O comportamento térmico, a obtenção e caracterização de formas cristalinas do anti-histamínico loratadina foram investigado. A escolha do anti-histamínico loratadina como objeto de estudo resulta do seu interesse farmacológico. A loratadina é a Denominação Comum Internacional (DCI) dada ao etil 4-(8-cloro-5,6-dihidro-11H-benzo[5,6]cicloheptano[1,2-b]piridino-11-ilideno)-1-piperidinocarboxilato, que é um potente antialérgico e anti-histamínicos tricíclico, não-sedativo de ação prolongada. Formas cristalinas foram preparadas e estudadas com vista à identificação de formas polimórficas. Os solventes utilizados na preparação das soluções foram: álcool etílico, acetonitrila, álcool isopropílico, acetona, álcool metílico, éter isopropílico, éter metil terc-butílico, tolueno, clorofórmio. A cristalização foi realizada por evaporação do solvente em diferentes temperaturas. A calorimetria exploratória diferencial (DSC), termogravimetria e termogravimetria derivada (TG/DTG), análise térmica diferencial (DTA), difração de raios X (DRX) e a ressonância magnética nuclear (RMN) foram às técnicas utilizadas na caracterização das formas polimórficas. A maioria das amostras obtidas pelas técnicas de cristalização consistiam de misturas de formas cristalinas, contendo, por vezes, formas metaestáveis e formas amorfas. Identificaram-se duas formas cristalinas como polimorfos da loratadina, cujas curvas DSC mostrou interconversão entre ambas. / The preparation, characterization and thermal behavior of the crystalline forms of the antihistamine loratadine has been developed. The selection of loratadine as an object of study results from its pharmacological interest. Loratadine is the International Common Denomination (ICD) given to ethyl 4-(8-chloro-5,6-dihydro-11H-benzo [5,6] cyclohepta[1,2-b]pyridin-11-ylidene)-1-piperidinecarboxylate, a potent anti-allergic and anti-histamincs, tricyclic, non-sedating long acting. Crystalline forms were prepared and studied for the identification of polymorphic forms. The solvents used in preparing the solutions were: ethanol, acetonitrile, isopropyl alcohol, acetone, methyl alcohol, isopropyl ether, methyl tert-butyl ether, toluene, chloroform. The crystallization was performed by evaporating the solvent at different temperatures. The differential scanning calorimetry (DSC), thermogravimetry and derivative thermogravimetry (TG/DTG), differential thermal analysis (DTA), X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) techniques were used to characterize the polymorphic forms. Most of the samples obtained by the crystallization were mixtures of crystalline forms, containing sometimes forms metastable and amorphous forms. It was identified as two crystalline polymorphic forms of loratadine, whose DSC curves demonstrated that they are interconvertable.

Made available in DSpace on 2014-12-17T15:41:40Z (GMT). No. of bitstreams: 1 AnaCPC.pdf: 1447913 bytes, checksum: 8f65c2f6df911f6db297163eb551fb69 (MD5) Previous issue date: 2008-02-29 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The metalic oxides have been studies due to differents applications as materials semiconductor in solar cells, catalysts, full cells and, resistors. Titanium dioxide (TiO2) has a high electric conductivity due to oxygen vacancies. The Ce(SO4)2.2H2O doped samples TiO2 and TiO2 pure was obtained sol-gel process, and characterized by X-ray diffractometry,thermal analysis, and impedance spectroscopy. The X-ray diffraction patterns for TiO2 pure samples shows at 700?C anatase phase is absent, and only the diffraction peaks of rutile phase are observed. However, the cerium doped samples only at 900?C rutile in the phase present with peaks of cerium dioxide (CeO2). The thermal analysis of the TiO2 pure and small concentration cerium doped samples show two steps weight loss corresponding to water of hydration and chemisorbed. To larger concentration cerium doped samples were observed two steps weight loss in the transformation of the doped cerium possible intermediate species and SO3. Finally, two steps weight loss the end products CeO2 and SO3 are formed. Analyse electric properties at different temperatures and concentration cerium doped samples have been investigated by impedance spectroscopy. It was observed that titanium, can be substituted by cerium, changing its electric properties, and increased thermal stability of TiO2 anatase structure / Os ?xidos met?licos t?m sido muito estudados devido suas diversas aplica??es como materiais semicondutores em c?lulas