Dissertations / Theses on the topic 'Kubelka-Munk'

Mestrado em Engenharia Física
Com este trabalho, pretendeu-se efectuar a caracterização de algunsparâmetros ópticos de filmes semicondutores, recorrendo a medidas dereflectância difusa, com o objectivo principal de determinar a energia de hiatodesses materiais. Desenvolveu-se um algoritmo computacional com base no modelo de Kubelka-Munk, modificando as expressões originais de acordo com as característicasdo filme e do tipo de iluminação utilizado. Optimizaram-se os resultados,aplicando o método do gradiente espectral projectado. A partir deste método,obtiveram-se os valores dos parâmetros do índice de refracção, espessura,coeficiente de dispersão e coeficiente de absorção, a partir do qual sedeterminou a energia de hiato do material. Testou-se o algoritmo no caso deum filme de dióxido de titânio (fase rutilo) num substrato de titânio, tendo sidopossível comparar com os resultados encontrados na literatura. Aplicou-se omesmo no caso de duas amostras de dióxido de titânio (fase anatáse)depositadas sobre um substrato de molibdénio, tendo-se obtido uma energiade hiato de 3,27 e 3,18 eV. ABSTRACT: With this work, it was pretended to do the characterization of some opticalparameters of semiconductor films, through diffuse reflectance measurements.The main objective was to determine the bandgap energy of those materials. A computational algorithm based on the Kubelka-Munk was developed,modifying the original expressions according to the film characteristics and thesort of illumination used. The results were optimized, applying the spectralprojected gradient method. Values for the refraction index, thickness,dispersion and absorption coefficient were obtained. The bandgap energy wasdetermined from the latter parameter. The algorithm was tested for a rutiletitanium dioxide film deposited on a titanium substrate, and from these results itwas possible to compare with the values from literature. The same algorithmwas applied in the case of two samples of anatase titanium dioxide depositedon a molibdenium substrate. A bandgap energy of 3.27 and 3.18 eV wasobtained.

O caolim é uma argila utilizada em diversos ramos da indústria: papel, tintas, plásticos, borrachas, produtos farmacêuticos, cosméticos e alimentícios, entre outros. Os caolins da região amazônica estão entre os melhores do mundo e as suas reservas estão entre as mais abundantes. Apesar de a sua lavra ser relativamente simples e barata, o processamento do caolim pode ser problemático em algumas ocasiões devido à presença de minerais contaminantes, principalmente hematita, goethita e anatásio. A alvura, principal parâmetro de qualidade do produto, é insuficiente para detectar a presença destes minerais no caolim in situ e ao longo das etapas de beneficiamento, e devido a isto ocorrem situações onde o minério não atinge as especificações de qualidade ao final do processo ou é mal aproveitado. Portanto, este trabalho desenvolveu uma técnica para a estimativa da concentração destes minerais contaminantes no caolim, proporcionando assim um maior controle do processo de beneficiamento e facilitando a sua classificação como minério ou estéril. Esta técnica é baseada na teoria de Kubelka-Munk, que utiliza o espectro de reflectância, no presente caso medido na região visível. Foi necessário o desenvolvimento de alguns procedimentos teóricos e experimentais para a aplicação da teoria ao caolim, que possibilitaram a realização de medidas de concentração a nível semi-quantitativo. Apesar de algumas dificuldades de ordem experimental encontradas, esta nova técnica tem potencial para reduzir custos operacionais e maximizar as reservas.
Kaolin is a clay used in many sections of the industry: paper, paints, plastics, rubbers and pharmacy, cosmetic and food products. The kaolins in Amazon region are among the best in the world and their reserves are among the most abundant. Besides its mining being relatively simple and cheap, kaolin processing can be problematic in certain cases due to the presence of contaminant minerals, mainly hematite, goethite and anatase. Brightness, the principal quality parameter of the final product, is insufficient for detecting the presence of these minerals on the kaolin in situ and along its processing, leading to situations where the ore fail quality specifications or is badly used to advantage. Therefore, this work developed a technique to estimate the concentration of these minerals in kaolin, providing then a better control over the process and facilitating kaolin classification between ore and waste. This technique is based on Kubelka-Munk theory, which uses the reflectance spectrum, in the present case measured in the visible range. It was necessary to develop some theoretical and experimental procedures to apply the theory on kaolin, which enabled concentration measurements with semiquantitative precision. Aside some practical difficulties encountered, this new technique brings the potential to reduce operational costs and maximize reserves.

