, biological, and optical properties. Some of the bio-optical properties were gathered for the first time in the region. The aim of this thesis was to characterize the optical properties of phytoplankton blooms along the Argentina shelf break e adjacent areas. For this purpose, the following measurements and data were considered: light absorption coefficients of particulate material that includes phytoplankton and detritus; light attenuation coefficient of particulate material at 660 nm; hyperspectral downwelling irradiance and upwelling radiance, from which one obtains the vertical attenuation coefficients for downwards irradiance and upwards radiance and in situ reflectance of remote sensing; total and size-fractionated chlorophyll-concentration, estimated by fluorimetric method; concentrations of chlorophyll-a and accessory pigments of phytoplankton obtained by HPLC; relative taxonomic abundance of phytoplankton estimated by CHEMTAX; a cell size parameter for phytoplankton estimated from the phytoplankton absorption spectra. Large variability was observed for absorption coefficients of phytoplankton, scattering of particles and the vertical attenuation coefficients for downwards irradiance for a given chlorophyll-a concentration. Such variability could be largely explained by variations in cell size of phytoplankton and therefore the "package" effect, as indicated by the cell size parameter. The characterization of the variability in the remote sensing reflectance (apparent optical property) measured in situ revealed phytoplankton as the dominant component on the optical properties of algal blooms in the region. Nevertheless, the variability in absorption and scattering coefficients (inherent optical properties) due to variations in cell size of phytoplankton was shown to impact the performance of bio-optical models that relies on band reflectance ratios of remote sensing to retrieve chlorophyll-a from satellite. The main taxonomic composition of the phytoplankton blooms (dominance of diatoms, haptophytes, and mixed contributions of these and others groups, but with no dominance) was consistently reflected on the spectral shape of light absorption of phytoplankton. Our results indicate a potential to discriminate phytoplankton assemblages in the region through optical data. Particularly, the identification of diatoms or haptophytes using one wavelength or through a phytoplankton cell size parameter, which can be estimated from satellite, has a potential of identifying the dominance of such taxonomic groups from remote sensing in the region.

In this dissertation, we study the optical property of 2D graded photonic super-crystals (GPSCs) for photon management. We focused primarily on manipulation and control of light by using the newly discovered GPSCs which present great opportunity for electromagnetic wave control in photonic devices. The GPSC has been used to explore the superior capability of improving the light extraction efficiency of OLEDs. The enhancement of extraction efficiency has been explained in term of destructive interference of surface plasmon resonance and out-coupling of surface plasmon through phase matching provided by GPSC and verified by e-field intensity distributions. A large light extraction efficiency up to 75% into glass substrate has been predicted through simulation. We also study the light trapping enhancement in GPSCs. Broadband, wide incident angle, and polarization independent light trapping enhancement is achieved in silicon solar cells patterned with the GPSCs. In addition, novel 2D GPSCs were fabricated using holographic lithography through the interference lithography by two sets of multiple beams arranged in a cone geometry using a spatial light modulator (SLM). Finally, we also report a fabrication of GPSCs with a super-cell size of 12a×12a by using e-beam lithography. Diffraction pattern from GPSCs reveals unique diffraction properties. In an application aspect, light emitting diode arrays can be replaced by a single light emitting diode shinning onto the diffraction pattern for a uniform fluorescence.

This diploma thesis is focused on study of electric and optoelectric properties of conjugated polymers. The theoretical part describes the relationship between molecular structure of conjugated materials and their chosen macroscopic physical properties like absorption of visible and ultraviolet radiation, electrical conductivity and photoconductivity. This part also describes photochromism and its utilization for construction of light driven current switch. The experimental part studies this switch based on change of photochromic species dipole moment dispersed in conjugated conducting polymer. The active switching unit is represented by photochromic spiropyran 1’,3’-dihydro-1’,3’,3’-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2’-(2H)-indol] which is dispersed in conjugated conducting polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylen]. The influence of the photochromic conversion on the polymer matrix was studied by absorption spectroscopy, current-voltage measurements and spectrally resolved steady state photoconductivity and transient photoconductivity.

Tato práce se zabývá rozšířením snímače otisků prstů Touchless Biometric Systems 3D-Enroll o jednotku detekce živosti prstu na základě žil. Bylo navrhnuto a zkonstruováno hardwarové řešení s využitím infračervených diod. Navržené softwarové řešení pracuje ve dvou různých režimech: detekce živosti na základě texturních příznaků a verifikace uživatelů na základě porovnávání žilních vzorů. Datový soubor obsahující přes 1100 snímků jak živých prstů tak jejich falsifikátů vznikl jako součást této práce a výkonnost obou zmíněných režimů byla vyhodnocena na tomto datovém souboru. Na závěr byly navrhnuty materiály vhodné k výrobě falsifikátů otisků prstů umožňující oklamání detekce živosti pomocí žilních vzorů.