A resonant cavity operating in TE011 mode was used to study the adsorption response of single walled carbon nanotubes (SWCNTs) and other nanomaterials for different types of gas molecules. The range of the frequency signal as a probe was chosen as geometry dependent range between 9.1 -9.8 GHz. A highly specific range can be studied for further experiments dependent on the type of molecule being investigated. It was found that for different pressures of gases and for different types of nanomaterials, there was a different response in the shifts of the probe signal for each cycle of gassing and degassing of the cavity. This dissertation suggests that microwave spectroscopy of a complex medium of gases and carbon nanotubes can be used as a highly sensitive technique to determine the complex dielectric response of different polar as well as non-polar gases when subjected to intense electromagnetic fields within the cavity. Also, as part of the experimental work, a range of other micro-porous materials was tested using the residual gas analysis (RGA) technique to determine their intrinsic absorption/adsorption characteristics when under an ultra-high vacuum environment. The scientific results obtained from this investigation, led to the development of a chemical biological sensor prototype. The method proposed is to develop operational sensors to detect toxin gases for homeland security applications and also develop sniffers to detect toxin drugs for law enforcement agency personnel.

A resonant frequency cavity was used to determine the dielectric properties of various preparations of Azotobacter vinelandii ATTC 12837. It was found that the bacteria investigated did interact with microwave radiation in the absence of free water. The data presented here indicate that bacteria demonstrate frequency specific dielectric properties. The techniques employed in these experiments may also be used to determine microwave spectra of other species of bacteria in different physiological stages.

This thesis represents one phase of a joint effort of research on the properties of liquids and solids. This work is concerned primarily with the microwave properties of solids. In this investigation the properties exhibited by conductor and semiconductor materials when they are subjected to electromagnetic radiation of microwave frequency are studied. The method utilized in this experiment is the perturbation of a resonant cavity produced by introduction of a cylindrically shaped sample into it.

Les PolyGlycosides d'Alkyle (APGs) sont des agro-tensioactifs dont les propriétés de surface, la biodégradabilité et l'innocuité vis-à-vis de la peau leur offrent de nombreuses applications dans les domaines de la détergence, de la cosmétique et de l'alimentaire. Les APGs sont synthétisés selon la réaction de glycosidation acido-catalysée de Fischer entre un sucre et un accepteur de glycosyle, tel qu'un alcool gras. A l'échelle industrielle, cette voie de synthèse présente plusieurs contraintes liées à la faible solubilité du sucre dans l'alcool lipophile, l'utilisation de pressions réduites et la manutention de catalyseurs acides toxiques et/ou corrosifs. Ces facteurs imposent un équipement spécifique, augmentent les coûts de production et favorisent la dégradation des APGs. Dans un premier temps, les sulfoxydes et les sulfones ont été utilisés comme solvants dans la synthèse d'APGs sans catalyseur et à pression atmosphérique. Cette méthodologie est transposable à de nombreux donneurs et accepteurs de glycosyle. Notre étude a montré que la réaction de glycosidation est catalysée par les acides organiques produits par caramélisation partielle du sucre. La faible solubilité des solvants soufrés dans les alcools gras à température ambiante a été mise à profit dans la mise au point d'un procédé de synthèse d'APGs permettant la récupération et le recyclage de ces solvants. Un milieu réactionnel biphasique décanol - sulfolane a été décrit pour l'obtention d'un rendement en xylosides de décyle supérieur à 80 % en un temps de réaction remarquablement court. La synthèse d'APGs par conversion directe de la biomasse lignocellulosique a fait l'objet de la seconde partie de ce