New optical designs have necessitated using refractive index data that is accurate to the third and fourth decimal points. Prism coupling refractometry could be attractive for this task because of a combination of factors. It allows for a direct assessment of the refractive index like interferometry or the minimum deviation method while being quick and convenient, like Kramers-Krönig analysis and spectroscopic ellipsometry. However, the accuracy, precision, and repeatability of this technique have not been revisited recently in the literature. This thesis seeks to identify the critical features of this technique that define its uncertainties and then provides some initial improvements to this system. The improvements explored are hardware-based and incorporate a novel approach to fitting this data. The resulting error budget defined by this strategy increases the measured precision, taking the first step towards making the method a standard metrology technique suitable for the shop floor.

Nesse trabalho, propomos uma modificação da técnica de caracterização de filmes conhecida por m-line para o desenvolvimento de um refratômetro para gases e líquidos. O principio dessa técnica consiste no acoplamento de ondas evanescentes em guias de ondas planares obtidos via o fenômeno da reflexão total interna frustrada através de dispositivos acopladores. Observa-se experimentalmente, após incidir um feixe de laser contínuo na base do acoplador óptico, uma grande atenuação da radiação refletida para determinados ângulos de incidência, que é justamente a radiação acoplada nos modos permitidos pelo guia de onda. Medindo-se os valores desses ângulos e usando a teoria de acoplamento, é possível determinar as características desconhecidas do sistema. Esse sistema consiste de um acoplador óptico semicircular de alto índice de refração em cuja base foram depositados, via evaporação, um filme de dióxido de silício (SiO2) e outro de dióxido de zircônio (ZrO2). Ou seja, o sistema resume-se a dois meios finitos (filmes) prensados entre dois meios semi-infinitos (prisma e amostra). Como a espessura dos filmes e os índices de refração complexos dos filmes e do prisma são conhecidos, a única variável é o índice de refração do quarto meio, que é a amostra da qual se deseja medir o índice de refração. Estudamos a influência que cada um dos parâmetros externos exerce sobre o perfil refletido, tais como comprimento de onda e polarização da radiação incidente, espessuras e índices de refração dos filmes e o formato dos dispositivos acopladores. Descrevemos o comportamento do sistema quando o feixe incidente possui perfil gaussiano, que é perfil dos lasers usualmente usados em pesquisa. As espessuras das camadas de SiO2 e de ZrO2 foram otimizadas tendo em vista a faixa dos valores do índice de refração das amostras que se deseja medir. A otimização do sistema é obtida via teoria de guiamento de radiação em guias de ondas planares para o caso de quatro meios. Para a aquisição e tratamento dos dados desenvolvemos um programa na plataforma LabVIEW® que processa a imagem detectada por uma câmera CCD no visível, possibilitando o acompanhamento da variação do feixe refletido em função da variação do índice de refração da amostra. Assim, além de determinar ponto a ponto a variação do perfil refletido, é possível determinar a dinâmica em que esse efeito se realiza, gerando possibilidades de aplicação da técnica em áreas relacionadas à dinâmica química e bioquímica. Para confirmação da efetividade da técnica, realizamos medidas da variação do índice de refração do ar em função da umidade relativa, temperatura, pressão e para soluções de glicose. O sistema demonstrou sensitividade suficiente para acompanhar mudanças do índice de refração do ar da ordem de 10-6. / In this work, we propose a modification of the technique for characterization of films known as the m-line for the development of a refractometer for liquids and gases. The principle of this technique is coupling evanescent waves in planar waveguides obtained by the phenomenon of frustrated total internal reflection devices through devices couplers. It is experimentally observed, after focusing a continuous laser beam at the base of the coupler, a large attenuation of the reflected radiation for certain angles of incidence, which is precisely the radiation coupled in the modes allowed by the waveguide. Measuring the values of these angles and using the coupling theory, it is possible to determine the unknown characteristics of the system. This system consists of a semicircular optocoupler high refractive index which in the base was deposited, via evaporation, a film of silicon dioxide (SiO2) and a zirconium dioxide (ZrO2). In other words, the system is similar to a two finite media (films) pressed between two semi-infinite media (prism and sample). As the film thickness and complex refractive indices of the film and the prism are known, the only variable is the index of refraction of the fourth medium that is the sample from which it is aimed to measure the refractive index. We studied the influence that each of the external parameters has on the reflected profile, such as wavelength and polarization of the incident radiation, thicknesses and refractive indices of the films and the format of the devices couplers. We describe the system behavior when the incident beam has a Gaussian profile, which is usually the profile of the lasers usually used in researches. The thicknesses of the layers of SiO2 and ZrO2 were optimized in function of the range of the refractive index values of the samples to be measured. System optimization is obtained via the guiding theory of radiation in planar waveguides for the case of four mediums. For acquisition and data processing, a program were developed in LabVIEW® platform that processes the image detected by a CCD camera in visible light, allowing us to relate the variation of the reflected beam to the value of the refractive index of the sample. Thus, besides determining the variation of the profile reflected, it is possible to determine the dynamic in which this effect takes place, generating opportunities for application of the technique in areas related to the dynamic chemistry and biochemistry. To confirm the effectiveness of the technique, we performed measurements of the variation of the refractive index of air as a function of relative humidity, temperature, pressure and glucose solutions. The system shows sufficient sensitivity to follow changes in the refractive index of air in the order of 10-6.