Orientador: Fernando Galembeck
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica
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Resumo: A morfologia de filmes compósitos preparados com fosfato de alumínio e látexes de poli(metacrilato de metila-co-acrilato de butila) e de poli(estireno-co-acrilato de butila) foi caracterizada por técnicas de microscopia eletrônica de transmissão e de varredura (TEM, SEM) e por técnicas de microscopia de varredura por sonda (AFM, DPFM). O grau de opacidade (razão de contraste) e os cálculos de coeficiente de espalhamento das partículas de fosfato de alumínio nos filmes compósitos foram obtidos através dos espectros de refletância. As micrografias das superfícies de desbaste dos filmes compósitos mostraram espaços vazios entre os agregados de partículas de fosfato de alumínio dispersos pela matriz polimérica. A adesão entre os agregados de partículas de fosfato de alumínio e polímero é muito boa nas interfaces de contato. A refletância dos filmes compósitos varia amplamente, dependendo da concentração das partículas de fosfato de alumínio, assim como da sua forma de uso em pó ou em dispersão e da dimensão dos espaços vazios entre os agregados de partículas. Os resultados das medidas óticas de opacidade mostraram que os filmes compósitos mais opacos foram os obtidos com fosfato de alumínio na forma de pó e com a dimensão dos vazios entre os agregados de partículas na mesma ordem de grandeza que o comprimento de onda da luz na região do visível (400 a 700 nm). Os coeficientes de espalhamento dos filmes de fosfato de alumínio/poli(estireno-co-acrilato de butila) foram calculados empiricamente usando o modelo de Kubelka-Munk e os resultados mostraram que os vazios contidos nos agregados de partículas de fosfato de alumínio justificam a opacidade dos filmes. O filme mais opaco, com razão de contraste de 88 %, apresentou ampla distribuição de dimensão dos vazios com média numérica igual a 650 nm. Além disso, os valores obtidos dos coeficientes de espalhamento experimentais são muito próximos dos coeficientes de espalhamento estimados pela teoria de Mie. A eficiência de espalhamento, predita pela teoria de Mie, de uma bolha de ar rodeada por fosfato de alumínio com diâmetro médio de 650 nm é apenas 12 % menor que a eficiência de espalhamento de uma partícula de dióxido de titânio, no seu diâmetro ótimo de 350 nm, dispersa no mesmo meio
Abstract: Composite films prepared with aluminum phosphate and latex of poly(methyl methacrylate-co-butyl acrylate) and poly(styrene-co-butyl acrylate) were characterized by electronic microscopy (TEM, SEM) and by different techniques of scanning probe microscopy (AFM, DPFM). Opacity (contrast ratio) and light scattering coefficients of composite films were obtained from reflectance spectra. SEM and TEM micrographs from composite films trimmed surfaces or thin cuts showed voids within aluminum phosphate particle aggregates. The adhesion between aluminum phosphate particle aggregates and polymer is very good at contact interfaces. Composite films reflectance changes widely, depending on void diameters, on aluminum phosphate particle concentration, as well as its use in the form of powder or dispersion. Opacity results showed that the most opaque composite films were obtained with aluminum phosphate powder and with void diameters in the same order of magnitude as the wavelength of light in the visible region (400 to 700 nm). Scattering coefficients of aluminum phosphate/poly(styrene-co-butyl acrylate) films were calculated empirically using the Kubelka-Munk model and the results showed that the observed voids account for films opacity. The most opaque composite film shows contrast ratio equal to 88 % and a broad distribution of void diameters, peaking at ca. 650 nm. Film scattering coefficient of the observed voids was calculated using Mie theory to evaluate their contribution to film opacity showing that the measured and estimated values are in reasonable agreement. The Mie calculations show that scattering efficiency for air trapped within the phosphate particles dispersed in polymer latex is in excess of 4 units in the 650 nm diameter range, which is only 12 % lower than the calculated values for optimum size TiO2 particles (350 nm) dispersed in the same polymer
Doutorado
Físico-Química
Doutor em Ciências

This research develops an extendible framework for reproducing watercolor in a digital environment, with a focus on interactivity using the GPU. The framework uses the lattice Boltzmann method, a relatively new approach to fluid dynamics, and the Kubelka-Munk reflectance model to capture the optical properties of watercolor. The work is demonstrated through several paintings produced using the system.

O principal parâmetro de avaliação da qualidade de carvões para uso na geração de energia termoelétrica é o percentual de cinzas. Em uma planta de beneficiamento, saber o percentual de cinzas da alimentação, concentrado e rejeito é de suma importância para os ajustes nos equipamentos de concentração. No caso do carvão da camada I1 do depósito mineral do Leão a janela de tempo entre o ponto mais adequado para amostragem e o fim da campanha de beneficiamento não propicia que se conheça o teor de cinzas da alimentação do processo de beneficiamento. Em virtude disso, este trabalho tem como objetivo de fornecer uma estimativa confiável do teor de cinzas da alimentação para propiciar a aplicação na planta de beneficiamento. Para esse intento utilizou-se a teoria de Kubelka-Munk que por meio de sua expressão matemática transforma a reflectância em uma grandeza aditiva que propicia a estimativa das porcentagens de matéria orgânica e mineral contida no carvão devido a diferença de reflectância entre esses materiais. Como resultado final foram gerados diversos modelos com intuito de verificar qual deles se adaptava melhor aos dados. Por fim, foi possível concluir que há possibilidade de estimar o teor de cinzas de carvão por meio da reflectância e com confiabilidade de 96,78% que toda a leitura agrega um erro máximo de ± 5% para o melhor modelo.
The main parameter in quality evaluation of coals employed in power generation is the ash content. In a beneficiation plant, knowing the ash content of the feed, concentrate an tailings is mandatory to set up the concentration equipment. In the case of the I1 coal seam of Leão’s deposit the time window between sampling routine and beneficiation routine does not allow to know the feed ash content before the beneficiation process. By this reason, this work aims to provide a reliable estimative of the feed ash content to propitiate its application in the beneficiation plant. For this purpose it was used Kubelka-Munk’s theory that, by using a mathematic expression, transforms reflectance into a additive quantity which allows to estimate mineral and organic matter present in coal by the difference of reflectance between these materials. As result, it was generated several models in order to analyze which one is better suited to the data. Finally, as a conclusion, it is possible to infer the ash content of coal by reflectance with confidence of 96,78% that all measure brings up a maximum error of ± 5% for the best model.

