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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
121

The Luminescence prosperties of the wide bandgap nitrides doped with rare earth ions and gallium nitride doped with conventional isoelectornic impurities

Jadwisienczak, Wojciech M. January 2001 (has links)
No description available.
122

A theoretical study of the HCP to omega martensitic phase transition in titanium

Trinkle, Dallas Rhea, III January 2003 (has links)
No description available.
123

Modelling and Simulation of Carbon Dioxide Transportation in Pipelines: Effects of Impurities

Peletiri, Suoton P. January 2020 (has links)
Carbon dioxide capture, transportation, and storage has been identified as the most promising way to reduce anthropogenic carbon dioxide (CO2) released into the atmosphere. Efforts made to achieve this purpose include the Paris (Climate) Accord. This agreement seeks to encourage countries to take the issue of rising global temperatures seriously. With nearly all countries signing this agreement, many CCTS projects are expected. Pipelines are employed in the transportation of CO2. CO2 fluids contain impurities that affect the fluid properties and flow dynamics, but pipelines are mostly designed assuming that the CO2 fluid is pure. CO2 pipeline fluids contain at least 90 % CO2 with the balance made up of impurities. The impurities include nitrogen, methane, oxygen, hydrogen, sulphur dioxide, hydrogen sulphide, carbon monoxide, ammonia, argon, etc. The effects of the impurities are studied using simulation software; Aspen HYSYS, gPROMS and HydraFlash. The results show that all impurities impacted negatively on transportation. At equal concentrations, hydrogen had the greatest effect on fluid properties and hydrogen sulphide the least impact. At the specified allowable concentration, nitrogen had the worst effect on pressure loss (32.1 %) in horizontal pipeline, density, and critical pressure. Carbon monoxide (with only 0.2-mol %) had the smallest effect in pressure drop (0.3 %). Analysis of supercritical and subcritical (or liquid) CO2 fluid transportation shows that subcritical fluids have higher densities (more volume transported) and lower pressure losses than supercritical fluids. Subcritical fluid transportation would therefore have lower pipeline transportation costs than supercritical fluids. Also, soil heat conductivity has greater effect than ambient temperature in buried pipelines. Simple equations that approximate binary CO2 fluid properties from pure CO2 properties were developed and presented.
124

High-Temperature Corrosion of Aluminum Alloys: Oxide-Alloy Interactions and Sulfur Interface Chemistry

Addepalli, Swarnagowri 12 1900 (has links)
The spallation of aluminum, chromium, and iron oxide scales is a chronic problem that critically impacts technological applications like aerospace, power plant operation, catalysis, petrochemical industry, and the fabrication of composite materials. The presence of interfacial impurities, mainly sulfur, has been reported to accelerate spallation, thereby promoting the high-temperature corrosion of metals and alloys. The precise mechanism for sulfur-induced destruction of oxides, however, is ambiguous. The objective of the present research is to elucidate the microscopic mechanism for the high-temperature corrosion of aluminum alloys in the presence of sulfur. Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) studies were conducted under ultrahigh vacuum (UHV) conditions on oxidized sulfur-free and sulfur-modified Al/Fe and Ni3Al(111). Evaporative deposition of aluminum onto a sulfur-covered iron surface results in the insertion of aluminum between the sulfur adlayer and the substrate, producing an Fe-Al-S interface. Aluminum oxidation at 300 K is retarded in the presence of sulfur. Oxide destabilization, and the formation of metallic aluminum are observed at temperatures > 600 K when sulfur is located at the Al2O3-Fe interface, while the sulfur-free interface is stable up to 900 K. In contrast, the thermal stability (up to at least 1100 K) of the Al2O3 formed on an Ni3Al(111) surface is unaffected by sulfur. Sulfur remains at the oxide-Ni3Al(111) interface after oxidation at 300 K. During annealing, aluminum segregation to the g ¢ -Al2O3-Ni3Al(111) interface occurs, coincident with the removal of sulfur from the interfacial region. A comparison of the results observed for the Al2O3/Fe and Al2O3/Ni3Al systems indicates that the high-temperature stability of Al2O3 films on aluminum alloys is connected with the concentration of aluminum in the alloy.
125

Influence des impuretés des kaolins sur les propriétés des produits de cuisson. / Influence of the kaolin impurities on the fired products properties.

