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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.
1

From lymph node embryogenesis to homeostasis : new insights into the functions of stromal RANKL (TNFSF11) / Etude de l'influence du TNFSF11 (RANKL) sur le développment et homéostasie des organes lymphoïdes secondaires

Cordeiro, Olga 07 December 2015 (has links)
RANKL et RANK sont membres de la superfamille des TNF et de la superfamille des TNF-récepteurs, respectivement. Ils sont connus pour jouer un rôle important dans la régulation de la masse osseuse et dans le développement et la fonction du système immunitaire. Cependant des questions restent. Nous avons utilisé des souris génétiquement modifiées pour répondre à certaines de ces questions, en particulier en utilisant une souris dont les cellules stromales réticulaires marginales manquent RANKL dans les ganglions lymphatiques. Les résultats obtenus lors de cette thèse fournissent de nouvelles informations importantes sur l'impact positif de RANKL stromal sur les macrophages des ganglions lymphatiques concomitantes avec une fonction des cellules B amélioré et une pathogénicité virale réduit. Nous avons constaté que RANKL stromal régule l'expression de lymphotoxine et CXCL13, deux molécules clés de l'homéostasie des cellules B et de l'intégrité cellulaire des organes lymphoïdes secondaires. L’activité du RANKL semble suivre une hiérarchie temporelle sur lymphotoxine/TNFα, vu que le phénotype causé par le déficit en RANKL a une pénétrance augmenté avec l'âge. De plus, nous démontrons que RANKL active les cellules endotheliales lymphatiques des ganglions lymphatiques et on a trouvé que l'intégrine ITGA2b est un nouvel indicateur pour les cellules endotheliales lymphatiques activés. Ainsi, avec MAdCAM-1, ITGA2b sert comme un nouveau marqueur pour les cellules endothéliales lymphatiques qui sont constitutivement activés par le RANKL stromal. Au total, les données confirment l'importance de RANKL pour l'homéostasie des ganglions lymphatiques et dévoile les mécanismes ci-inconnus des fonctions de RANKL. À la lumière de cela et le fait que RANKL est sensible aux hormones féminines, nous avons étudié le rôle de RANKL dans le syndrome de Sjögren, une maladie inflammatoire chronique des glandes salivaires et lacrymales avec une forte polarisation de sexe féminin. Nous apportons la preuve que la neutralisation du RANKL réduit la taille des organes lymphoïdes tertiaire. En perspective, une éventuelle diaphonie entre les cellules endothéliales lymphatiques et les macrophages ou les cellules réticulaires marginales reste à clarifier. En outre, d'autres travaux sont nécessaires pour élucider le mécanisme par lequel RANKL stimule les maladies inflammatoires chroniques présentant des structures lymphoïdes tertiaires, afin de faire RANKL une nouvelle cible pour la thérapie. / RANKL and RANK are members of the TNF-superfamily and TNF-receptor superfamily, respectively. They are known to play an important role in the regulation of bone mass and in the development and the function of the immune system. However questions still remain. We have used genetically modified mice to address some of these questions, in particular by using a mouse whose lymph node marginal reticular stromal cells lack RANKL. The results obtained during this PhD provide important new insights into the positive impact of stromal RANKL on lymph node macrophages concomitant with enhanced B cell function and reduced viral pathogenicity. We found that stromal RANKL regulates lymphotoxin and CXCL13 expression, two key molecules for B cell homeostasis and secondarylymphoid organ cellular integrity. RANKL activity seems to follow a temporal hierarchy over lymphotoxin/TNFα, as the phenotype caused by stromal RANKL-deficiency has increased penetrance with age. Furthermore, we demonstrate that RANKL activates lymph node lymphatic endothelial cells and found that the integrin ITGA2b is a new indicator for activated lymphatic endothelial cells. Thus, together with MAdCAM-1, ITGA2b serves as a novel marker for those lymphatic endothelial cells that are constitutively activated by stromal RANKL. Altogether, the data reinforce the importance of RANKL for the lymph node homeostasis and uncover here to unknown mechanisms of RANKL functions.In light of this and the fact that RANKL is responsive to female hormones, we studied the role of RANKL in the Sjögrens syndrome, a chronic inflammatory disease of salivary and lacrimal glands with a strong female sex bias. We provide evidence that RANKL neutralization reduces tertiary lymphoid organ size. On the perspective side, a possible cross talk between lymph node lymphatic endothelial cells and macrophages or marginal reticular cells remains to be clarified.Furthermore, further work is required to elucidate the mechanism by which RANKL stimulates chronic inflammatory diseases presenting tertiary lymphoid structures, in order to make RANKL a new target for therapy.
2