solares, catalisadores, c?lulas combust?veis e resistores. O Di?xido de Tit?nio possui uma alta condutividade el?trica devido ?s suas vac?ncias de oxig?nio. Amostras de TiO2 puro, obtidas pelo m?todo sol-gel e dopadas com solu??es de Ce(SO4)2.2H2O, foram analisadas atrav?s de difratometria de raios-X, an?lise t?rmica e espectroscopia de imped?ncia. Atrav?s dos difratogramas de raios-X observou-se a transi??o completa das fases anat?sio-rutilo, para a amostra do TiO2 puro a partir de 700?C. Entretanto, para as amostras dopadas, essa transi??o s? ? completa a partir de 900?C, aparecendo picos correspondentes ao ?xido de c?rio. Atrav?s da an?lise t?rmica se observou uma perda de massa, para o TiO2 puro e dopado com a menor concentra??o de c?rio, correspondente ? desidrata??o e a ?gua quimissorvida. Para as amostras dopadas em uma maior concentra??o, foram observados dois est?gios de perda de massa, devido a decomposi??o do dopante em intermedi?rios e SO3. Essas amostras apresentaram mais duas perdas de massa devido a forma??o do CeO2 e SO3. A partir da espectroscopia de imped?ncia analisou-se as propriedades el?tricas das amostras em fun??o da temperatura de calcina??o e em fun??o da concentra??o do dopante. Tamb?m foi observado que o c?rio, por ter a capacidade de substituir o tit?nio na sua estrutura cristalina, modifica suas propriedades el?tricas e tem o poder de estabiliz?-lo termicamente em certas temperaturas

In the present dissertation the formation of microstructure, the kinetics of densification and the formation of surface layers developing during liquid phase sintering of silicon carbide are studied. The focus is on the additive systems Al2O3 plus Y2O3 and AlN plus Y2O3. Phase and especially liquid phase formation in both of the systems SiC, Al2O3 , Y2O3 and AlN, Al2O3 , Y2O3 are investigated in detail examining 12 espectively 17 different compositions per system. Melting temperatures have been determined by TG/DTA, in both systems for the first time. Phase composition of samples was analysed by the combination of XRD, SEM and EDX. In the system SiC, Al2O3 , Y2O3 the formation of the phases expected from the quasibinary Al2O3 , Y2O3 could be observed thus silicon carbide has to be in equilibrium with the oxide additives. The low solubility of SiC in the oxide melt, which was suggested by Hoffmann and Nader, could be confirmed. In the system AlN, Al2O3 , Y2O3 the formation of phases as stated by Medraj was confirmed, except for the dimension of the stability region of the γ- spinel and YAG which is wider in the present work. For the first time diffusion coefficients of the species Y3+ and Al3+ in the oxide melt formed by Al2O3 and Y2O3 at temperatures above 1825 ◦ C were determined. The values are in the order of 2 · 10−6 cm2 /s which results in a diffusion length of 14.1 μm for a diffusion time of one second. This allows the fast equilibration of Y and Al deficiencies. Kinetics of densification was modeled by kinetic field, master curve and thermokinetic method, based on detailed experimental investigation of the shrinkage during liquid phase sintering of SiC. It could be proved that the first 30 − 40 % of densification are controlled by solid phase reactions which accelerate particle rearrangement without presence of a liquid phase. During the remaining 60 − 70 % of densification a liquid is present, resulting in the predominance of mechanisms of liquid phase sintering. The models deliver activation energies in the range from 608 KJ/mol to 1668 kJ/mol and allow, within the scope of validity of each method the prediction of densification during liquid phase sintering of silicon carbide. When sintering silicon carbide with Al2O3 plus Y2O3 the formation of several surface layers, depending on atmosphere, maximum temperature, dwelling time and amount and composition of additives was observed. In nitrogen atmosphere with low partial pressures a surface layer consisting of AlN is forming whilst at high partial pressures SiAlON- polytypes occur. After sintering in Argon or Ar-CO- atmosphere three main types of surface layers are present. One consists of alumina, one contains only YAG and one shows highly porous, additive depleted regions. An explanation for the formation of the several surface layers could be given by the combination of the determined diffusion coefficients with the results achieved in the thermodynamics part. The results achieved in this work can be a contribution to the knowledge based design of the production process of liquid phase sintering of silicon carbide.