travail. La réaction de transglycosidation du xylane et des hémicelluloses de peuplier a été réalisée sous activation thermique, sans solvant ou en présence de diméthylsulfoxyde, et sous irradiations micro-ondes. L'efficacité de chaque mode d'activation à promouvoir la réaction de transglycosidation a été discutée en fonction de l'origine botanique et de la composition chimique des matières végétales. / Alkyl PolyGlycosides (APGs) are biobased and biodegradable amphiphilics with good surfactant properties and low skin irritability, which are sought in cosmetics, detergents and food. APGs are synthesized by acid-catalyzed Fischer's glycosidation of a carbohydrate source and a glycosyl acceptor such as a long-tailed alcohol. Industrial APGs production suffers from various drawbacks such as the poor solubility of the carbohydrate in the fatty alcohol, the pressure management and the use of toxic or corrosive acid catalysts. Those issues impose more stringent demand on equipment, increase the production costs and favor APGs degradation reactions.Firstly we have been involved in developing an innovative strategy for the catalyst-free synthesis of APGs under atmospheric pressure. Sulfoxides and sulfones have been efficiently used for the manufacture of APGs starting from various glycosyl donors and acceptors. The reaction was induced by organic acids produced by partial carbohydrate caramelisation. Interestingly some of the sulfur-containing solvents were not soluble in fatty alcohols at room temperature whereas the reaction medium was homogenous at the glycosidation temperature. These solvents have been easily recovered and recycled without decrease of APGs yields. A decanol-sulfolane biphasic reaction medium has been designed for the production of decyl-D-xylosides in short reaction times and yields up to 83 %.The second phase of this work was focused on the direct conversion of lignocellulosic materials into APGs. The transglycosidation reaction of xylan and poplar hemicelluloses has been studied under thermal activation, without solvent or in the presence of dimethylsulfoxide, and under microwave irradiations. The efficiency of each activation mode has been discussed as a function of the botanical origin and the chemical composition of lignocellulosic substrates.

Le chauffage par micro-ondes (MO) est employé depuis plus de 20 ans dans nombreux laboratoires pour l’activation de réactions en synthèse chimique. Il existe un débat sur l’existence d’effets MO sur la vitesse des réactions puisque des augmentations des vitesses des réactions ont été parfois observées. Des caractéristiques du chauffage MO peuvent être intéressantes pour l’intensification des procédés mais cette technique a rarement fait l’objet de productions à grande échelle. Peu de méthodes d’extrapolation de ces applications ont été proposées et celles qui existent sont purement empiriques. Nous avons voulu établir une méthodologie d’extrapolation de réacteurs MO en nous servant d’observations expérimentales fiables. La méthodologie des travaux a d’abord consisté au choix d’une réaction cible pour nos études : l’estérification de l’acide acétique avec le pentanol catalysée par une résine acide d’échange ionique. Nous avons conçu et construit un réacteur agité avec application monomode des MO. Des études dans le pilote ont montré le comportement hydrodynamique parfaitement agité du réacteur, la reproductibilité et la haute efficacité du chauffage. De plus, aucun gradient de température dans le réacteur n’a été mis en évidence. Des tests chimiques sous MO en réacteur fermé et en continu, ainsi qu’en milieu peu polaire ont montré que l’application des MO n’a pas eu d’influence sur la cinétique de la réaction cible. Finalement, nous avons développé une procédure d’extrapolation de réacteurs micro-ondes de type cuve agitée, qui est basée sur l’absence d’effet MO sur la chimie et sur le contrôle des zones chaudes dans le réacteur / Microwave (MW) assisted organic synthesis has been employed in many laboratories since more than 20 years. There is a controversy concerning the effects of MW on the kinetics of reactions since some enhancement of reaction rates have been observed. While