GS-MBE Growth of Ga(ln)AsN Nitrides for Long Wavelength Semiconductor Lasers

Yuan, Lixiang January 2000 (has links)
Quaternary GalnAsN containing a small amount of nitrogen (<2%) is a potentially promising material for realizing long-wavelength emission lasers for applications in optical communication systems. Such devices should have better high-temperature characteristics than conventional InGaAsP lasers due to an increase of the conduction band offset. In this thesis, the GS-MBE growth of quaternary GalnAsN and ternary GaAsN was carried out. Active N was produced by passing high purity nitrogen gas into either an RF or an ECR plasma source. The RF plasma source was found to produce better quality nitrides. Characterization techniques such as photoluminescence, X-ray diffraction, TEM, SIMS, and Hall effect measurements were used to characterize thick layers (e.g. 1 pm) and quantum wells of these nitride materials. The concentration of N incorporated into GalnAs and GaAs is very dependent on growth conditions and plasma conditions. The incorporation of a small amount of N into compressively strained InGaAs reduces the strain and produces a red-shift of photoluminescence peak. However, compared to N-free InGaAs materials, the optical quality is dramatically degraded yielding reduced photoluminescence intensity and a broadened FWHM of the PL peak. Hall effect measurements on un-doped, Si-doped, Bedoped thick GalnAsN layers indicate the presence of a high concentration of electron and hole traps. The results of SIMS suggest that impurity H might be responsible for the deep level defects formed. However, the nature of the defects is currently unknown. From TEM observations and comparison to samples grown with a He-plasma instead of a Nplasma, spinodal decomposition and ion-induced damage in GalnAsN may produce the reduced quality of materials, but these are not the major reasons responsible for the dramatic degradation of optical quality. Thermal annealing was found to be an effective method for significantly improving the optical quality of GalnAsN with a low N concentration. Optimum annealing conditions were obtained. Hall effect measurements on annealed samples indicate that electron and hole traps are reduced but still present after anneal. / Thesis / Master of Engineering (ME)
3

ERP LN implementation in an industrial context at ID6-Consultoria e Gestão

Bessa, Mariana Palhares da Cunha January 2011 (has links)
Tese de mestrado integrado. Engenharia Industrial e Gestão. Universidade do Porto. Faculdade de Engenharia. 2011
4

Simula??o de digest?o in vitro acoplada a modelos de transporte g?strico e intestinal para estimar a capta??o e absor??o de antocianinas em frutos / Simulation of in vitro digestion coupled to gastric and intestinal transport models to estimate the uptake and absorption of anthocyanins in fruits