Un alliage métallique complexe (CMA) est un composé intermétallique dont la maille élémentaire est constituée d’un nombre important d’atomes formant bien souvent des aggrégats de haute symmétrie. De la complexité de ces composés peuvent découler des propriétés physico-chimiques intéressantes pour divers domaines d’application. Le système binaire aluminium-iridium est un système qui présente de nombreux composés intermétalliques dont la moitié sont des CMA. Malgré l’étude approfondie dont ce système a fait l’objet dans la littérature, certaines incertitudes demeuraient irrésolues, nous amenant ainsi à réexaminer le diagramme de phase Al-Ir. Nous avons également exploré les systèmes ternaires dits "push-pull" Al-Au-Ir et Al-Ag-Ir, propices à la formation de phases CMA selon certains auteurs. Au total, une centaine d’échantillons ont été préparés par fusion à l’arc puis analysés par diverses techniques de caractérisations: diffraction des rayons X (XRD), microscopie électronique à balayage (SEM), analyse dispersive en énergie (EDS) et analyse thermique différentielle (DTA). Quatre nouveaux composés intermétalliques ont ainsi été identifiés: Al2.4Ir, Al72Au2.5Ir29.5, Al3AuIr et Al11SiIr6, ce dernier étant issu d’une manipulation accidentelle. La structure cristallographique de chacun de ces composés a été résolue, révélant Al2.4Ir et Al72Au2.5Ir29.5 comme étant des CMA possédant une centaine d’atomes dans la maille. Des calculs basés sur la théorie de la fonctionnelle de la densité (DFT) sont venus apporter des précisions concernant la stabilité des composés Al3AuIr et Al11SiIr6. Pour le système Al-Ir, une variante structurale de deux CMA déjà connus de la littérature a également pu être mise en évidence. Les structures cristallographiques de la variante de Al2.75Ir et de celle de Al28Ir9 ont ainsi été approchées, présentant 240 et 444 atomes dans leur maille respective. Les propriétés de surface comptent parmi les aspects les plus intéressants des CMA, par exemple pour la catalyse hétérogène. En l’absence de monocristaux de taille macroscopique, nous avons étudié la possibilité de former des composés de surface par dépôt de Ir sur une surface Al(100) suivi de recuits. Des caractérisations par diffraction d’électrons lents (LEED), spectroscopie de photoélectrons excités par rayons X (XPS) et microscopie à effet tunnel (STM) supportés par ces calculs ab initio ont révélé qu’à partir de 320°C, le composé Al9Ir2 se formait en surface mais également dans une partie du volume du substrat / A complex metallic alloy (CMA) is an intermetallic compound whose unit cell contains a large number of atoms oftenly forming highly-symmetric clusters. From the complexity of these compounds can arise physical and chemical properties interesting for various fields of application. The aluminium-iridium binary system exhibits numerous intermetallic compounds of which half of them are actually CMAs. Despite this system being extensively studied in the literature, some uncertainies remained unsolved, leading us to reinvestigate the Al-Ir phase diagram. In addition, the "push-pull" systems Al-Au-Ir and Al-Ag-Ir, favorable for the formation of CMA according to the literature, have been explored. Thus, near a hundred of samples have been prepared by arc-melting before being analyzed with different characterizations techniques: X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and differential thermal analysis (DTA). From this study, 4 new intermetallic compounds could be identified: Al2.4Ir, Al72Au2.5Ir29.5, Al3AuIr and Al11SiIr6, the latter being the result of a fortuitous manipulation. The crystallographic structure of each of these compounds has been solved, revealing Al2.4Ir and Al72Au2.5Ir29.5 to be two CMAs with around one hundred of atoms in their unit cell. Calculations based on the density functional theory (DFT) brought further details about the stability of the two other Al3AuIr and Al11SiIr6 compounds. In the Al-Ir binary system, a structural variant of two well-known CMAs has been also unveiled. The crystallographic structures of the Al2.75Ir and Al28Ir9 variant have been approached, revealing 240 and 444 atoms in their respective unit cell. The CMAs oftently exhibit interesting surface properties. In order to study the Al-Ir compound surfaces, iridium adsorption on Al(100) surface followed by annealing has been investigated. The characterizations by lowenergy electrons diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and scanning tunneling miscoscopy (STM) supported by ab initio calculations revealed that, from 320 C, the Al9Ir2 compound is formed at the surface but also in the substrate bulk