MW heating advantages could be of interest for processes intensification, this technique has rarely been employed for large-scale productions. Scaling-up methods are rare and the existed techniques are generally empirical. The aim of our project is to propose a methodology for the extrapolation of MW reactors, using experimental reliable observations. Our research strategy has enabled us the choice of the target reaction to be carried out under MW irradiation: the esterification of acetic acid with pentanol over an acidic cation-exchange resin. A stirred reactor with MW single mode application was designed and constructed. Studies on the pilot have showed the perfectly stirred hydrodynamic behaviour of the reactor, the stability and the high heating efficiency. Moreover, no thermal gradients in the reactor have been observed. Tests in the reactor operated in batch and continuous mode, as well as in weak polar media, showed that there is no influence of MW heating on the kinetics of the target reaction. Finally, a guideline for the scaling-up of MW reactors was developed, based on the absence of MW effects on the reaction kinetics and on the control of hot zones in the reactor

Com a proposta de selecionar a melhor conformação de um forno para redução carbotérmica com micro-ondas, dois tipos de cavidades com formatos paralepipédico e hexagonal foram projetadas e construídas. Os dois com uma característica em comum, o pleno controle da potência fornecida e da medida da energia de micro-ondas efetivamente aplicada à carga em processo de redução podendo assim realizar balanços de energia e determinação de taxa de reação com altos níveis de confiança. Eles permitem, sobretudo, a medida simultânea de temperatura e de massa do material sob redução, e a fácil reprodutibilidade das condições de ensaio. Os fornos paralepipédico e hexagonal operam com geradores de micro-ondas de 2,45 GHz e potência ajustável até 6 kW. Durante os ensaios as amostras foram mantidas sob atmosfera de argônio. Nos testes operacionais dos fornos procedeu-se à redução carbotérmica de minério de ferro de Carajás, utilizando carvão mineral Chipanga como redutor através de pelotas auto redutoras. Obtiveram-se curvas cinéticas de redução de minério de ferro, temperatura e de consumo de energia durante o processo. Os dados colhidos com estes fornos permitiram realizar análises estatísticas da eficiência de cada tipo de forno através da taxa de reação obtida além da energia de micro-ondas efetivamente consumida na redução do minério. Ainda, foi construído um forno cilíndrico, portanto extrapolando o formato hexagonal, com potência de 15 kW, com o objetivo de averiguar como o conjunto pelotas/cavidade se comporta em condições mais drásticas. / This work deals with two different types of microwave cavities to be used in carbothermic reduction that were designed and built in order to select a better furnace conformation. Parallepipedic and hexagonal shapes were used for this purpose. Both of them share some common characteristics: full control of the power supplied to the furnace, and measurement of the effective microwave power applied to the load under reduction process. These characteristics help to achieve energy balance and reaction rate with high confidence levels. Simultaneous measurements of mass and temperature versus time are also easily done and helps reproduction of each test condition. The parallelepiped and hexagonal ovens are excited by 2.45 GHz microwave generators with adjustable power up to 6 kW. Argon gas atmosphere was used when processing the samples. Operational tests of the carbothermic reduction of iron ore from Carajás were done by the use of self-reducing pellets of Chipanga coal. Temperature and other data collected during the processes allowed calculation of their kinetic curves and energy consumption. The efficiency of each kind of furnace was obtained from statistical analysis of the data using reaction rate as well as the microwave energy consumption. Finally, going further from the hexagonal shape, a cylindrical furnace was built in order to verify the behavior of the pellets/cavity groups in heavier conditions with applied power up to 15 kW.