Nesse trabalho, propomos uma modificação da técnica de caracterização de filmes conhecida por m-line para o desenvolvimento de um refratômetro para gases e líquidos. O principio dessa técnica consiste no acoplamento de ondas evanescentes em guias de ondas planares obtidos via o fenômeno da reflexão total interna frustrada através de dispositivos acopladores. Observa-se experimentalmente, após incidir um feixe de laser contínuo na base do acoplador óptico, uma grande atenuação da radiação refletida para determinados ângulos de incidência, que é justamente a radiação acoplada nos modos permitidos pelo guia de onda. Medindo-se os valores desses ângulos e usando a teoria de acoplamento, é possível determinar as características desconhecidas do sistema. Esse sistema consiste de um acoplador óptico semicircular de alto índice de refração em cuja base foram depositados, via evaporação, um filme de dióxido de silício (SiO2) e outro de dióxido de zircônio (ZrO2). Ou seja, o sistema resume-se a dois meios finitos (filmes) prensados entre dois meios semi-infinitos (prisma e amostra). Como a espessura dos filmes e os índices de refração complexos dos filmes e do prisma são conhecidos, a única variável é o índice de refração do quarto meio, que é a amostra da qual se deseja medir o índice de refração. Estudamos a influência que cada um dos parâmetros externos exerce sobre o perfil refletido, tais como comprimento de onda e polarização da radiação incidente, espessuras e índices de refração dos filmes e o formato dos dispositivos acopladores. Descrevemos o comportamento do sistema quando o feixe incidente possui perfil gaussiano, que é perfil dos lasers usualmente usados em pesquisa. As espessuras das camadas de SiO2 e de ZrO2 foram otimizadas tendo em vista a faixa dos valores do índice de refração das amostras que se deseja medir. A otimização do sistema é obtida via teoria de guiamento de radiação em guias de ondas planares para o caso de quatro meios. Para a aquisição e tratamento dos dados desenvolvemos um programa na plataforma LabVIEW® que processa a imagem detectada por uma câmera CCD no visível, possibilitando o acompanhamento da variação do feixe refletido em função da variação do índice de refração da amostra. Assim, além de determinar ponto a ponto a variação do perfil refletido, é possível determinar a dinâmica em que esse efeito se realiza, gerando possibilidades de aplicação da técnica em áreas relacionadas à dinâmica química e bioquímica. Para confirmação da efetividade da técnica, realizamos medidas da variação do índice de refração do ar em função da umidade relativa, temperatura, pressão e para soluções de glicose. O sistema demonstrou sensitividade suficiente para acompanhar mudanças do índice de refração do ar da ordem de 10-6. / In this work, we propose a modification of the technique for characterization of films known as the m-line for the development of a refractometer for liquids and gases. The principle of this technique is coupling evanescent waves in planar waveguides obtained by the phenomenon of frustrated total internal reflection devices through devices couplers. It is experimentally observed, after focusing a continuous laser beam at the base of the coupler, a large attenuation of the reflected radiation for certain angles of incidence, which is precisely the radiation coupled in the modes allowed by the waveguide. Measuring the values of these angles and using the coupling theory, it is possible to determine the unknown characteristics of the system. This system consists of a semicircular optocoupler high refractive index which in the base was deposited, via evaporation, a film of silicon dioxide (SiO2) and a zirconium dioxide (ZrO2). In other words, the system is similar to a two finite media (films) pressed between two semi-infinite media (prism and sample). As the film thickness and complex refractive indices of the film and the prism are known, the only variable is the index of refraction of the fourth medium that is the sample from which it is aimed to measure the refractive index. We studied the influence that each of the external parameters has on the reflected profile, such as wavelength and polarization of the incident radiation, thicknesses and refractive indices of the films and the format of the devices couplers. We describe the system behavior when the incident beam has a Gaussian profile, which is usually the profile of the lasers usually used in researches. The thicknesses of the layers of SiO2 and ZrO2 were optimized in function of the range of the refractive index values of the