Bouzidi, Nedjima 23 September 2012 (has links)
Ce travail concerne l’étude de l’effet des impuretés sur les phénomènes physico-chimiques apparaissant durant le frittage des kaolins entre 900 et 1600 °C et les propriétés physiques qui en découlent. Le kaolin est utilisé dans le domaine des céramiques : céramique traditionnelle, porcelaine, céramiques réfractaires (mullite, chamotte), porcelaines électrotechniques, etc… Il est d’usage de contrôler la teneur et la nature des impuretés car leur présence peut limiter leurs applications.Sept kaolins ont été choisis pour les impuretés qu’ils contiennent à savoir ;• Feldspaths, quartz et oxydes de fer pour les kaolins de Tamazert (Algérie)• Matières organiques et oxyde de manganèse pour les kaolins de Djebel Debbagh (Algérie).• Matières organiques, oxydes de fer, gibbsite et anatase pour les kaolins des Charentes (France). La kaolinite ou l'halloysite, de même composition, est le minéral majeur dans chaque cas. L'ensemble des matériaux a été réduit par broyage à la taille de 63 μm. Le premier volet de l’étude consiste en une caractérisation physico-chimique des différents kaolins pour identifier et quantifier les principaux minéraux qui les composent. Le second volet concerne la compréhension des transformations thermiques qui se produisent lors du processus de deshydroxylation de la kaolinite (metakaolin) et lors de la formation de la mullite et de la cristobalite à de hautes températures (1600 °C). La microstructure, le retrait, la densification, la porosité sont les principaux paramètres étudiés dans ce volet.Le troisième volet porte sur les propriétés des kaolins lors du frittage à savoir : Les propriétés colorimétriques, mécaniques et diélectriques. L’effet des impuretés ainsi que la microstructure lors du frittage sur ces propriétés (colorimétrique, mécaniques et diélectriques) sont largement développés. Lors du frittage des différents kaolins la taille des cristallites de mullite augmente avec la température. Ces cristallites incorporent les impuretés colorantes tels que Fe2+/Fe3+, Ti4+/Ti2+ et Mn4+/Mn2+ (selon la température), ce qui résulte dans l’augmentation de la chromaticité et la diminution de la clarté à partir de 1100 °C. La transformation de la phase anatase à la phase rutile diminue le paramètre de clarté des kaolins des charentes. La présence de cristobalite dans le cas du kaolin de Djebel Debbagh riche en manganèse participe à l’augmentation de sa clarté au delà de 1400 °C. La présence de feldspath dans les kaolins de Tamazert améliore leurs propriétés diélectriques grâce à la formation de la phase vitreuse. Lors de l’augmentation de la température à1300 °C, ces propriétés augmentent, elles diminuent avec l’augmentation des fréquences (107-109Hz). Les pertes diélectriques sont plus importantes par rapport à celles rencontrées dans les matériaux céramiques (Porcelaines) utilisés dans les diélectriques qui sont en générale <10-3. Une dernière partie est consacrée à l’application d'un kaolin naturellement riche en anatase dans le domaine des porcelaines diélectriques. L’identification et la quantification des phases formées durant le frittage à 1300 °C , la porosité, la microstructure (observée par MEB) et les propriétés mécaniques et diélectriques sont déterminés. La