O comportamento térmico, a obtenção e caracterização de formas cristalinas do anti-histamínico loratadina foram investigado. A escolha do anti-histamínico loratadina como objeto de estudo resulta do seu interesse farmacológico. A loratadina é a Denominação Comum Internacional (DCI) dada ao etil 4-(8-cloro-5,6-dihidro-11H-benzo[5,6]cicloheptano[1,2-b]piridino-11-ilideno)-1-piperidinocarboxilato, que é um potente antialérgico e anti-histamínicos tricíclico, não-sedativo de ação prolongada. Formas cristalinas foram preparadas e estudadas com vista à identificação de formas polimórficas. Os solventes utilizados na preparação das soluções foram: álcool etílico, acetonitrila, álcool isopropílico, acetona, álcool metílico, éter isopropílico, éter metil terc-butílico, tolueno, clorofórmio. A cristalização foi realizada por evaporação do solvente em diferentes temperaturas. A calorimetria exploratória diferencial (DSC), termogravimetria e termogravimetria derivada (TG/DTG), análise térmica diferencial (DTA), difração de raios X (DRX) e a ressonância magnética nuclear (RMN) foram às técnicas utilizadas na caracterização das formas polimórficas. A maioria das amostras obtidas pelas técnicas de cristalização consistiam de misturas de formas cristalinas, contendo, por vezes, formas metaestáveis e formas amorfas. Identificaram-se duas formas cristalinas como polimorfos da loratadina, cujas curvas DSC mostrou interconversão entre ambas. / The preparation, characterization and thermal behavior of the crystalline forms of the antihistamine loratadine has been developed. The selection of loratadine as an object of study results from its pharmacological interest. Loratadine is the International Common Denomination (ICD) given to ethyl 4-(8-chloro-5,6-dihydro-11H-benzo [5,6] cyclohepta[1,2-b]pyridin-11-ylidene)-1-piperidinecarboxylate, a potent anti-allergic and anti-histamincs, tricyclic, non-sedating long acting. Crystalline forms were prepared and studied for the identification of polymorphic forms. The solvents used in preparing the solutions were: ethanol, acetonitrile, isopropyl alcohol, acetone, methyl alcohol, isopropyl ether, methyl tert-butyl ether, toluene, chloroform. The crystallization was performed by evaporating the solvent at different temperatures. The differential scanning calorimetry (DSC), thermogravimetry and derivative thermogravimetry (TG/DTG), differential thermal analysis (DTA), X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) techniques were used to characterize the polymorphic forms. Most of the samples obtained by the crystallization were mixtures of crystalline forms, containing sometimes forms metastable and amorphous forms. It was identified as two crystalline polymorphic forms of loratadine, whose DSC curves demonstrated that they are interconvertable.

This thesis describes possible applications of Prony's method in timing analysis of digital circuits. Such applications include predicting the future shape of the waveform in DTA(Dynamic Timing Analysis) and delay look-up table in STA(Static Timing Analysis). Given some equally spaced output values, the traditional Prony's method can be used to extract poles and residues of a linear system, i.e. to characterize a waveform using an exponential function. In this thesis, not only values but also equally spaced derivatives are tested. Still using same idea of the traditional Prony's method, poles and residues can also be extracted with those values and derivatives. The resultant poles and residues will be used to predict the output waveform in DTA analysis. The benefits brought by the using of derivatives include less simulation steps and less CPU time consuming than the regular constant step simulation. As a matter of fact, the Prony's method can precisely approximate a complicated waveform. Such property can be applied for STA analysis. The Prony's approximation can be used to precisely record an output waveform, which is used as an entry of the look-up table of STA. Since the accuracy of STA analysis relies on the accuracy of the input and output waveform in the look-up table, the accuracy of the Prony's approach is promising.