A água de coco, como comercializada atualmente, é esterilizada e adicionada de conservante químico ou antioxidante, o que ocasiona a redução de suas qualidades sensorial e nutricional. Para evitar esses efeitos indesejados tem se estudado o aquecimento da água de coco através da radiação por micro-ondas, o que possibilitaria uma bebida de melhor qualidade sensorial e sem adição de conservante ou com menor quantidade dessa substância. Esta pesquisa teve como objetivo avaliar a viabilidade da pasteurização da água de coco por micro-ondas, utilizando esporos de B. coagulans como indicador biológico do processo. Esporos de B. coagulans CCGB (LFB-FIOCRUZ) 1433 foram inoculados em amostras de água de coco, obtida diretamente de frutos verdes (Cocos nucífera L.) e previamente acidificada (ácido ascórbico e cítrico), seguida de pasteurização em micro-ondas com frequência de 2450 MHz. Os ensaios, provenientes de um Delineamento Central Composto Rotacional, com 4 variáveis (temperatura, quantidade e composição dos ácidos e potência do aparelho de micro-ondas) foram realizados aleatoriamente, com tempo de processo de até 20 minutos. Os testes foram conduzidos com 3 repetições do ponto central. Também foi realizado o processo em manta de aquecimento a fim de comparar os dois métodos. Os resultados da inativação foram expressos em log número de esporos/mL de água de coco. A temperatura é o fator preponderante para o processo de pasteurização da água de coco através da análise dos resultados obtidos pela DCCR. Também foi possível observar que, nas seguintes condições: a) potência de 120 W; b) 76 mg de ácidos adicionados à bebida e c) composição dos ácidos de 22% ascórbico e 78% cítrico, houve uma separação dos resultados em dois grupos. Um grupo à temperatura de 86 °C, em que, a redução da população de esporos foi menor (entre 0,5 log e 3,7 log número de esporos/mL de água de coco), e outro à temperatura de 92 °C, que apresentou maiores reduções logarítimicas do micro-organismo (entre 3,4 log e 7,0 log número de esporos/mL de água de coco). Realizado o teste ANOVA, ficou comprovado que o aumento predito foi significativo. Houve diferença estatisticamente significativa na comparação entre o aquecimento por micro-ondas e o convencional. Porém, essa diferença não foi considerada uma vez que microbiologicamente pode ser desprezada. Quanto ao tempo de processo, são necessários, em média, 10 a 15 minutos de retenção na temperatura desejada para atingir o maior nível de inativação de esporos nas condições do ponto central (89 °C, 125 W, 75 mg de ácidos adicionados à água de coco e a composição desses ácidos de 75% cítrico e 25% ascórbico). A pasteurização da água de coco por micro-ondas mostrou-se viável, mas outros estudos são necessários para otimizar o processamento. / Coconut water, as currently marketed, is sterilized and added with chemical preservative or antioxidant, which reduces its sensory and nutritional qualities. In order to avoid these undesired effects, the heating of coconut water through microwaves radiation has been studied, which would allow a drink of better sensorial quality and without addition of preservatives or with reduced amount of these substances. The objective of this study was to evaluate the viability of the pasteurization of coconut water by microwave, using spores of B. coagulans as biological indicator of the process. Spores of B. coagulans CCGB (LFB-FIOCRUZ) 1433 were inoculated in samples of coconut water, obtained directly from green fruits (Cocos nucífera L.) and previously acidified (ascorbic and citric acid), followed by pasteurisation using microwaves with frequency of 2450 MHz. The tests, from a Rotational Composite Central Design, with 4 variables (temperature, quantity and composition of the acids and power of the microwave apparatus) were carried out randomly, with a process time of up to 20 minutes. The tests were conducted with 3 replicates of the central point. The conventional heating process was also carried out in order to compare the two methods. Inactivation results were expressed as log of spores /mL of coconut water. Temperature is the preponderant factor for the process of pasteurization of coconut water through the analysis of the DCCR. It was also possible to observe that, under the following conditions: a) power of 120W; b) 76 mg of acids added to the beverage and c) composition of acids of 22% ascorbic and 78% citric acid, the results were separated into two groups: one group at a temperature of 86 °C, where the reduction of the spore population was lower (between 0,5 log and 3,7 log of spores/mL of coconut water), and another one at a temperature of 92 °C, which presented higher logarithmic reductions of the microorganism (between 3,4 log and 7,0 log of spores/mL of coconut water). Once the ANOVA test was performed, it was verified that the predicted increase was significant. There was a difference statistically significant between conventional and microwave heating. However, this difference was not taken into account because microbiologically it could be neglected. As for processing time, an average of 10 to 15 minutes of retention at the desired temperature is required to achieve the highest level of inactivation of spores at the center point conditions (89 °C, 125 W, 75 mg of acids added to the cocnut water and the composition of acids of 75% cítrico e 25% ascórbico). The pasteurisation of coconut water by microwave has proved to be feasible, but other studies are needed to optimize processing.