Mestrado em Engenharia Química
A cor está presente em tudo o que nos rodeia, e é, na generalidade, um fator determinante em diversos acontecimentos e fenómenos, não somente sobre os que respeitam à atividade humana, mas dos seres vivos em geral. Na indústria das tintas é incontestável a importância que a cor apresenta, pois o sucesso dos produtos que dessa indústria resultam, passa, seguramente, pelas características da cor que apresentam. Sendo, portanto, vital para esta indústria o estudo das cores. Neste contexto a empresa CIN revela o interesse no estudo da cor, procedendo à criação de bases de dados de formulação de cor para os seus produtos. Surgindo o presente trabalho como demonstração desse mesmo estudo, contribuindo com os resultados da criação e otimização de bases de dados de formulação de cor, que serão utilizadas como ponto de partida para a afinação da cor. Neste trabalho, descrevem-se algumas das teorias essenciais para a análise às propriedades das cores, bem como o procedimento da criação e otimização das bases de dados que, de forma sucinta, consiste no armazenamento das propriedades óticas das pastas pigmentos utilizadas para a produção de cor nos produtos, através do software adequado, que neste caso se baseia na teoria de Kubelka-Munk, e, posteriormente procedendo à reprodução de formulações de cor e consequente avaliação. A avaliação é feita recorrendo aos métodos de diferença de cor do sistema CIELab. Se necessário, o ajuste das pastas pigmentos no software é feito através da força pigmentos da pasta de pigmentos, voltando a ser reproduzidas formulações de cor para as mesmas cores padrão, e avaliadas novamente. O trabalho proposto foi concluído com sucesso, tendo sido, para o efeito, construídas e otimizadas três bases de dados que disponibilizam formulações de cor, com pequenas diferenças, relativamente à cor pretendida.
The colour is present in everything that surrounds us, and generally, it is a determinant factor in many events and phenomena, not only regarding human’s activity, but also on all living beings’ actions. In the paint industry is undeniable the importance of the colour, bearing in mind that the success of the products that arise from this industry depends on the characteristics of the colour. For this reason, it is vital, for this kind of Industry, assure the necessary analyses for the colour’s development. In this context, CIN (the company) reveals its interest in the study of the colour. For that purpose, the company has proposed the creation of databases with the intention of formulating colour for their products. This work should consist in a demonstration of that investment and, consequently, its results based on the creation and optimization of those databases. In this work, some theories about the colour’s properties are described, as well as the procedure of creating and optimizing the database. The process regarding the database includes saving the optical properties of the colorants on the database, using software that applies the Kubelka-Munk theory to obtain thus properties. The next step is the optimization of the database that consists in the production of coloured paints with the formulation provided by the software. This colour is evaluated using the CIELab system based in differences of colour method, if necessary is possible to modified the colour strength of the colorant in the software, and, than, the coloured paints returned to be reproduced and evaluated. The proposed work has been completed successfully, and as a result, three databases were created and optimized giving predictions with insignificant differences to the standard colour that was set out as a target.

This thesis is about modelling and predicting the perceived whiteness of plain paper from the paper composition, including fluorescent whitening agents. This involves psychophysical modelling of perceived whiteness from measurable light reflectance properties, and physical modelling of light scattering and fluorescence from the paper composition. Existing models are first tested and improvements are suggested and evaluated. A colour appearance model including simultaneous contrast effects (CIECAM02-m2), earlier tested on coloured surfaces, is successfully applied to perceived whiteness. An extension of the Kubelka-Munk light scattering model including fluorescence for turbid media of finite thickness is successfully tested for the first time on real papers. It is extended to layered constructions with different layer optical properties and modified to enable parameter estimation with conventional d/0° spectrophotometers used in the paper industry. Lateral light scattering is studied to enable simulating the spatially resolved radiance factor from layered constructions, and angle-resolved radiance factor simulations are performed to study angular variation of whiteness. It is shown that the linear CIE whiteness equation fails to predict the perceived whiteness of highly white papers with distinct bluish tint. This equation is applicable only in a defined region of the colour space, a condition that is shown to be not fulfilled by many commercial office papers, although they appear white to most observers. The proposed non-linear whiteness equations give to these papers a whiteness value that correlates with their perceived whiteness, while application of the CIE whiteness equation outside its region of validity overestimates perceived whiteness. It is shown that the fluorescence efficiency of FWA is essentially dependent only on the ability of the FWA to absorb light in its absorption band. Increased FWA concentration leads accordingly to increased whiteness. However, since FWA absorbs light in the violet-blue region of the electromagnetic spectrum, the reflectance factor decreases in that region with increasing FWA amount. This violet-blue absorption tends to give a greener shade to the paper and explains most of the observed greening and whiteness saturation at larger FWA concentrations. A red-ward shift of the quantum efficiency is observed with increasing FWA concentration, but this is shown to have a negligible effect on the whiteness value. The results are directly applicable to industrial applications for better instrumental measurement of whiteness and thereby optimising the use of FWA with the goal to improve the perceived whiteness.
PaperOpt