PEIXOTO, Fernanda Marques 08 December 2016 (has links)
Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-09-05T20:11:17Z No. of bitstreams: 1 2016 - Fernanda Marques Peixoto.pdf: 14003225 bytes, checksum: 89c95a9ad22b1e74cdf2bda273665230 (MD5) / Made available in DSpace on 2017-09-05T20:11:17Z (GMT). No. of bitstreams: 1 2016 - Fernanda Marques Peixoto.pdf: 14003225 bytes, checksum: 89c95a9ad22b1e74cdf2bda273665230 (MD5) Previous issue date: 2016-12-08 / A lot of interest in the consumption of anthocyanins increased after the association of their intake and reduced risk of chronic diseases. Despite of in vitro evidences of anthocyanins benefits to health, there is still a gap in the knowledge of the mechanisms of absorption of anthocyanins by the human body. It is known that concentration of food anthocyanins doesn't reflect the amount of these compounds which are absorbed, metabolized, distributed and biologically active in humans. Some in vitro models have been developed to evaluate the steps of cell release and transport ( uptake) of these compounds from food. The objective of this study was to evaluate the in vitro absorption of food anthocyanins using the in vitro digestion followed by uptake and transport in Caco-2 human intestinal cell line and MKN-28 human gastric cell line. Initially, anthocyanins bioaccessibility of diverse fruits was evaluated in order to select the better sources for transport assays. The bioaccessibility assays were performed using an in vitro digestion model, which mimics the human oral, gastric and intestinal stages. Quantification and characterization of anthocyanins profile were performed by high-performance liquid chromatography (HPLC) with Thermo Scientific? C1s 2.4 (4.6 x 10mm) column. After selection of the most promising fruits, the bioaccessibility tests were followed by transport assays. To assess gastric absorption, the product from gastric digestion was applied on the MKN-28 cell monolayer, which was obtained after 7 days of culture of 2.5 x 10^5 MKN-28 cells seeded in RPMI culture media in transwell? plates. The permeate was collected after 30, 60, 120 andl80 minutes oftransport. For evaluation of intestinal absorption after digestion, the digesta from the intestinal phase was applied on the Caco-2 cell monolayer, which was obtained after 21 days of culture of 2.5 x 105 Caco-2 cells seeded in DMEM culture media in TRANSWELL? plates. The permeate was collected after 30, 60 and 120 minutes of transport. All analyses were made by forming CLUE / photodiode array detector (Thermo? Scientific) at 520nm. Peel powder from jabuticaba, jambo and Jamel?o were the most promising sources. The bioaccessibility of anthocyanins after gastric digestion was 13% for jabuticaba, 45 % for jambo and 65 % for jamel?o. In addition, the intestinal bioaccessibility was 1 O % for jabuticaba, 15 % for jambo and 45 % for jamel?o. The transport assay with the MKN-28 gastric cell line, revealed 19.7%, 9.7 % and 14.1 % of transport efficiency, respectively, for jambo, jabuticaba and jamel?o digestion products. While Caco-2 intestinal cell model showed 0.8 %, 0.2 % and 0.3 % oftransport efficiency, respectively, for jambo, jabuticaba and jamel?o. These results suggest food anthocyanins are preferentially absorbed by the human gastric mucosa and to a lesser extent by the human intestinal epithelium. / O interesse pelo consumo das antocianinas aumentou ap?s o surgimento da rela??o entre o seu consumo e a redu??o do risco de doen?as cr?nicas. Apesar das evid?ncias in vitro quanto a esses beneficios ? sa?de, ainda h? uma lacuna que permanece sob investiga??o: o mecanismo de absor??o das antocianinas pelo organismo humano. Sabe-se que a quantidade desses compostos, nos alimentos, n?o reflete a quantidade absorvida, metabolizada, distribu?da e biologicamente ativa em humanos. Alguns modelos in vitro t?m sido desenvolvidos para avaliar as etapas de digest?o e transporte celular (absor??o) de compostos dos alimentos. Assim, o objetivo deste trabalho foi avaliar o transporte in vitro de antocianinas em alimentos utilizando modelos de digest?o in vitro seguido do transporte em c?lulas intestinais Caco-2 e c?lulas g?stricas MKN-28. Na 1? etapa, oito frutos foram analisados quanto aos valores de bioacessibilidade (BCSS) fornecidos pelas antocianinas presentes, para posterior sele??o para os ensaios de transporte. Os ensaios de BCSS foram realizados com um modelo de digest?o in vitro, para simula??o das fases oral, g?strica e intestinal humana. A quantifica??o e determina??o do perfil de antocianinas foram realizadas por Cromatografia l?quida de alta efici?ncia (CLAE), com coluna Thermo? Scientific C1s 2,4 (4,6 x 100mm). Na 2? etapa, realizou-se os ensaios de BCSS, anteriormente aos ensaios de transporte, nos frutos potencialmente mais promissores. Para a avalia??o do transporte g?strico, na sequ?ncia, o digerido g?strico foi aplicado sobre a monocamada de c?lulas MKN-28, com 2,5 x 10^5 c?lulas, em meio RPMI, em placa transwell? e, ap?s 7 dias de cultivo, o permeado foi coletado nos tempos 30, 60, 120, 180 minutos. Para o transporte intestinal, sequencial, o digerido intestinal foi aplicado sobre a monocamada celular Caco-2, com 2,5 x 105 c?lulas, em meio DMEM, em placas transwell? e, ap?s 21 dias de cultivo, o permeado foi coletado nos tempos 30, 60 e 120 minutos de transporte. Todas as an?lises foram realizadas por CLUE/detector de arranjo fotodiodo (Thermo? Scientific), a 520 nm. Os p?s da casca da jabuticaba, jambo e jamel?o foram as matrizes mais promissoras. A BCSS das antocianinas, ap?s a digest?o g?strica, foi de 13 % parajabuticaba, 45 % parajambo e 65 % parajamel?o, enquanto a BCSS intestinal foi de 10% para jabuticaba, 15 % para jambo e 45 % para jamel?o. Os ensaios de transporte (ET) com os modelos de c?lula MKN-28 resultaram em 19,7; 9,7 e 14,1 % de ET, respectivamente, para os p?s do jambo, jabuticaba, e jamel?o, enquanto que o modelo Caco-2, resultaram em 0,8, 0,2 e 0,3 % de ET, respectivamente. Estes resultados sugerem que as antocianinas s?o preferencialmente absorvidas pela mucosa g?strica.
5