O presente trabalho trata do estudo, projeto, desenvolvimento, construção e medida de lentes discretas planares (DLAs). Estes dispositivos atuam como sistemas irradiantes, especialmente com características multi-feixes. A construção destas lentes utiliza tecnologias compatíveis com a fabricação de circuitos impressos, com alguns detalhes que são característicos da área de antenas e circuitos planares. O estudo aborda as equações de projeto e considerações gerais relativas ao atendimento de especificações técnicas preliminares. Foram desenvolvidas duas lentes discretas, uma na frequência de 8GHz (banda X) e outra na frequência de 40GHz (banda Ka- faixa de ondas milimétricas). São apresentados os resultados de medidas destas duas lentes, que comprovam a possibilidade de uso em aplicações multi-feixes, bem como seu efeito de foco, análogo ao observado em lentes óticas comuns. / The object of this work is the study, design, development, fabrication and measurement of discrete lens arrays (DLAs). These devices act as radiant systems, especially with multi-beam characteristics. Their construction follows the same procedures and techniques normally found in printed circuit fabrication, with some further details that are pertinent to the antenna and planar circuit field. This study contains the design equations and general remarks as to fulfill preliminary technical specifications. Two real designs were developed, one in the X-band (8GHz) and another in the millimeter range, Ka band (40GHz). Their respective measurement results are presented, which proved their possible application in multi-beam systems, as well as their focusing effect, which is analogous to that observed in common optical lenses.

Os corantes azo são amplamente utilizados em muitas indústrias, entre elas as alimentícias, farmacêuticas e têxteis. Quando essas moléculas estão presentes no efluente industrial tornam o seu tratamento, que na maioria dos casos é biológico, difícil. Suas complexas estruturas são altamente estáveis e a presença de grupos sulfônicos (-SO3H) torna o corante ácido e altamente solúvel em água. Um exemplo deste tipo de corante é a tartrazina que pode causar efeitos adversos para a saúde humana, como alergia. Desde o início dos anos 70, quando os Processos Oxidativos Avançados (POAs) foram reconhecidos por sua capacidade de degradar poluentes em meio aquoso, houve um aumento significativo nas pesquisas por duas razões: a diversidade de tecnologias envolvidas e a grande variedade de efluentes que os POAs são capazes de tratar. A fotoquímica assistida por microondas (MO) consiste na combinação de dois tipos distintos de radiação eletromagnética, microondas e UV/VIS, na ativação de reações químicas. Frequentemente está associada ao uso de uma lâmpada de descarga sem eletrodo (LDE) que gera radiação ultravioleta (UV) sob a influência de um campo de microondas. O presente trabalho tem como objetivo tratar uma solução de tartrazina (25 mg L-1) utilizando o processo H2O2/UV/MO e otimizando-o a fim de se obter a maior degradação com a utilização da menor quantidade de oxidante possível. Para tanto, elaborou-se um planejamento fatorial com a finalidade de observar o comportamento das variáveis independentes pH e concentração inicial de peróxido de hidrogênio no processo. A partir dos resultados, elaborou-se um planejamento composto central a fim de se ajustar um modelo polinomial aos dados obtidos. A condição ótima de tratamento para as variáveis independentes foi: pH = 2,6 e [H2O2] = 2 × 10-3 mol L-1. A variável-resposta observada foi a remoção de cor (por meio da integração da área dos espectros na região do visível). A cinética obtida para o processo H2O2/UV/MO foi de ordem zero, com k = 3,9 × 10-2 u.a.-1 min-1 e, aproximadamente, 92% de descoramento em 24 minutos. A biodegradabilidade (DBO5/DQO) e a análise de carbono orgânico total (COT) não apresentaram variação significativa. No entanto, pôde-se observar, através da CE50, que o processo H2O2/UV/MO reduziu a fitotoxicidade da solução de tartrazina, indicando a possível formação de intermediários de degradação menos tóxicos que a molécula original. A avaliação do efeito das microondas foi feita pelo estudo da degradação da solução de tartrazina através dos processos H2O2, MO, H2O2/MO e UV/MO, sendo que o descoramento não passou de 20%, indicando que as MO influenciam no processo H2O2/UV devido ao possível sinergismo com a radiação UV e também pelos possíveis efeitos térmicos e não térmicos exercidos por essa radiação. / Azo dyes are extensively used in many industries such as