This thesis is about modelling and predicting the perceived whiteness of plain paper from the paper composition, including fluorescent whitening agents. This includes psycho-physical modelling of perceived whiteness from measurable light reflectance properties, and physical modelling of light scattering and fluorescence from the paper composition. Existing models are first tested and improvements are suggested and evaluated. The standardised and widely used CIE whiteness equation is first tested on commercial office papers with visual evaluations by different panels of observers, and improved models are validated. Simultaneous contrast effects, known to affect the appearance of coloured surfaces depending on the surrounding colour, are shown to significantly affect the perceived whiteness. A colour appearance model including simultaneous contrast effects  (CIECAM02-m2), earlier tested on coloured surfaces, is successfully applied to perceived whiteness. A recently proposed extension of the Kubelka-Munk light scattering model including fluorescence for turbid media of finite thickness is successfully tested for the first time on real papers. It is shown that the linear CIE whiteness equation fails to predict the perceived whiteness of highly white papers with distinct bluish tint. This equation is applicable only in a defined region of the colour space, a condition that is shown to be not fulfilled by many commercial office papers, although they appear white to most observers. The proposed non-linear whiteness equations give to these papers a whiteness value that correlates with their perceived whiteness, while application of the CIE whiteness equation outside its region of validity overestimates perceived whiteness. It is shown that the quantum efficiency of two different fluorescent whitening agents (FWA) in plain paper is rather constant with FWA type, FWA concentration, filler content, and fibre type. Hence, the fluorescence efficiency is essentially dependent only on the ability of the FWA to absorb light in its absorption band.  Increased FWA concentration leads accordingly to increased whiteness. However, since FWA absorbs light in the violet-blue region of the electromagnetic spectrum, the reflectance factor decreases in that region with increasing FWA amount. This violet-blue absorption tends to give a greener shade to the paper and explains most of the observed greening and whiteness saturation at larger FWA concentrations. A red-ward shift of the quantum efficiency is observed with increasing FWA concentration, but this is shown to have a negligible effect on the whiteness value. The results are directly applicable to industrial applications for better instrumental measurement of whiteness and thereby optimising the use of FWA with the goal to improve the perceived whiteness. In addition, a modular Monte Carlo simulation tool, Open PaperOpt, is developed to allow future spatial- and angle-resolved particle level light scattering simulation.
PaperOpt

La spectroscopie de réflectance diffuse dans le domaine du visible est une technique paradoxalement rarement utilisée pour identifier les matériaux des couches picturales des oeuvres d'art. Quand elle est malgré tout mise en oeuvre, l'identification de pigments à partir de ce type de mesures repose toujours sur la comparaison avec une base de données spectrophotométriques de pigments de référence. Au sein du Centre de Recherche et de Restauration des Musées de France, la base de données est composée des spectres de réflectance de pigments purs, secs et en poudre. Une couche picturale est au contraire constituée de pigments parfois mélangés et dispersés dans un liant. Ces deux caractéristiques des couches picturales ont permis de distinguer deux axes de recherche pour le travail de thèse. I. La caractérisation des mélanges de pigments La modélisation de Kubelka-Munk s'est avérée pertinente pour la gamme usuelle des couleurs utilisées dans les oeuvres d'art, et ce même dans le cas extrême des mélanges dans lesquels un des composants est nettement minoritaire. Il est à présent possible, pour un mélange binaire, de déterminer les composants du mélange dans la majorité des cas par traitement numérique des mesures spectrophotométriques. Une fois la nature des composants déterminée, il est de plus systématiquement possible d'en retrouver les proportions relatives. Les résultats obtenus sur les échantillons modèles ont pu être adaptés au cas d'une oeuvre d'art : la Vierge d'Annonciation attribuée à Giovanni di Paolo. Dans ce tableau italien du XVe siècle, la couleur du visage est réalisée à partir d'un mélange de blanc de plomb et de vermillon a tempera. Les proportions relatives calculées de ces deux pigments sont en accord avec ce qui est observable au microscope optique sur des prélèvements et mesurable ensuite par traitement des images. II. L'influence du liant Des échantillons de couches picturales ont été réalisés par un artiste selon une recette traditionnelle. La concentration de pigments et le nombre de couches de matière picturales varient selon les échantillons. Ces derniers ont été étudiés parallèlement en spectrophotométrie, en diffractométrie des rayons X et en microfluorimétrie X. Les résultats obtenus par ces méthodes d'analyse concordent. La méthode de Rietveld d'affinement des diffractogrammes permet notamment d'aboutir à des valeurs de concentration de pigment dans le liant tout à fait en accord avec les résultats obtenus par la modélisation de la propagation de la lumière dans les milieux absorbants et diffusants utilisée pour interpréter les mesures spectrophotométriques. L'aboutissement de ce travail de thèse devrait permettre aux scientifiques de la conservation, aux historiens d'art et aux restaurateurs d'envisager la spectrophotométrie comme une technique d'analyse qualitative et quantitative, sans prélèvement, sans contact et réalisable in situ, qui fournit la nature et les proportions des différents constituants de la matière picturale.