This thesis describes possible applications of Prony's method in timing analysis of digital circuits. Such applications include predicting the future shape of the waveform in DTA(Dynamic Timing Analysis) and delay look-up table in STA(Static Timing Analysis). Given some equally spaced output values, the traditional Prony's method can be used to extract poles and residues of a linear system, i.e. to characterize a waveform using an exponential function. In this thesis, not only values but also equally spaced derivatives are tested. Still using same idea of the traditional Prony's method, poles and residues can also be extracted with those values and derivatives. The resultant poles and residues will be used to predict the output waveform in DTA analysis. The benefits brought by the using of derivatives include less simulation steps and less CPU time consuming than the regular constant step simulation. As a matter of fact, the Prony's method can precisely approximate a complicated waveform. Such property can be applied for STA analysis. The Prony's approximation can be used to precisely record an output waveform, which is used as an entry of the look-up table of STA. Since the accuracy of STA analysis relies on the accuracy of the input and output waveform in the look-up table, the accuracy of the Prony's approach is promising.

Das Ziel der Dissertation besteht darin, einen Beitrag zur Entwicklung von Hochtemperaturloten auf Eisenbasis mit Liquidustemperaturen von < 1100 °C zu leisten. Die Lote sollen als alternative Werkstoffe für die derzeit verwendeten Nickelbasislote im Werkzeug- und Wärmetauscherbau Anwendung finden. Als Grundwerkstoffe kommen Werkzeugstähle sowie rost- und säurebeständige Stähle in Betracht. Wichtige Legierungselemente sind Silizium, Nickel, Chrom und Bor. Eine Verbesserung gegenüber den Nickelbasisloten soll die Gefügeausbildung in Abhängigkeit der Lötspaltbreite sowie das Korrosionsverhalten darstellen. Entsprechende Ergebnisse werden aufgezeigt und mit Daten zur Zugfestigkeit, zum Zähigkeitsverhalten im Schlagbiegeversuch sowie zur Härteverteilung über die Lötnaht vervollständigt. Für ein Verständnis des Schmelzverhaltens dienen DTA-Untersuchungen. Eine Einordnung der entwickelten Lote in den derzeitigen Stand der Forschung wird gegeben. Weiterführendes Forschungs- und Entwicklungspotenzial wird aufgezeigt.

This thesis describes possible applications of Prony's method in timing analysis of digital circuits. Such applications include predicting the future shape of the waveform in DTA(Dynamic Timing Analysis) and delay look-up table in STA(Static Timing Analysis). Given some equally spaced output values, the traditional Prony's method can be used to extract poles and residues of a linear system, i.e. to characterize a waveform using an exponential function. In this thesis, not only values but also equally spaced derivatives are tested. Still using same idea of the traditional Prony's method, poles and residues can also be extracted with those values and derivatives. The resultant poles and residues will be used to predict the output waveform in DTA analysis. The benefits brought by the using of derivatives include less simulation steps and less CPU time consuming than the regular constant step simulation. As a matter of fact, the Prony's method can precisely approximate a complicated waveform. Such property can be applied for STA analysis. The Prony's approximation can be used to precisely record an output waveform, which is used as an entry of the look-up table of STA. Since the accuracy of STA analysis relies on the accuracy of the input and output waveform in the look-up table, the accuracy of the Prony's approach is promising.