food, drugs, and textiles ones. When these molecules are present in the industrial wastewaters, they make their treatment, which is in most cases a biological one, quite difficult. Their complex structures are very stable and the presence of sulfonic groups (-SO3H) makes the azo dyes acid and highly water-soluble. Tartrazine is an example of these dyes and can cause adverse effects to human health, like allergy. Since the early 70\'s, when Advanced Oxidation Processes (AOPs) were recognized by their capacity of degrading pollutants in aqueous media, there was a significant increase in research and for two reasons: the diversity of technologies involved and the many kinds of wastewaters that AOP can treat. The microwave-assisted photochemistry is the combination of two distinct types of electromagnetic radiations: microwave (MW) and UV/VIS. It is often associated with the use of an electrodeless discharge lamp (EDL), which generates ultraviolet (UV) radiation when placed in a microwave field. The aim of the present work is to treat a solution of tartrazine (25 mg L-1) by the H2O2/UV/MW process, as well as optimizing the process in order to obtain degradation with the use of the lowest possible amount of oxidant. For that purpose, a factorial design was performed to observe the effect of the independent variables pH and hydrogen peroxide concentration. With the results obtained, a composite central design was performed to fit a polynomial model to the data. The optimum treatment condition was: pH = 2.6 and [H2O2] = 2 × 10-3 mol L-1. The response variable was color removal (measured by the area under the spectra obtained in the visible region). The decolorization kinetics of the H2O2/UV/MW process followed a zero order model, with k = 3,9 × 10-2 u.a.-1 min-1 and color removal achieved 92% in 24 minutes. The biodegradability (BOD5/COD) ratio and total organic carbon (TOC) analyses showed no significant changes. However, through the CE50 maybe observed that the H2O2/UV/MW process reduced the toxicity of the tartrazine solution, indicating the possible formation of less toxic intermediates than the original molecule. The microwaves effect was assessed in a degradation study of the tartrazine solution by H2O2, MW, H2O2/MW, and UV/MW processes, and the decolorization did not exceed 20%, indicating that the MW influence the H2O2/UV process because of the possible synergism with the UV radiation and thermal and non-thermal effects exerted by the radiation.

The research described in this dissertation mainly covers the development of novel technologies for co-crystallisation along with the discovering of plumbagin co-crystal and thermodynamic interrelationship between the co-crystal polymorphs. Co-crystallisation is a fast growing field in the area of crystal design and has shown potential advantages in the field of pharmaceutical. Currently, many research groups are working on the development of new technologies for the synthesis of pure and stoichiometrically controlled co-crystals. In present study, three novel technologies have been developed for co-crystallisation, which include microwave assisted co-crystallisation, spherical crystallisation and microwave assisted sub-critical water processing. The microwave assisted co-crystallisation is a slurry based technology where, effects of drug solubility and dielectric properties of the solvent were investigated using caffeine / maleic acid as a model co-crystal pair. The mechanism of co-crystallisation under microwave irradiation has been proposed. The co-crystals of plumbagin with improved solubility were obtained with the coformers such as hydroquinone, resorcinol and urea using microwave assisted co-crystallisation technique. The spherical crystallisation technology was developed for co-crystallisation of carbamazepine / saccharin co-crystal pair and demonstrated its application for polymorphic control and as a potential technique for the purification of desired crystal form through surface energetic based separation. The thermodynamic interrelationship between Form I and Form II of carbamazepine / saccharin co-crystal was studied using different thermodynamic tests. The results obtained suggest that the carbamazepine / saccharin co-crystal polymorphs are monotropic. Microwave assisted sub-critical water processing has been explored as a green technology for the synthesis of co-crystals. Carbamazepine / saccharin co-crystal pair has been used as a model pair and effects of processing variables on the resulting crystal form and degradation of an API have been studied.