O estudo da propagação da luz nas porcelanas é importante para entender seu comportamento óptico frente a situações clínicas como fotoativação de cimentos resinosos e sua resposta estética, quando observada sobre diferentes fundos. Este trabalho estudou a influência da espessura, cor, opacidade e marca comercial das porcelanas feldspáticas na propagação da luz visível, através da teoria de KubelkaMunk (KM), nos intervalos de comprimento de onda de 410500nm e de 410700nm. Foram confeccionados discos de 12,5mm por 1 mm de espessura de porcelana feldspática de duas opacidades, corpo (B) e corpo opaco (BO), das marcas Vintage Halo (HALO), Noritake Super Porcelain EX3 (NORI) e IPS dSIGN (IPS), nas cores A1, A35 e B3 (n=7). Os discos foram polidos através de uma série de lixas abrasivas até a granulação 600 e acondicionados individualmente em ambiente seco. Os discos tiveram suas curvas espectrais de refletância obtidos em contato óptico, sobre fundo branco e preto, através do uso de um espectrofotômetro com esfera de integração acoplada, no intervalo de comprimento de onda de 410700nm. As curvas de refletância foram inseridas na teoria KM, para obtenção e análise quantitativa e qualitativa das propriedades ópticas de cada material. As análises qualitativas envolveram a observação do comportamento espectral das curvas de espalhamento, absorção, espessura infinita e reflexão para todos aos materiais em função do comprimento de onda. As análises quantitativas envolveram a obtenção das espessuras ópticas estimadas em extinções crescentes de 50% (X50), 90% (X90), 95% (X95) e infinita 99.9% (X99.9), para o intervalo de comprimento de onda de 410500nm e a obtenção da espessura óptica infinita 99.9% (X) e dos Parâmetros de Translucidez (TP), estimados nas espessuras de 0.5mm (TP0.5), 1.25mm (TP1.25) e 2.00mm (TP2.00), para o intervalo de comprimento de onda de 410700nm. Os Parâmetros de Translucidez foram utilizados para avaliar o efeito de mascaramento da porcelana sobre os fundos utilizados. Os resultados mostraram que todos os fatores (cor, opacidade e marca comercial) exerceram influência para atenuar a propagação da luz através dos espécimes. De maneira geral, a maior atenuação de luz esteve ligada à porcelanas de corpo opaco e mais saturadas (cor A35 e B3). Em relação à marca comercial a porcelana IPS, atenuou de maneira geral mais luz nas cores A35 e B3 em relação às mesmas cores das marcas HALO e NORI nas espessuras ópticas estudadas. Os valores de espessura óptica infinita (espessura onde a energia transmitida é praticamente zero), para ambos os intervalos de comprimento de onda, para todos os materiais, superaram os limites de espessura clínica indicados pela literatura. Isto implicou que, no caso do intervalo de 410 a 500nm, a energia transmitida pode girar de 20 a 5% para as porcelanas de corpo, e de 10 a 5%, para as de corpo opaco e, no caso do mascaramento, as porcelanas serão mais influenciadas por fundos que apresentarem resposta colorimétrica acentuada nas regiões alaranjadas e avermelhadas do espectro visível. As análises qualitativas mostraram que para todos os materiais e espessuras a luz será preferencialmente atenuada no início do espectro, intervalo de 410 a 500nm e menos atenuada em direção ao final do espectro visível. Os resultados também mostraram que com o aumento da espessura, a atenuação aumentou, e que a relação entre espessura e atenuação é não linear.
The study of light propagation through porcelains is important to understand its optical behavior in front of clinical situations such as the photoactivation of luting cements and their esthetic responses, when observed against different backgrounds. This research studies the influence of thickness, shade, opacity, and commercial brands of feldspatic porcelains on the propagation of visible light through the Kubelka Munk Theory for the wavelength intervals of 410500nm and 410700nm. Discs with 12,5mm in diameter and thickness of 1mm were prepared with feldspatic porcelain in two opacities, body (B) and opaque body (BO), three commercial brands; Vintage Halo (HALO), Noritake Super Porcelain EX3 (NORI), and IPS dSIGN (IPS), and three shades, A1, A35, and B3 (n=7). The discs were polished with a series of waterproof sandpapers down to a #600 grade sandpaper, and individually stored in a dry environment. The spectral reflectance curves were acquired from the disks on optical contact, against white and black backgrounds, with a spectrometer with a diffuse reflectance attachment (an attached integration sphere), in the wavelength interval of 410700nm. The reflectance spectra were inserted in the KM theory to quantitatively and qualitatively obtain and analyze the optical properties of each material. The qualitative analyses were obtained from the observation of the spectral behavior of scattering, absorption, infinite optical thickness, and reflection spectra for all materials as a function of the wavelength. The quantitative analyses involved obtaining the predicted optical thicknesses in extinctions with increments of 50% (X50), 90% (X90), 95% (X95) and infinite 99.9% (X99.9), for the wavelength interval of 410500nm and the obtaining of the infinite optical thickness 99.9% (X) and the translucency parameter (TP) estimated as 0.5mm (TP0.5), 1.25mm (TP1.25) e 2.00mm (TP2.00) thicknesses, for the wavelength interval of 410700nm. The Translucency parameters were used to evaluate the porcelain masking effect against the tested backgrounds. The results showed that all factors (Shade, Opacity, and Commercial Brand) exerted influence to attenuate the light propagation through the specimens. In general, a higher light attenuation was linked to porcelains exhibiting more saturated shades (A35, and B3) and body opaque types. The commercial brand IPS porcelain shades A35 and B3, generally attenuated more light than the same shades of HALO and NORI for the studied optical thicknesses. The infinite optical thicknesses values (thicknesses where the transmitted light is close to zero) is above the clinical thickness reported in the literature for all materials and both wavelength intervals. This fact implied that regarding the 410500nm interval, the body porcelain could transmit from 20 to 5% of the energy, while the opaque body transmits from 10 to 5%. The masking effect of the porcelains will be increasingly translucid against the background with increased colorimetric response on the Red Orange regions of the visible spectra. The qualitative analysis showed that for all materials and thicknesses, the light will preferably be attenuated in the beginning of the spectra, on the 410500nm interval e and will be less attenuated towards the ending of the visible spectra. The results also showed that the attenuation increased with the increase of the thickness, and the relationship between thickness and attenuation is nonlinear.