permittivité relative théorique des porcelaines obtenues, calculée en utilisant la règle des mélanges des phases minéralogiques formées est en bon accord avec les valeurs expérimentales trouvées. / This work concerns the study of the effect of impurities on the physico-chemical phenomena occurring duringthe sintering of kaolin between 900 and 1600 °C and the resulting physical properties. Kaolin is used in the field ofceramics: traditional ceramics, porcelain, refractory ceramic (mullite, chamotte), electrotechnical porcelain, etc. ... It iscustomary to control the content and nature of impurities that may limit their applications.Seven kaolin were selected for the impurities they contain namely; Feldspar, quartz and iron oxides in kaolin of Tamazert (Algeria). Organic matters and manganese oxide for kaolin of Djebel debbagh (Algeria). Organic matter, iron oxides, gibbsite and anatase in kaolin of Charentes basin (France).Kaolinite and halloysite, with the same composition, is the major mineral in each case. All the materials werereduced by grinding to the size of 63 μm.The first part of the study consists of physico-chemical characterizations of different kaolin to identify andquantify the major minerals that compose them.The second part concerns the understanding of thermal transformations that occur during the process ofdehydroxylation of kaolinite (metakaolin) and during the formation of mullite and cristobalite at high temperatures(1600 ° C). The microstructure, shrinkage, densification, the porosity are the main parameters studied in this part.The third part deals with the properties of kaolin during sintering where colorimetric, mechanical and dielectricproperties were studied.The effect of impurities and the microstructure during sintering of these properties (color, mechanical anddielectric) are widely developed. During sintering, crystallite size of mullite of different kaolins increases withtemperature. These crystallites incorporate impurities coloring such as Fe2 +/ Fe3 +, Ti4 +/ Ti2 + and Mn4 +/ Mn 2 +(depending on temperature), resulting in the increase of the chromaticity and the decrease in brightness from 1100 ° C.The transformation of anatase to rutile phase decreases the parameter of clarity of the charente kaolin. Presence ofcristobalite in the case of kaolin of Djebel Debbagh (which is rich in manganese) participates to the increase in claritybeyond 1400 ° C. The presence of feldspar in kaolin of Tamazert improves their dielectric properties through theformation of the glassy phase. When increasing the temperature at 1300 ° C, these properties increase. Relativepermittivity of the calcined kaolin decrease with increasing frequency (107-109Hz). The dielectric losses are largercompared to those found in materials used in the dielectric which are in general <10-3.The last part is devoted to the application of kaolin naturally rich in anatase in the field of dielectric porcelain.The identification and quantification of phases formed during sintering at 1300 °C, porosity, microstructure (observedby SEM) and mechanical and dielectric properties are determined. The theoretical relative permittivity obtained bycalculation using a mixing rule of the mineralogical phases formed agrees with the experimental values.
126