Comparing CAPM and APT in the Chinese Stock Market

Zhang, Lina, Li, Qian January 2012 (has links)
As the stock market plays an important role in the global economy and Chinese economy become progressively significant part of the world economy, we are interested in the Chinese stock market. After we compared the methods on the stock market, we choose to use the CAPM and the APT model on Chinese stock market. As a lot papers study on the Main Board of Chinese stock market, we pay our attention on the SME Board and the ChiNext Board of Chinese stock market. We put the samples from the SME Board and the ChiNext Board into the regression models which are based on the CAPM and the APT model, and then we can use the regression models to forecast the long returns. Comparing the forecast ln returns with the true ln returns, we may find that the CAMP or the APT model can forecast better on the SME Board and the ChiNext Board. The systematic risk is the only factor we put the regression model based on the CAPM. For the regression model based on the APT model, we use three factors which are the systematic risk, daily exchange volume and the volatility. Our results show that the APT model can explain factors better than the CAPM for the samples from the SME Board and the ChiNext Board. On the other hand, we could not find evidence that the APT Model can forecast better than the CAPM for the SME Board and the ChiNext Board.
6

Output Feedback Control of Nonlinear Systems with Unstabilizable/Undetectable Linearization

Yang, Bo January 2006 (has links)
No description available.
7

NON-LINEAR MAPS BETWEEN SUBSETS OF BANACH SPACES

Sbeih, Reema 24 September 2009 (has links)
No description available.
8

Impact of Li non-stoichiometry on the performance of acoustic devices on LiTaO3 and LiNbO3 single crystals / Effet de nonstoechiométrie en Li sur la performance des dispositifs à ondes élastiques à base de monocristaux de LiTaO3 et LiNbO3

Gonzalez, Minerva 19 July 2016 (has links)
Les technologies de filtres, résonateurs, oscillateurs et capteurs sont des éléments essentiels dans lesindustries des télécommunications, automobile, militaire, médical, etc. Les monocristaux de LiTaO3 (LT) etLiNbO3 (LN) sont les matériaux les plus utilisés pour la fabrication de filtres de radiofréquence à ondesélastiques des téléphones portables, car ils possèdent un facteur de couplage électromécanique (K2) élevé.Cependant, ils présentent une problématique liée à la variation de la fréquence de fonctionnement avec latempérature (CTF), dont la valeur est environ de -40 à -95 ppm/°C. D’autre part, il a été démontré dans lalittérature que les propriétés de LT et LN changent avec la non-stoechiométrie du Li.L’objectif de cette thèse a été l’étude de l’effet de la concentration en Li2O sur la performance desdispositifs acoustiques à ondes élastiques de surface, utilisant comme substrat piézoélectrique desmonocristaux de LT coupe YXl/42 (42 RY-LT) et LN coupe YXl/128 (128 RY-LT). Cette étude vise àl’amélioration du CTF sans la dégradation d’autres propriétés (K2 et pertes d’insertion) dans le cas du 42 RYLTet la stabilité de dispositifs utilisés à haute densité de puissance dans le cas du 128 RY-LN. Tout d’abord,nous avons préparé des monocristaux de LT et LN avec différente concentration en Li2O :48.5-50 mol%, enutilisant la méthode d’équilibration par transport en phase vapeur (VTE). Ensuite, nous avons fabriqué etcaractérisé des dispositifs à ondes élastiques de volume et de surface à base de LT et LN, traités par VTE, afind’étudier l’effet de la non-stoechiométrie de Li et l’effet des domaines ferroélectriques sur leur performance. / The filter technologies, resonators, oscillators and sensors are essential elements fortelecommunications, automotive, military, medical industries. The most of radio frequency surface acousticwave (RF-SAW) filters, present in mobile phones, are based in LiNbO3 (LN) and LiTaO3 (LT) single crystalsbecause they have high electromechanical coupling factor (K2). However, these materials have a problemrelated to the variation of the operating frequency with temperature (TCF), whose value is about -40 to -95ppm / ° C. On the other hand, it has been previously shown in the literature that the physical and structuralproperties of LT and LN change with Li non-stoichiometry, including elastic properties.The aim of this work was the investigation of the impact of Li2O concentration on the performance ofSAW devices based on YXl/42 (42 RY-LT) and YXl/128 (128 RY-LN) single crystals. In the case of 42 RY-LT,we focused in the reduction of TCF without the degradation of other properties (K2 and insertion losses) andin the case of 128 RY-LN crystals we focused in the stability of devices at high power densities. First, singlecrystals of LT and LN with different Li2O concentration: 48.5-50 ml% were prepared, by using the VaporTransport Equilibration (VTE) method. Afterwards, SAW and bulk acoustic wave (BAW) devices based on LTand LN VTE treated crystals, were fabricated and characterized, in order to study the effect of Li nonstoichiometryand the effect of ferroelectric domains on the performance of devices.
9