samples to be measured. System optimization is obtained via the guiding theory of radiation in planar waveguides for the case of four mediums. For acquisition and data processing, a program were developed in LabVIEW® platform that processes the image detected by a CCD camera in visible light, allowing us to relate the variation of the reflected beam to the value of the refractive index of the sample. Thus, besides determining the variation of the profile reflected, it is possible to determine the dynamic in which this effect takes place, generating opportunities for application of the technique in areas related to the dynamic chemistry and biochemistry. To confirm the effectiveness of the technique, we performed measurements of the variation of the refractive index of air as a function of relative humidity, temperature, pressure and glucose solutions. The system shows sufficient sensitivity to follow changes in the refractive index of air in the order of 10-6.

Orientadores: Matthieu Tubino, Glauco Favilla Bauerfeldt / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T16:02:39Z (GMT). No. of bitstreams: 1 RochaJunior_JoseGeraldo_D.pdf: 3381652 bytes, checksum: a5f7a7055b03e667d7fafb7571329b76 (MD5) Previous issue date: 2013 / Resumo: O biodiesel é comumente produzido pela transesterificação dos triglicerídeos com o metanol (metanólise) empregando catalisadores alcalinos. Neste trabalho foi investigada a atividade catalítica do NaOCH3, KOCH3, NaOH e do KOH na metanólise do óleo de soja nas temperaturas de 30 à 60 °C, sob agitação de 400 rpm. O progresso desta reação foi monitorado pelas medidas do índice de refração utilizando um refratômetro portátil digital, ao qual foi acoplado uma peça cônica de Teflon® para permitir o monitoramento online das amostras em fluxo contínuo. O método proposto é simples, rápido, barato, não-destrutivo e não requer pré-tratamento complexo. Foi observado que a etapa de mistura dos reagentes consome grande parte do tempo necessário para a conversão. A lei de velocidade da metanólise pôde ser bem representada por uma cinética de ordem zero, com a reação ocorrendo na interface da mistura metanol/óleo. Os catalisadores contendo o potássio promoveram reações mais rápidas do que os seus análogos de sódio, sugerindo que um mecanismo de reação envolvendo a participação de pares iônicos de metóxidos alcalinos como catalisadores seria mais adequado para representar a metanólise do que aquele catalisado pelos íons metóxidos. Em comparação aos metóxidos alcalinos, nas reações em que se empregaram os hidróxidos as suas velocidades são menos sensíveis à variação da temperatura. Neste caso, os sabões formados com os hidróxidos poderiam estar amenizando a influência da temperatura na difusão dos reagentes fazendo com que a velocidade da reação seja menos afetada. A água parece atuar como um inibidor desta reação, por inativação do catalisador, o que se reflete na menor velocidade observada nas reações com os hidróxidos frente às com os metóxidos. Entretanto isto não é percebido à baixas temperaturas, quando o efeito difusional é predominante / Abstract: Biodiesel is commonly produced by the transesterification of triglycerides with methanol (methanolysis) using alkaline catalysts. In this work we investigated the catalytic activity of NaOCH3, KOCH3, NaOH and KOH in methanolysis of soybean oil at temperatures of 30 to 60 °C, under 400 rpm agitation. The progress of the reaction was monitored by measuring the refractive index using a portable digital refractometer, to which was attached a piece conical Teflon® to allow online monitoring of samples at continuous flux. The proposed method is simple, fast, inexpensive, non-destructive and not requires complex pretreatment. It was observed that the step of mixing the reactants consumes much of the time required for conversion. The rate law of methanolysis can be represented by a zero-order kinetics, with the reaction occurring at the interface of methanol / oil. The catalysts containing potassium promoted reactions faster than its analogs sodium, suggesting that a reaction mechanism involving the participation of ionic pairs of alkaline methoxides would be more suitable to represent the methanolysis than that catalyzed by ions methoxides. In reactions that utilized hydroxides their speeds are less sensitive to temperature variation than the alkaline methoxides. In this case, the soaps formed with the hydroxides could be decreasing the influence of temperature on diffusion of the reactants so that the reaction rate is less affected. The water seems to act as an inhibitor of this reaction by inactivation of the catalyst, which is reflected in the lower velocity observed in reactions with hydroxides towards methoxides. However this is not observed at lower temperatures, when the diffusion effect is predominant / Doutorado / Quimica Analitica / Doutor em Ciências