Contrôle du rayonnement dans les plasmas de fusion par confinement magnétique

Dachicourt, Remi 01 October 2012 (has links)
La résolution d'un certain nombre de problèmes physiques est nécessaire au développement de réacteurs électrogènes utilisant la fusion thermonucléaire contrôlée. Le travail présenté ici traite du contrôle du rayonnement dans le cadre général de la tenue des matériaux aux flux de chaleur, ainsi que de l'opération d'un tokamak à forte densité. Ces deux points concernent plus particulièrement le futur réacteur de démonstration, appelé DEMO, pas intermédiaire entre ITER et un réacteur commercial. L'opération de DEMO sera contrainte par la nécessité de rayonner dans un large volume afin de limiter le dépôt de puissance localisé sur les plaques du divertor. Une grande fraction de rayonnement (80 à 90% de la puissance extraite) devra être obtenue tout en conservant un excellent confinement et une pollution réduite au cúur du plasma. Les études actuelles montrent que cette fraction de rayonnement est atteignable tout en limitant la contamination du plasma, mais l'amélioration des modèles de rayonnement est indispensable, tout comme les études concernant la compatibilité entre un bord fortement rayonnant et l'existence d'une barrière de transport permettant l'accès à un régime de confinement amélioré, le mode H. En parallèle, une forte densité (fraction de Greenwald supérieure à l'unité) est aussi indispensable pour atteindre la fraction de rayonnement désirée. De plus, la puissance fusion, et donc le bilan économique d'un réacteur est directement liée à la densité dans la zone de réaction, au centre du plasma. / The route presently envisaged towards the development of a commercial fusion power plant includes that a few remaining physics issues are solved. The present work addresses two of them: plasma radiation control, as a part of the more general power handling issue, and high density tokamak operation. These two issues will be most critical in the demonstration reactor, called DEMO, intermediate step between ITER and a future commercial reactor. For DEMO, the need to radiate a large fraction of the power so as to limit the peak power load on the divertor will be a key constraint. High confinement will have to be combined with high radiated power fraction, and the required level of plasma purity. A fractional radiated power, including bremsstrahlung radiation, of 80-90% of the total power loss will be required. Present studies suggest that this level of radiation could be achieved with acceptable levels of plasma contamination, but improvements are required in models of plasma radiation, and compatibility with the edge transport barrier of the H-mode has to be further assessed. Correlatively, high plasma density (typically with a Greenwald fraction above unity) is required, both because it allows efficient radiation of exhaust power to the reactor walls, and because the final cost of electricity is directly influenced by the achieved Greenwald value.
127

Espalhamento e interferência eletrônica entre estados induzidos por impurezas em semimetais de Dirac e Weyl /

Marques, Yuri Policei. January 2019 (has links)
Orientador: Antonio Carlos Ferreira Seridonio / Resumo: Embora o estado fundamental de moléculas covalentes diatômicas na natureza seja inevitavelmente ligante com primeiro estado excitado antiligante, foi demonstrado teoricamente que um par de impurezas, colocadas dentro de um semimetal de Dirac tridimensional, pode exibir um estado fundamental antiligante. Esse contraste com a natureza de moléculas isoladas surge devido a emergência de uma inesperada interação de longo alcance mediada pelos elétrons de condução com comportamento relativístico inerente ao semimetal de Dirac. Os perfis dos orbitais moleculares ligante e antiligante desse estado molecular são obtidos por meio da determinação teórica da densidade local de estados na superfície, cuja medida experimental pode ser realizada com auxílio da microscopia de corrente de tunelamento. Para o semimetal de Weyl, foi evidenciado que a quebra de simetria de reversão temporal é responsável por uma transição energética de s- para p-wave nos orbitais individuais das impurezas. Como consequência dessa transição e da característica direcional dos orbitais p-wave, a interferência entre as impurezas produz orbitais do tipo sigma quando frontais e do tipo \pi quando paralelas. Além disso, foi verificado que o surgimento do efeito magneto quiral, devido a separação dos nós de Weyl com quiralidades opostas, produz polarização nos orbitais moleculares via oscilações de Friedel. Por fim, foi analisado o efeito dos graus de liberdade de vibração da rede, presentes em qualquer sistema realísti... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Although the ground state of the diatomic molecules in nature is inevitably bonding with its first excited state is antibonding, it was demonstrate theoretically that a pair of impurities, placed buried in three-dimensional Dirac semimetals, may exhibit an antibonding ground state. This contrast with the nature of isolated molecules emerges due to an unexpected long-range interaction mediated by the conduction electrons with relativist behavior inherent to Dirac semimetal. The bonding and antibonding molecular profiles were obtained by theoretical determination of the local density states on the system surface, whose experimental measurement can be performed with the help of tunneling current microscopy. For theWeyl semimetal, it was evidenced that the time reversal symmetry break is responsible for an energy transition from s- to p-wave in the individual orbitals of the impurities. As a consequence of this transition and the directional characteristic of the p-wave orbitals, the interference between the impurities produces p-type orbitals when frontal and -type orbitals when parallel. In addition, it was found that the appearance of the chiral magneto effect, due to the separation of the Weyl nodes with opposite chiralities, produces polarization in the molecular orbitals via Friedel oscillations. Lastly, it was addressed the effect of vibrational degrees of freedom, which are present in any realistic system, in the formation and features of (anti)bonding molecular state, ... (Complete abstract click electronic access below) / Doutor
128