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The 2:1 expandable clay minerals have high importance when present in soil, even in small amount, as in the case of soil with a high degree of secondary alteration. The study of these minerals is essential to understanding the physical and chemical behavior of soils, however, the techniques have not always permitted their suitable concentration, in order to facilitate their study. Therefore, this study aimed to analyze the concentration of phyllosilicates clay minerals with 2:1 structure through the technique of selective dissolution of oxides and kaolinite, aiming their study by X-ray diffraction and thermal analysis. The samples were collected in Rio Grande do Sul, in different weather conditions in profiles of Regosols (RRd and RRe), Ferralsol (LVd) and Vertisol (VEo). The clay fraction of A and B horizons of soil were separated and subjected to treatment with dithionite-citrate-bicarbonate and then with warm NaOH in 10 different concentrations, from 0.5 to 5 mol L-1. For mineralogical characterization we used the techniques of X-ray diffraction (XRD), thermogravimetry (TG) and differential thermal analysis (DTA). The results obtained by the analysis of X-ray diffraction showed that for most weathered soils as the Ferrasol, the NaOH solution does not contribute to the concentration of the 2:1 mineral. However, to the Vertisol the solution of NaOH 4.0 mol L-1 was more efficient in the concentration of minerals. To the Regossol RRd no concentration of NaOH solution was effective and to the RRe the concentration of 2.5 mol L-1 solution of NaOH was most suitable for concentrating the 2:1 clay. The extraction of kaolinite and gibbsite by NaOH solution was only partial for kaolinite. The thermal analysis showed predominance of kaolinite and gibbsite in relation to the 2:1 minerals in the samples free of oxides. The most effective treatment for the thermal analysis for 2:1 mineral concentration was NaOH 4 mol L-1 for samples LVd B, RRh A, RRe A and Veo A. The NaOH 3 mol L-1 treatment was more efficient for samples LVd A and VEo B. The relative concentration of 2:1 was higher in samples with dystrophic character. / Os argilominerais 2:1 expansíveis apresentam elevada importância quando presentes nos solos, mesmo em quantidade pequena, como no caso de solos com elevado grau de alteração secundária. O estudo destes minerais é fundamental para o entendimento do comportamento físico-químico dos solos, no entanto, as técnicas utilizadas nem sempre tem permitido a sua concentração adequada, de forma a facilitar o seu estudo. Por isso, este trabalho teve como objetivo analisar a concentração de argilominerais filossilicatos com estrutura 2:1 através da técnica de dissolução seletiva de óxidos e caulinita, visando o seu estudo por difratometria de raios-X e por análise térmica. As amostras analisadas foram coletadas no Rio Grande do Sul, em diferentes condições climáticas, em perfis de Neossolos (RRd e RRe), Latossolo (LVd) e Vertissolo (VEo). A fração argila dos horizontes A e B destes solos foram separadas e submetidas ao tratamento com ditionito-citrato-bicarbonato de sódio e posteriormente com NaOH a quente em 10 concentrações diferentes, a partir de 0,5 até 5 mol L-1. Para a caracterização mineralógica utilizou-se as técnicas de difração de raios-X (DRX), termogravimetria (TG) e análise térmica diferencial (ATD). Os resultados obtidos pelas análises de difratometria de raios-X mostraram que para solos mais intemperizados como o Latossolo a solução de NaOH não contribui para a concentrar os minerais 2:1. No entanto, para o Vertissolo a solução de NaOH 4,0 mol L-1 foi mais eficiente na concentração desses minerais. Os Neossolos apresentaram comportamento distinto, sendo que para o RRd nenhuma concentração da solução de NaOH foi eficiente e para o RRe a concentração de 2,5 mol L-1 da solução de NaOH foi a mais adequada para a concentração dos argilominerais 2:1. A extração da caulinita e gibbsita através da solução de NaOH foi apenas parcial para a caulinita, observou-se a permanência deste mineral em boa parte das concentrações. As análises térmicas mostraram predominância de caulinita em relação à gibbsita e minerais 2:1 nas amostras desferrificadas. O tratamento mais eficiente, pela análise térmica, para concentração de minerais 2:1 foi o NaOH 4 mol L-1 para as amostras LVd B, RRh A, RRe A e VEo A e o tratamento NaOH 3 mol L-1 para as amostras LVd A e VEo B. A concentração relativa de 2:1 foi maior nas amostras com caráter distrófico.