Nowadays a lot of physical techniques are available in order to have information about an historical painting. They are able to know which chemical elements are present in the paint layer, or they are also able to show the pattern under the colored layer, but there is not a non-destructive technique able to study the artist technique of painting or the historical pigments used in order to obtain the particular nuance we can observe. In this thesis we study an evolution of the VIS-NIR-spectroscopic technique with these goals. In particular we start from a preliminary historical study of the artist’s pigments available for paintings and, starting from the colorimetric technique till the spectrophotometetric technique we create a representative pigments Database and we study a new method for pigment grindings identification, pigment’s mixture recognition and pigments layer technique studies. The international method for color measurements provides the use of colorimeter but the sizes of these instruments don’t allow to perform measurements in any cases. Applications in the field of cultural heritage like as pigment characterizations on statues or ceramic and sometimes paintings don’t allow the use of integrating sphere. So we study the applicability of optical fiber for the realization of optical fiber remote probes. The use of optical fibre is consolidated for spectroscopy measurements (in particular for UV-VIS-NIR spectroscopy), but it may introduce an error in the detection of the spectra and, in consequence, a further error in the definition of the color of the sample analyzed. The first goal of this work was therefore the evaluation of compatibility of CIE colorimetric results obtained using Fiber Optic Reflectance Spectroscopy (FORS) and those values obtained with a standard colorimeter and then we extend the use of remote probe in NIR range for the measure of the pigments reflectance spectra. After the test of the remote probe setup we have studied spectra obtained for well-defined mixtures of the most important artist’s pigments with the barium sulphate white pigment, the same used like standard sample for color measurements. These mixture simulate the different desaturation degree of the main color like in the earlier paintings techniques before Renaissance age. In order to have the best numerical characterization we fit the main behavior of the spectra using two analytical models: the Gaussian function (with 4 free parameters) and the sigmoidal function (with 4 free parameters): the comparison of their parameters allow to define the change of the spectra for different concentration of each colored pigment in the white one when thy were mixed in oil or without oil (as in oil renaissance paint technique and in the tipical affresco Middleage paint technique). Determination of weight mixture Pigment to white were: pigment pure, 1:1, 1:2, 1:5, 1:10, 1:20, 1:50. The pigments analyzed with sigmoidal fit were: Cadmium Red , Lacca rossa (Red Laquel), Chromium Orange, Cadmium Yellow, Naple Yellow (with Lead), Green Chromium oxide, Cobalt Blue, Cobalt Violet and Ultramarine Green. Pigments studied using Gaussian fit were: Green Chromium oxide, Cobalt Violet, Ultramarine Green, Verderame (Copper Green), Azurite, Ultramarine blue (artificial), Lapislazuli, Green earth, Malachite Green, Zinc Yellow and Cinabrum. The next step is the research of a model able to study mixtures of two different colored pigments. The best historical model able to describe the interaction light-pigment was the Kubelka-Munk theory. In this model the Absorbtion (K) and Scattering (S) coefficients are needed. Here we study a method to obtain this coefficient from the reflectance spectra of the pigments and the spectra of their mixtures with barium sulphate and we use the same method in order to obtain the spectra of a mixture of two different colored pigment in an oil-paint layer. The change of the color due to the presence of the oil is finest and the normal remote probes (optical fiber) setup is not enough to solve the differences, like it is not able for study the effect of the different grindings of the pigment’s powders. We realized an high-definition setup for reflectance measurements without optical fibers and a Fianium white LASER source (collaboration wit AMOLF-Fom institute, Amsterdam) creating also samples with characteristics nearest the Kubelka-Munk request. Using this high sensitivity setup we obtain the reflectance spectra for all the selected pigments and we study the difference of color due to the different grindings of the powder for the azurite and verderame pigments. We were able also to study color differences of specific paint techniques of ancient painters: the “Italian” Renaissance technique based on the mixtures of color pigments and the “Flamish” technique based on the overlapping of translucent glaze of different color in order to obtain the deep in the paint and the famous sfumato.