Propriétés physiques et optiques du manteau neigeux sur la banquise arctique / Physical and optical properties of Arctic marine snow

Verin, Gauthier 18 February 2019 (has links)
L’océan Arctique est marqué par une forte saisonnalité qui se manifeste par la présence d’une banquise permanente dont l’extension varie entre 6 et 15 millions de kilomètres carré. Interface plus ou moins perméable, la banquise limite les échanges atmosphère - océan et affecte le budget énergétique global en réfléchissant une part importante du rayonnement incident. Le manteau neigeux qui se forme à sa surface est un élément essentiel notamment parce qu’il contribue fortement aux propriétés optiques de la banquise. D’une part par son albédo, proche de l’unité dans le visible, qui retarde sensiblement la fonte estivale de la glace. Et d’autre part, il est majoritairement responsable de l’extinction verticale de l’éclairement dans la banquise. Or, la faible intensité lumineuse transmise à la colonne d’eau constitue un facteur limitant important à l’accumulation de biomasse des producteurs primaires souvent des micro-algues, à la base des réseaux trophiques. Le manteau neigeux en surface, par ces propriétés physiques et leurs évolutions temporelles, joue donc un rôle essentiel en impactant directement l’initiation et l’amplitude de la floraison phytoplanctonique printanière. Dans le cadre du réchauffement climatique actuel, les mutations que subit la banquise : amincissement, réduction de son extension estivale et variations des épaisseurs du manteau neigeux bouleversent d’ores et déjà la production primaire arctique à l’échelle globale et régionale.Cette thèse vise à mieux comprendre la contribution du manteau neigeux au transfert radiatif global de la banquise, afin de mieux estimer son impact sur la production primaire arctique. Elle s’appuie sur un jeu de données collecté lors de deux campagnes de mesures sur la banquise en période de fonte. Les propriétés physiques de la neige, SSA et densité, permettent une modélisation précise du transfert radiatif de la neige qui est validée, ensuite, par les propriétés optiques comprenant : albédo, profils verticaux d’éclairement dans le manteau neigeux et transmittance à travers la banquise.Au printemps, la neige marine, marquée par une importante hétérogénéité spatiale, évolue suivant quatre phases distinctes. La fonte, d’abord surfacique puis étendue à toute l’épaisseur du manteau, se caractérise par une baisse de la SSA de 25-60 m2kg-1 à moins de 3 m2kg-1 provoquant une diminution de l’albédo dans le proche infrarouge puis à toute longueur d’onde ainsi qu'une augmentation de l’éclairement transmis à la colonne d’eau. Cette période est chaotique, et marquée par une forte variabilité temporelle des propriétés optiques causées par la succession d’épisodes de fonte et de chutes de neige. Les propriétés physiques de la neige sont utilisées par un modèle de transfert radiatif afin de simuler les profils verticaux d'éclairement, l’albédo et la transmittance de la banquise. La comparaison entre ces simulations et les profils d’éclairement mesurés met en évidence la présence d’impuretés dans la neige dont leurs natures et leurs concentrations sont estimées. En moyenne, la neige échantillonnée contenait 600 ngg-1 de poussières minérales et 10 nng-1 de suies qui réduisaient par deux l’éclairement transmis à la colonne d’eau. Enfin, la modélisation de l’éclairement à toute profondeur de la banquise, représentée de manière innovante par des isolumes, est mise en