Le captage de polluants des effluents industriels, et plus particulièrement du CO2, est un défi majeur à relever. Le procédé de captage du CO2 basé sur l’absorption par des solutions aqueuses d’amines est la technique la plus maîtrisée pour le traitement des fumées en postcombustion. La substitution des colonnes à garnissage par des colonnes à pulvérisation présente un intérêt économique car la surface d’échange entre les phases gazeuse et liquide est très importante réduisant ainsi la taille de la colonne d’absorption. De plus, les pertes de charge côté gaz sont évitées et les coûts de maintenance réduits. L’objectif de ces travaux de thèse est de caractériser le transfert de matière dans un spray au cours d'une absorption du CO2 par une solution aqueuse de monoethanolamine (MEA) en utilisant une nouvelle méthode.Ainsi, l’étude s’intéresse à la caractérisation locale du transfert de matière entre un spray de MEA à 30% massique et une atmosphère de CO2. Pour cela, une technique optique non-intrusive est utilisée : la réfractométrie arc-en-ciel globale (GRT). Cette technique est une mesure de l’indice de réfraction d’un ensemble de gouttes localisé dans une partie du spray. C’est donc une mesure locale dans un volume de l’ordre de quelques millimètres cubes. L’indice de réfraction d’une solution dépend de sa température et de sa concentration. Ainsi, à l’aide d’un étalonnage préalable dans un réacteur agité, les indices de réfraction des solutions aqueuses de MEA chargées sont reliés à leurs températures et à leurs concentrations de CO2 absorbé. La mesure d’indice de réfraction permet donc de suivre l’avancement du transfert de matière à travers la concentration de CO2 absorbé à une température moyenne du volume de mesure. La GRT est donc utilisée pour la mesure d’indice de réfraction au cours de l’absorption avec réaction chimique et, la quantité de CO2 captée par unité de volume est mesurée à plusieurs hauteurs de chute. Les mesures sont ensuite comparées aux prédictions d’un modèle de transfert de matière dans une goutte résolu numériquement sous COMSOL Multiphysics. Dans un deuxième temps, l’étude s’intéresse à la caractérisation du transfert de matière côté gaz en mesurant par spectrométrie infra-rouge la quantité de CO2 présente dans la phase gaz lors de l’absorption de celui-ci par une solution aqueuse de MEA à 30 % massique. Les résultats sont présentés sous forme d’efficacité de captage et un coefficient de transfert de matière côté gaz est calculé, en fonction de paramètres opératoires tels que les débits gazeux et liquide.Ces travaux de thèse, appliqués au captage du CO2, traite principalement de la mesure de transfert de matière grâce à la GRT pour la première fois utilisée à une absorption avec réaction chimique. La méthode développée permettra son utilisation pour d’autres systèmes chimique. / Pollutant capture, especially of CO2, is still a major challenge nowadays.CO2 capture based on absorption with chemical reaction by aqueous solutions of amines is the most mature technique for post-combustion gas cleaning.The substitution of packed columns by spray columns presents an economical interest since the exchange area between both gas and liquid phases is very important, reducing the size of the absorption column. In addition, gas side pressure losses are avoided and maintenance costs are reduced.The aim of this thesis is to characterize mass transfer in a spray column during a CO2 absorption by an aqueous solution of monoethanolamine (MEA) by using a new optical technique.The study focuses on the characterization of the local mass transfer between MEA spray and a CO2 atmosphere. In order to achieve this, a non-intrusive optical technique is used: Global Rainbow Technique (GRT). This technique measures the refractive index of droplets in a local portion of the spray. Therefore, the measurement is local with a volume of few cubic millimeters.The refractive index of a solution depends on its temperature and its concentration. Thus, by using a prior calibration in a stirred reactor, the refractive indices of CO2 loaded MEA solutions are correlated with their temperatures and CO2 absorbed concentration. Therefore, measuring refractive index is a measurement of mass transfer extent.GRT is then used during CO2 