碩士
中國文化大學
材料科學與製造研究所
88
Abstract MATHEMATICAL EQUATIONS FROM THE KUBELKA-MUNK DIFFERENTIALS by Jeremy Chia-Wei Kan The two-constant Kubelka-Munk (K/M) theory has been exploited in many industries including plastics, paint, cosmetics, textile, and paper. This theory was developed in 1931. Regardless its long-term applications in industries, the detailed derivations of the basic equations have not been published in the literature. All equations published are in the form of final results. In addition, based on the published discussions of the basic equations, it is plausible that new equations could be generated through mathematical derivation. In the current thesis research, the objective is to create new equations for calculating optical properties of paper. The thesis approach is to first familiarize K/M theory and the derivation process for the basic equations. Then use the mathematical experiences gained to accomplish the research objective. It can be concluded that all basic equations of the K/M theory are derived from skills of algebra, hyperbolic functions, natural logarithmic and exponential functions, and simple definite integration. Moreover, two new equations have been created, based on the same mathematical skills, for calculating optical properties of paper. The first equation is for determining Tappi opacity (C0.89) using parameters of R∞ (Reflectivity) and SX (Scattering power). The second equation is for determining Printing opacity (C∞) using the same parameters. These two equations can be applied to find either C0.89 or C∞ when one of them is pre-known. Finally either of these two new equations can be used to back-derive some significant K/M parameters such as S (Scattering coefficient), K (Absorption coefficient), and R∞ (Reflectivity）.

碩士
中國文化大學
材料科學與製造研究所
93
The objective of this work is to apply the Kubelka-Munk theory to analyze optical dot gain in inkjet halftone. Optical dot gain is a significant technical problem because it lowers the contrast of a halftone. By researching the details of relevant literature, this thesis finds that there is still no optical dot gain function being developed in imaging engineering. Thus, this research proposes a design to find that function. The design is mainly based on Kubelka-Munk theory and the assumption of optical dot gain being a part of the ink thickness.

碩士
中國文化大學
資訊傳播學系
98
In the publishing and textile industry, one of the most important process throughout the production lifecycle is the color combination of ink and dye. By relying on experienced workers’ manual judgment of color matching often result in inconsistency and inaccuracy of the colors produced. The Computer Color Matching system (in short CCM) is a color matching computational method which combines color reproduction theory, ink compatibility, and numerical analysis technologies to minimize the inconsistencies and to improve the color accuracy in colors production. Although such technology is available overseas, it is still unavailable locally. This research is based on the Kubelka-Munk theory and it combines the relevant spectrum color theory to build a CCM model. We then use the model to find formulas of different ink brands in order to compare the color deviation between them. This research is based on the the CCM model developed by color reproduction model for color prediction. To come out with the findings, we used, 2 different brands of ink and 30 kinds of standard color samples together with the CCM model. The result obtained in terms of color deviation (∆E*ab) between samples and the standard average values are 5.89 and 6.94 respectively. This result falls out of the acceptable range of the tolerance level for the industrial publishing standards. The CFI(Curve Fit Index) test cases arrive at thesame conclusion. As a result, we conclude that the color matching model based on Kubelka-Munk theory still requires further fine-tuning and more in-depth analysis. In addition, the precision of the ink sets reflectance database should also be an important factor affecting the accuracy of colors. Computer color matching system is able to use precise numerical calculation to resolvethe complex issue of the color accuracy and inconsistency of ink matching. This research aims to spur further analysis into this area locally.

L'étude d'une batterie optique flexible, capable de moduler sa réflexion dans l'infrarouge et basée sur la technologie PLiON, est présentée dans cette thèse. Dans une première partie, une étude du trioxyde de tungstène monohydraté en fonction de la morphologie du matériau a permis de comprendre et d'améliorer les performances. Le contraste observé sur un film de WO3.H2O est de 40 % (8-12 µm). Une deuxième partie du document analyse le choix de matériaux actifs pour obtenir un contraste important. En fonction du type de matériaux (métal ou semi-conducteur), l'influence de la nature, de la morphologie et de leur structure sur leurs propriétés optiques est soulignée. Dans la dernière partie, nous avons montré que le temps de commutation pouvait être amélioré en utilisant une contre-électrode rapide, en réduisant l'épaisseur des films électroactifs et en remplaçant les ions lithium par des protons. Deux batteries fonctionnant en milieux protonés sont proposées.