relation avec l’évolution temporelle de la biomasse dans la glace. Il apparaît que la croissance des algues de glace est systématiquement corrélée avec une augmentation de l’éclairement, et ce, jusqu’à des niveaux d’intensité de l’ordre de 0.4 uEm-2s-2. Ces variations d’éclairement sont causées par le métamorphisme et la fonte de la neige en surface. / The Arctic ocean shows a very strong seasonality trough the permanent presence of sea ice whose extent varies from 6 to 15 millions km2. As an interface, sea ice limits ocean - atmosphere interactions and impacts the global energy budget by reflecting most of the short-wave incoming radiations. The snow cover, at the surface, is a key element contributing to the optical properties of sea ice. Snow enhances further the surface albedo and thus delays the onset of the ice melt. In addition, snow is the main responsible for the vertical light extinction in sea ice. However, after the polar night, this low light transmitted to the water column is a limiting factor for primary production at the base of the oceanic food web. The snow cover, through the temporal evolution of its physical properties, plays a key role controlling the magnitude and the timing of the phytoplanktonic bloom. In the actual global warming context, sea ice undergoes radical changes including summer extent reduction, thinning and shifts in snow thickness, all of which already alter Arctic primary production on a regional and global scale.This PhD thesis aims to better constrain the snow cover contributions to the radiative transfer of sea ice and its impact on Arctic primary production. It is based on a dataset collected during two sampling campaigns on landfast sea ice. Physical properties of snow such as snow specific surface area (SSA) and density allow a precise modeling of the radiative transfer which is then validated by optical measurements including albedo, transmittance through sea ice and vertical profiles of irradiance in the snow.During the melt season, marine snow which shows strong spatial heterogeneity evolves fol- lowing four distinctive phases. The melting, which first appears at the surface and gradually propagates to the entire snowpack, is characterized by a decrease in SSA from 25-60 m2kg-1 to less than 3 m2kg-1 resulting in a decrease in albedo and an increase in sea ice transmittance. This is a chaotic period, where optical properties show a very strong temporal variability induced by alternative episodes of surface melting and snowfalls. The physical properties of snow are used in a radiative transfer model in order to calculate albedo, transmittance through sea ice and vertical profiles of irradiance at all depths. The comparison between these simulations and measured vertical profiles of irradiance in snow highlights the presence of snow absorbing impurities which were subsequently qualitatively and quantitatively studied. In average, impurities were composed of 660 ngg-1 of mineral dust and 10 ngg-1 of black carbon. They were responsible for a two-fold reduction in light transmitted through sea ice. The light extinction, calculated at all depths in sea ice, and represented by isolums, was compared to the temporal evolution of ice algae biomass. The results show that every significant growth in ice algae population is related to an increase of light in the ice. These growths were observed even at very low light intensities of 0.4 uEm-2s-2. Light variations in the ice were linked by snow metamorphism and snow melting at the surface.
129