absorption with chemical reaction, and the amount of CO2 captured per volume unit is measured at several column heights. The experimental results are then compared with mass transfer predictions in a droplet with a model numerically solved in COMSOL Multiphysics.In another hand, gas side mass transfer is characterized by measuring the amount of CO2 in the gas phase with infrared spectrometry during CO2 absorption in an aqueous solution of 30 % MEA. The results are presented in term of capture efficiency and a gas-side mass transfer coefficient is calculated as a function of operating parameters such as gas and liquid flow rates.This work, applied to CO2 capture, deals with mass transfer measurement with GRT through a first application to absorption with chemical reaction. The developed method in this thesis will allow its use for other chemical systems.

Afin de modéliser correctement les phénomènes liés à l'évaporation, les numériciens souhaitent obtenir des mesures expérimentales fiables, leur permettant d'améliorer leurs modèles. A l'opposé, de nombreux industriels souhaitent pouvoir réaliser des mesures in situ, avec des techniques expérimentales appliquées aux conditions réelles.C'est dans ce cadre que s'est inscrite cette thèse. L'objectif principal, a été de démontrer la faisabilité, et la stabilité, de mesures en réfractométrie d'arc-en-ciel sur des gouttes uniques en écoulement afin d'obtenir le taux d'évaporation de ces gouttes.L'utilisation d'un dispositif dédié habituellement à la PIV a servi à réaliser des acquisitions de couples d'images, séparées par un délai temporel variable. Une méthode très fine de la mesure de variation de diamètre a été introduite, autorisant la mesure du taux d'évaporation instantané d'une goutte en écoulement par le biais du déphasage de la structure de ripple. / In order to model correctly the evaporation phenomenon, numerical simulations needs to work with reliable experimental data, allowing to improve the existing models. On the other side, industrialists needs to realize in situ measurements, with experimental techniques that apply to real conditions. This is the framework of this thesis. The main work has been to prove that measurements with rainbow refractometry on unique droplets in a flow were possible, obtain the evaporation rate from those measurements, and prove their stability.The use of a specific setup, most of the time used in PIV, allowed us to realize acquisitions of couple images with a temporal delay. A very fine method for the measurement of variation of diameter has been introduced, allowing the measurement of instantaneous evaporation rate of unique droplets in a flow, using the ripple structure phase shift.

La caractérisation des propriétés optiques de gouttes de combustible aux alentours de la pression critique est un défi. L’objectif de la thèse est de mesurer la taille et l’indice de réfraction de fluides dans des conditions de pression élevée proche du point critique. A cet effet, une installation expérimentale d’injection de gouttes à haute pression a été conçue. La réfractométrie d’arc-en-ciel a été développée et adaptée pour travailler d’abord sur des gouttelettes d’eau et d’éthanol dans le domaine de pression 1 - 40 bar. Des évolutions de leur indice de réfraction avec la pression ont été obtenues. Pour les mesures se rapprochant d’un fluide proche du point critique, l’éthane a été sélectionné car son point critique est à 48,7 bar et 32,2°C. Des mesures de réfraction d’index sur des gouttes liquides d’éthane ont ensuite été réalisées dans le domaine 40 - 46 bar et 18 - 25°C. Une mesure de l’indice de réfraction de gouttes d’éthane donne alors une valeur de 1,255 ± 0.002. / The characterization of the optical properties of fuel drops around the critical pressure is a challenge. The aim of the thesis is to measure the size and the refractive index of fluids under high pressure conditions close to the critical point. For this purpose, an experimental installation of injection of high-pressure drops has been designed. Rainbow refractometry has been developed and adapted to work first on water and ethanol droplets in the pressure range 1 - 40 bar. Evolutions of their index of refraction with the pressure were obtained. For measurements approaching a fluid near the critical point, ethane was selected because its critical point is 48.7 bar and 32.2 ° C. Index refractive measurements on liquid drops of ethane were then carried out in the range 40 - 46 bar and 18 - 25 ° C. A measurement of the refractive index of ethane drops then gives a value of 1.255 ± 0.002.