Il faut et on peut construire des systèmes de commerce électronique à interface en langue naturelle restreints (et multilingues) en utilisant des méthodes orientées vers les sous-langages et le contenu

Daoud, Daoud 20 September 2006 (has links) (PDF)
Aucun système de commerce électronique opérationnel n'est capable de traiter en ligne des requêtes d'utilisateurs exprimées en langue naturelle spontanée. Certains systèmes évitent le problème difficile du développement et du support d'une interface en langue naturelle en simplifiant le type d'interaction de l'utilisateur, par l'utilisation de formulaires à remplir ou d'un langage naturel contrôlé. D'autres systèmes ont cherché mais échoué à offrir une interface en langue naturelle spontanée, parce qu'ils utilisaient des techniques de TALN inadaptées.<br />Le but de cette thèse est de montrer qu'il est nécessaire et possible de construrie des systèmes de commerce électronique à interface en langue naturelle restreints (et multilingues) en utilisant des méthodes orientées vers les sous-langages et le contenu. L'analyse du sous-langage et l'intégration de méthodes orientées vers le contenu augmentent en effet l'exactitude et la robustesse du traitement de façon décisive.<br />Pour vérifier cela, nous avons construit un système expérimental, CATS, comme "preuve de concept". C'est un système de petites annonces en langue naturelle (actuellement l'arabe) basé sur les SMS destiné à mettre en contact des personnes désirant vendre ou acheter des voitures d'occasion, de l'immobilier, etc. Pour analyser le sous-langage très particulier de ces petites annonces en SMS, nous sommes partis d'un corpus web de messages de ce type (mais pas en SMS) pour construire un système de base couvrant l'occasion automobile et l'immobilier en Jordanie. Ce premier système a été déployé, ce qui nous a permis de collecter un corpus réel de SMS "spontanés" dans ces domaines, et d'ajuster finement CATS à ces domaines.<br />Le traitement sémantique étant nécessaire, nous avons défini CRL-cats, un langage de représentation du contenu très simple, mais suffisant pour exprimer le contenu de telles petites annonces. Nous avons écrit l'extracteur de contenu dans le langage spécialisé pour la programmation linguisitique EnCo, dans lequel nous avions déjà écrit le premier "enconvertisseur" arabe-UNL. Ce langage étant d'assez bas niveau, et n'offant aucune aide à la programmation modulaire, nous avons développé une méthodologie qui facilite l'écriture d'enconvertisseurs aussi bien que d'extracteurs de contenu, et permet un codage systématique et efficace.<br />La génération des réponses est basée sur une reconnaissance de patrons sémantiques, différents selon qu'il s'agit d'une annonce de recherche ("look for") ou d'offre ("sell"), et sur un mécanisme de raisonnement, de sorte qu'on peut traiter les situations "sans réponse". À la différence d'autres systèmes expérimentaux, CATS a été conçu dès le départ pour être un "système de production". Il est actuellement déployé en Jordanie par le plus grand opérateur de téléphonie mobile (Fastlink), qui lui a d'abord fait passer des tests sévères. Le test de l'extracteur de contenu sur du texte réel et bruité a donné une f-mesure de 90%. Le temps de réponse moyen est d'environ 10 à 30 secondes à une heure de pointe (10 annonces par minute).
10