Propriedades vibracionais de nitretos do grupo III e de suas ligas / Vibrational properties of group-III nitrides and their alloys

Santos, Adriano Manoel dos 23 April 2004 (has links)
Os nitretos do grupo III (BN, AIN,Gan e InN) e suas ligas ternárias Al-GaN e InGaN proporcionam, recentemente, um extraordinário avanço na fabricação de dispositivos opto-eletrônicos operando na região do espectro correspondente ao verde-azul-UV e na produção de dispositivos eletrônicos de alta frequência, alta temperatura e alta potência. Estes materiais semicondutores de gap largo atraíram enorme atenção dos pesquisadores nos últimos anos. O objetivo desta tese é o estudo das propriedades vibracionais dos nitretos do grupo III referente tanto ao cristal perfeito, quanto ao cristal com defeito. Utilizamos como base a Teoria Clássica do Crital Harmônico e o Método das Funções de Green. Com a Teoria Clássica do Cristal Harmônico, juntamente com o Método do Valence Force Filed e o Método da Soma de Ewald, que permitem gerar a matriz dinâmica do sistema, determinamos o comportamento vibracional dos nitretos binários e das ligas ternárias. A utilização destes métodos permitiu a obtenção do espectro de fônons dos nitretos binários, e o estudo do comportamento dos modos ópticos em para as ligas ternárias. A partir da Função de Green do cristal perfeito e da Função de Green do cristal com defeito, obtivemos as frequências e os modos vibracionais localizados e ressonantes introduzidos pela impureza de C e As em GaN. A partir das densidades de estados do cristal perfeito e do cristal com defeito, calculamos a entropia de formação da vacância de N em GaN. Os resultados obtidos foram usados na interpretação de dados experimentais disponíveis na literatura, relativos às propriedades vibracionais dos nitretos na estrutura wurtzita, e na predição e análise de dados experimentais obtidos pelo grupo do Laboratório de Novos Materiais Semicondutores do Instituto de Física da USP para os nitretos zincblende. / The group-III nitrides (BN, AIN, GaN and InN) and their ternary alloys AlGaN and InGaN generated recently an extraordirlary progress in the production of optoelectronic devices operating in the green-blue-UV region of the spectrum, and in the production of electronic devices of high frequency, high temperature and high power. These wide gap semiconductor materials attracted enormous attention in the last years. The objective of this Thesis was to study the vibrational properties of the bulk III nitrides, without and with defects. To accomplish this study we used the Classic Theory of the Harmonic Crystal and the Method of the Green\'s Functions. With the Classic Theory of the Harmonic Crystal, together with the Valence Force Field Method and the Method of the Ewald\'s Sum, that allow to generate the dynamic matrix of the system, we determined the vibrational behavior of the binary nitrides and of the ternary alloys. The use of these methods allowed us to obtain the phonon spectra of the binary nitrides and to study the behavior of the optical modes at of the ternary alloys. Starting from the Green\'s Function of the perfect crystal and the Green\'s Function of the crystal with defect, we obtained the frequencies and the localized and resonant vibrational modes introduced by the C and As impurities in GaN. Starting from the densities of states of the perfect crystal and of the crystal with defect, we calculated the formation entropy of the N vacancy in GaN. The obtained results were used in the interpretation of experimental data related to the vibrational properties of the wurtzite nitrides available in the literature, and in the prediction and analysis of experimental results obtained for zincblende nitrides by the group of the New Semiconductors Materials Laboratory of t11c Physics Institute at USP.
130

Avaliação de métodos empregando a espectrometria de massas com plasma acoplado (ICP-MS) para determinação de impurezas elementares e especiação química de arsênio e mercúrio em fármacos e excipientes / Evaluation of methods using coupled plasma mass spectrometry (ICP-MS) for determination of elemental impurities and chemical speciation of arsenic and mercury in drugs and excipients