Durch neue Ansätze zur Charakterisierung molekularer und nanokristalliner Materialien spiegelt die vorliegende Arbeit die Synergie von linearer Optik über Ultrakurzzeitphysik zur nichtlinearen Optik wider. Angefangen mit der linearen diffusen Reflektanz (Remission) zur Bestimmung des spektralen Reflexionsvermögens von Pulverpartikeln, erlaubt die hier gezeigte alternative Herangehensweise (s. Kapitel 2) nicht nur ein vereinfachtes Messen der Remission zur Analyse von Materialzusammensetzungen, Verunreinigungen und Co-Dotierungen, sondern eröffnet zudem über Monte-Carlo Simulationen, kombiniert mit der Kubelka-Munk Theorie und der Mie Streuung, auch den Zugang zu dem ansonsten experimentell unzugänglichen Absorptionskoeffizienten von nicht-transluzenten Proben. Die präsentierten Mess- und Simulationsergebnisse an Pulvertabletten aus Rutil-Titandioxid (TiO2) und Cer-dotierten Yttrium Aluminium Granat (YAG:Ce3+) sind mit den bisherigen in der Literatur vorliegenden Ergebnissen konsistent oder zumindest vergleichbar. Auch lassen sich nach Modifikation der Kubelka-Munk Funktion die Bandkanten-Energien Eg der mikro- und nanokristallinen Pulverproben mittels so genannter Tauc Plots verifizieren. Basierend auf einer starken Temperatur- und Konzentrationsabhängigkeit lassen sich die Emissionsspektren der oben genannten YAG:Ce3+-Leuchtstoffe aufgrund von Überlappung oder Verschiebung der energetischen Grundniveaus 2F5/2 und 2F7/2 variieren (s. Kapitel 3). Während sich bei Tieftemperaturen um 19K die doppelbandige Natur der Leuchtstoffe zeigt, verbreitern sich die Emissionsbanden bei Raumtemperatur zu einer Einzelbande, womit eine spektral sehr breite Fluoreszenz einhergeht. Mathematische Entfaltungen dieser Spektren zeigen jeweils den prozentualen Beitrag der Relaxation aus dem untersten angeregten Zustand 5d1 in einen der beiden Grundzustände 2F5/2 und 2F7/2 und ebenso den Einfluss der Temperatur und Cer-Konzentration. Tatsächlich führen die experimentellen Ergebnisse der vorliegenden Arbeit zu der Erkenntnis, dass eine der vier untersuchten YAG:Ce3+-Proben eine erhöhte Cer-Konzentration aufweisen muss. Anders als bei den schwach konzentrierten YAG:Ce3+-Proben ist die spektrale Doppelbande des stark konzentrierten Leuchtstoffs selbst bei 19K nur zu erahnen, während der Beitrag des 5d1 --> 2F7/2 Übergangs auf die Gesamtfluoreszenz retrograd zum 5d1 --> 2F5/2 Übergang mit steigender Temperatur sogar abnimmt. Im direkten Anschluss an die spektrale Vermessung der Proben folgen zeitaufgelöste Lebensdauermessungen zur Bestimmung der Nachleuchtdauern dieser Leuchtstoffe mittels Pikosekunden-Laserpulsen (ps-Pulse) (s. Kapitel 3.3). Auch hier stellen sich Unterschiede zwischen den genannten YAG:Ce3+-Proben heraus und untermauern erneut die Annahme unterschiedlicher Cer-Konzentrationen: Während die Nachleuchtdauer der niedrig konzentrierten Leuchtstoffe von der Temperatur nahezu unberührt bleibt, zeigt sich eine bemerkenswerte Temperaturabhängigkeit des 5d1 --> 2F5/2 Übergangs beim YAG:Ce3+ mit hohem Cer-Gehalt. Auf Basis sämtlicher experimenteller Erkenntnisse und einer ausgiebigen Literaturrecherche kann schließlich eine Fremddotierung der Leuchtstoff-Proben nahezu vollständig ausgeschlossen und ein Energieschema für die vorliegenden YAG:Ce3+-Leuchtstoffe mit den wichtigsten optischen Übergängen erstellt werden. In Hinblick auf potentielle holographische Applikationen wie der optischen Datenspeicherung oder Echtzeit-Holographie erweisen sich die in Polydimethylsiloxan eingebetteten photoschaltbaren Ruthenium-Sulfoxide aufgrund der äußerst geringen Beugungseffizienz von < 10−2 als nicht pragmatisch für die Praxis (s. Kapitel 4). Vergleichbare photoschaltbare Materialien, wie zum Beispiel Natriumnitrosylprussiat, erreichen hingegen Effizienzen von bis zu 100 %. Dennoch zeichnen sich die in Publikation 2 (s. Anhang A.2) vorgestellten Resultate an OSO-PDMS durch ihre äußerst hohe Qualität aus. Sowohl die dynamische Hologramm-Entstehung als auch die Rocking-Kurve folgen den physikalischen Theorien einwandfrei und lassen sich mit den bekannten mathematischen Anpassungen exakt wiedergeben, womit sich entsprechend intrinsische Größen ableiten lassen. Zudem beeindruckt der experimentelle Aufbau mit der präzisen Messung der oftmals nicht detektierbaren Nebenmaxima der gezeigten Rocking-Kurve sowie des Winkel-Multiplexings. Bemerkenswert ist außerdem aus physikalischer Sicht der immense Unterschied zwischen cw- und fs-Holographie. Hier deuten sich nichtlineare Effekte an, die zu der Erkenntnis führen, dass sich die bekannten Theorien mit cw-Lasern nicht ohne Weiteres deckungsgleich auf die Holographie mit ultrakurzen Laserpulsen anwenden lassen. Ein möglicher Erklärungsansatz ist in Kapitel 4.1 beschrieben. Einen praktischen Zweck zur Nutzung nichtlinearer Effekte erfüllt die vorgestellte Messmethode zur Unterscheidung polarer und nicht-polarer Materialien mittels intensiver fs- Puls-Anregung von sogenannten harmonischen (Upconversion-)Nanopartikeln (s. Kapitel 5). Denn anders als die zu Beginn behandelten Leuchtstoffe, weisen die harmonischen Nanopartikel eine starke Anti-Stokes Verschiebung durch Frequenzkonversion zweier oder dreier Photonen zu einem energiereicheren (kurzwelligen) Photon auf. Diese als SHG (second harmonic generation) und THG (third harmonic generation) bekannte Lichtemission wird spektral vermessen, wobei die zu Beginn der Arbeit beschriebenen linearen diffusen Reflektanzmessungen den zu erwartenden Spektralbereich ohne nennenswerte Absorption eingrenzen. Die eigens definierte Gütezahl fR, bestehend aus dem integrierten SHG- und THG-Emissionsspektrum einer Probe, kategorisiert dann die polare (fR > 1) oder nicht-polare (fR << 1) Natur des Materials.