Structures, Thermodynamics and Phase Relations in Selected Oxide Systems

Lwin, Kay Thi 10 1900 (has links)
Understanding of the interrelationship between structure, thermodynamic properties and phase diagrams is very useful for rationalizing the behavior of materials and development of predictive models, which can be used to optimize the composition of materials and their fabrication processes. The properties of materials are governed by its electronic and crystallographic structure. Chemical bonding determines the electronic structure of materials. Furthermore, the electronic structure plays a predominant role in determining the physical, electrical, magnetic, thermal and optical properties of materials. Crystal structure also influences most properties of materials. Since changes in thermodynamic variables such as temperature, pressure, and composition dramatically alter the physical properties of materials and its structure, it is desirable to study the thermodynamic stability of materials in conjunction with phase relations. Phase diagrams can indicate the ranges of pressure, temperature and chemical composition where specific phases and mixtures of phases are stable. If the Gibbs energies of all the phases involved are known, phase diagram can be computed using Gibbs energy minimization algorithms. In recent times, one of the important uses of thermodynamics in materials science has been in the computation of phase diagrams. To materials scientists phase diagrams are like maps to travelers. They guide the path through the composition space to find phases, fulfilling specific materials performance requirements. As phase diagrams are the graphic representations of minimizations of Gibbs energy under given constraints, computational thermodynamics significantly expands our capability to walk in the multi-component space of engineering materials. High-temperature phase-equilibrium studies, thermodynamics and materials processing have had a close relationship over a number of decades. Successful utilization of ceramic materials under different environmental conditions at high temperatures requires accurate thermodynamic data. Focus of the present investigation is to obtain correct phase relations and accurate thermodynamic data in selected technologically important ceramic oxide systems in which the data are either not available or are inconsistent. Based on the experimental data, different types of phase diagrams are computed for the systems of contemporary relevance. After a brief introduction, Chapter 1 discusses the brief overview of the experimental techniques available for determining the phase relations and thermodynamic properties at high temperatures and the methods used in this study. The chapter reviews the possible sources of errors in experimental techniques and tests for correct functioning. In Chapter 2, systematic studies on high-temperature phase equilibria and thermodynamic properties of compounds in the ternary systems Ln-Pd-O (Ln = La, Pr, Eu, Gd, Tb, Dy, Ho and Er) are presented. Some of the ternary oxides on the Ln-Pd-O systems have potential application in catalysis and electrochemistry. To optimize the parameters for the synthesis and to understand the behavior of the catalysts, it is useful to have information on the thermodynamic stability domain of each compound. Quantitative information on the stability of the ternary oxides is also useful for assessing the interaction of metal Pd with ceramic compounds containing rare-earth elements under different environments. Furthermore, the thermodynamic data are beneficial for the design of processes for the recovery of rare earth and precious metals from scrap. There is very little thermodynamic and phase diagram information on the Ln-Pd-O systems. Isothermal sections of phase diagram for the ternary system La-Pd-O at 1200 K and for the systems Ln-Pd-O (Ln = Pr, Eu, Gd, Tb, Dy, Ho and Er) at 1223 K, were established by the isothermal equilibration technique at high temperatures. Phases were identified after quenching by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive X-ray spectroscopy (EDS). Based on the phase relations, the thermodynamic properties of ternary interoxide compounds were determined by the solid-state galvanic cell technique over a range of temperature between 925 - 1400 K. An advanced version of the solid-state cell incorporating a buffer electrode was used for high temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. These novel features enhanced the accuracy of thermodynamic data. From electrochemical measurements, the standard enthalpies of formation of these oxides from elements and their standard entropies at 298.15 K were also evaluated. The variation of the lattice parameters and unit cell volume as a function of rare earth atomic number for the three ternary compounds Ln4PdO7, Ln2PdO4 (Ln = La, Pr, Nd, Sm, Eu, Gd) and Ln2Pd2O5 (Ln = La to Er) are discussed. The