Aguiar, Giovanna de Fatima Moreno 13 September 2017 (has links)
Com o aumento das exigências regulatórias e estabelecimento de limites mais restritos para impurezas elementares em fármacos e excipientes usados em formulações farmacêuticas, ocorreu uma busca por técnicas analíticas capazes de quantificar elementos em níveis traço e assegurar a qualidade e a segurança dos medicamentos. A espectrometria de massas com plasma acoplado indutivamente (ICP-MS) é uma técnica multielementar, que apresenta alta sensibilidade e é empregada com eficiência na análise de elementos traço em diferentes matrizes. O ICP-MS, acoplado a um sistema separador como o cromatógrafo líquido de alta eficiência (HPLC), possibilita a especiação de elementos químicos, o que é importante, pois a toxicidade pode estar diretamente ligada à forma química do elemento, como ocorre para o Hg e As. Neste sentido, os objetivos deste trabalho foram desenvolver e validar um método de análise simples, rápido e com alta sensibilidade, para determinação de 15 impurezas elementares: As, Cd, Cr, Cu, Ni, Pb, V, Ir, Pd, Pt, Rh, Ru, Hg, Os e Mo, em diferentes fármacos e excipientes, em níveis que atendam aos novos critérios estabelecidos pelos órgãos regulatórios, avaliar a utilização da cela de reação dinâmica (DRC) para eliminação de interferências espectrais na determinação de As, Cr e V, realizar a especiação de As e Hg, e aplicar esta metodologia para análise de diversas amostras comprovando sua robustez, versatilidade e vantagens para utilização em rotina. Foram avaliadas cinco estratégias de preparo de amostra: digestão em micro-ondas sistema fechado e digestão em micro-ondas - sistema aberto, digestão em banho-maria, diluição direta em meio ácido e extração utilizando ponteira de ultrassom. Através de ensaios de recuperação e materiais de referência certificados, os melhores resultados (84 a 101%) foram obtidos com a digestão das amostras em sistema fechado de micro-ondas e extração por ponteira de ultrassom. Os limites de detecção variaram entre 0,001 ng g-1 (103Rh) e 0,083 ng g-1 (75As). Em seguida, a metodologia analítica foi empregada para determinação dos elementos em estudo em 74 amostras de fármacos e excipientes. O elemento mais frequentemente encontrado foi o Cu, seguido por Cr, Mo, Ni, Pd e V. Já os elementos químicos Ir, Pt, Os e Ru não foram detectados. Cabe destacar que as concentrações de Pd, Rh, As, Cd, Cr, Cu, Ni, V e Mo encontraram-se acima do limite preconizado pela farmacopeia americana em algumas amostras. A análise por especiação química de As mostrou que as amostras possuíam apenas as formas inorgânicas e mais tóxicas. Em relação ao Hg, apenas uma amostra apresentou níveis detectáveis deste elemento, mas a concentração estava abaixo do limite estabelecido pela farmacopeia americana. / Due to quality and safety reasons, regulatory requirements and establishment of more restricted limits for elemental impurities in drugs and excipients are increasing. These regulations promoted a search for simple and robust analytical techniques for quantification of trace elements. Inductively coupled plasma mass spectrometry (ICP-MS) is an attractive technique for this purpose, presenting multielement and high sensitivity capabilities. ICP-MS can be hyphenated to separation techniques such as high-performance liquid chromatography (HPLC), enabling chemical speciation analysis. Speciation analysis may reveal the chemical form of the element that may be more directly related to the toxicity. In this sense, the objectives of this work were to develop and validate a simple, fast and highly sensitive method for the determination of 15 elemental impurities: As, Cd, Cr, Cu, Ni, Pb, V, Ir, Pd, Rh, Ru, Hg, Os and Mo, in different drugs and excipients, at levels that meet the new criteria established by the regulatory agencies. We also evaluated the use of the dynamic reaction cell (DRC) to eliminate spectral interferences for As, Cr And V. Finally, for As and Hg, speciation methods were applied. All analysis were performed focusing on robustness, versatility and sample high-throughput. We tested five sample preparation strategies: closed microwave system digestion, microwave digestion - open system, water bath digestion, direct acid dilution and ultrasound probe extraction. Recovery studies in ordinary samples and reference certified materials were observed with the closed microwave digestion system and ultrasound probe extraction (84 and 101%). Detection limits ranged from 0.001 ng g-1 for 103Rh to 0.083 ng g-1 for 75As. The analytical methodology was then applied for the determination of the elements in study in 74 samples of drugs and excipients. The most frequently found element was Cu, followed by Cr, Mo, Ni, Pd and V. The chemical elements Ir, Pt, Os and Ru were not detected. It should be mention that the concentrations of Pd, Rh, As, Cd, Cr, Cu, Ni, V and Mo were above the limit recommended by the American pharmacopeia in some samples. Only inorganic arsenic (most toxic forms) was found in samples by applying speciation analysis. Regarding Hg, only one sample had detectable levels of this element, but the concentration was below the limit established by the American pharmacopeia

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