Calves are born agammaglobulinemic and rely on colostrum consumption for the transfer of maternal passive immunity. Calves that fail to absorb adequate amounts of maternal antibodies from colostrum are commonly referred to as having failed transfer of passive immunity (FTPI). The overall aim of this dissertation was to explore the usefulness of FTPI testing in neonatal beef calves to predict their risk for subsequent illness or death. The objectives were to evaluate the impact of FTPI on pre-weaning disease in beef and dairy calves, quantify and compare the variance in IgG concentrations measured by radial immunodiffusion and serum total protein (STP) values measured by optical refractometry, and evaluate the correlation between herd-level prevalence of FTPI and herd-level prevalence of pre-weaning disease in beef calves. Evaluation of literature relevant to FTPI was compiled and assessed to quantify the impact of FTPI on pre-weaning disease in beef and dairy calves. A series of randomized trials were used to evaluate the variance in IgG concentrations and STP values from banked serum. Health records from multiple farms and IgG results were used to evaluate the relationship between FTPI and disease at the individual and herd-level. Failed transfer of passive immunity had a variable association with pre-weaning disease in beef and dairy calves. IgG concentrations were less precise than STP values especially when dilution was required. IgG concentrations and STP values were associated with an increased risk of disease in pre-weaned beef calves, but FTPI cut-off values poorly classified the risk for subsequent disease. The proportion of calves with FTPI was not correlated with the proportion of calves that developed pre-weaning disease. Using a single immunological factor, such as IgG concentration or STP, to predict disease results in the misclassification of disease risk and does not consider additional component causes of disease.

<p>During operation of heavy ion accelerators a significant pressure rise has been observed when the intensity of the high energy beam was increased. The cause for this pressure rise is ion induced desorption, which is the result when beam ions collide with residual gas molecules in the accelerator, whereby they undergo charge exchange. Since the change in charge state will affect the bending radius of the particles after they have passed a bending magnet, they will not follow the required trajectory but instead collide with the vacuum chamber wall and gas are released. For the Future GSI project FAIR (Facility for Antiproton and Ion Research) there is a need to upgrade the SIS18 synchrotron in order to meet the requirements of the increased intensity. The aim of this work was to measure the desorption yields, η, (released molecules per incident ion) from materials commonly used in accelerators: 316LN stainless steel, Cu, Etched Cu, gold coated Cu, Ta and TiZrV coated stainless steel with argon and uranium beams at the energies 5-100 MeV/u. The measurements were performed at GSI and at The Svedberg Laboratory where a new dedicated teststand was built. It was found that the desorption yield scales with the electronic energy loss to the second power, decreasing for increasing impact energy above the Bragg Maximum. A feasibility study on the possibility to use laser refractometry to improve the accuracy of a specific throughput system was performed. The result was an improvement by up to 3 orders of magnitude, depending on pressure range.</p>

Tubulin, microtubules and associated proteins were studied theoretically, computationally and experimentally in vitro and in vivo in order to elucidate the possible role these play in cellular information processing and storage. Use of the electric dipole moment of tubulin as the basis for binary switches (biobits) in nanofabricated circuits was explored with surface plasmon resonance, refractometry and dielectric spectroscopy. The effects of burdening the microtubular cytoskeleton of olfactory associative memory neurons with excess microtubule associated protein TAU in Drosophila fruitflies were determined. To investigate whether tubulin may be used as the substrate for quantum computation as a bioqubit, suggestions for experimental detection of quantum coherence and entanglement among tubulin electric dipole moment states were developed.