systematic variations of thermodynamic properties of all the ternary compounds as a function of rare earth atomic number are presented and correlated with structural features. Thermodynamic and structural parameters of uninvestigated Ln-Pd-O systems (Ln = Ce, Pm) can be obtained by interpolation. Based on the thermodynamic information obtained in this study and auxiliary data on binary compounds available in the literature, different types of phase diagrams, isothermal oxygen potential diagrams, isobaric phase diagrams, isothermal two dimensional and three-dimensional chemical potential diagrams for the systems Ln-Pd-O (Ln = La, Pr, Eu, Gd, Tb, Dy, Ho and Er) are constructed. Chapter 3 contains the studies on partial phase diagrams of the systems M-Ru-O (M = Ca and Sr) at 1300 K and determination of Gibbs energies of formation of calcium and stronsium ruthenates in the temperature range from 925 to 1350 K using solid-state cells with yttria-stabilized zirconia as the electrolyte and Ru + RuO2 as the reference electrode. Gibbs energies, enthalpies and entropies of formation of calcium and strontium ruthenates from their component binary oxides were deduced. The standard enthalpies of formation of these oxides from elements and their standard entropies at 298.15 K were also evaluated. Based on the thermodynamic data obtained in this study and auxiliary information from the literature, the three dimensional representation of oxygen potential diagram for the M-Ru-O systems (M = Ca and Sr) as a function of composition and temperature are computed. The purpose of this chapter is to determine the thermodynamic stability of alkaline earth metal ruthenates in the perovskite related layered system Mn+1RunO3n+1 (n = 1, 2, and ¥ for Ca-Ru-O system and n = 1, 2, 3 and µ for Sr-Ru-O system) since these calcium and stronsium ruthenates have interesting magnetic and electronic device applications. Moreover, there is no literature available for thermodynamic properties on first and second members of the Ruddelsdon-Popper (R-P) series in Ca-Ru-O system, Ca2RuO4, Ca3Ru2O7 and third member of R-P series in Sr-Ru-O system, Sr4Ru3O10. Some of the available literature information on thermodynamic properties for other compounds of R-P series in Mn+1RunO3n+1 (M = Ca, Sr) are found to be based on incorrect assumptions and erroneous calculation. Thus, this chapter provides the complete thermodynamic information for all the electronically and magnetically applicable alkaline earth metal ruthenates for optimizing the deposition condition in device fabrications. Chapter 4 gives the structure-properties correlations of 2-3 spinel compounds and spinel-corundum equilibria for the system NiO-Al2O3-Cr2O3 at 1373 K. Nickel, aluminum and chromium are important base-constituent elements of high-temperature oxidation-resistant alloys. A spinel phase is usually found in the protective scale formed on the surface of the alloys. There is no thermodynamic data on spinel solid solution NiAl2O4-NiCr2O4. Thus, the phase relations and mixing properties of the spinel solid solution have been determined in this chapter. The inter-crystalline ion-exchange equilibrium between NiAl2+2xO4+3x-NiCr2O4 spinel solid solution and Al2O3-Cr2O3 solid solution with corundum structure in pseudo-ternary system NiO-Al2O3-Cr2O3 have been determined by the conventional tie-line rotation method at 1373 K. The nonstoichiometry of NiAl2+2xO4+3x has been taken into consideration. Lattice parameters were used to obtain the compositions of the corundum and spinel solid solutions at equilibrium. Formation of homogeneous solid solutions and attainment of equilibrium were confirmed by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). From the experimental tie-line information and thermodynamic data on Al2O3-Cr2O3 solid solution available in the literature, the activities in the spinel solid solution were derived by using a modified Gibbs-Duhem integration technique. Gibbs energy of mixing of the spinel solid solution has been calculated from the derived activity data. Since high temperature data generation is expensive and time consuming, it is useful to develop models, which relate thermodynamic properties to electronic and crystallographic structure, leading to predictive modeling of mixing properties. By comparing the results from models with experimental information, one can evolve methodologies for the prediction of the properties of uninvestigated system. A model can be used to discriminate among conflicting experimental data and extrapolate the data into regions where direct measurements are lacking or difficult to perform. In this chapter, a model approach has also been considered to analyze the activity-composition relationship in the NiAl2O4-NiCr2O4 spinel solid solution in terms of the intra-crystalline exchange of cations between the tetrahedral and octahedral sites of the spinel structure governed by site preference energies of the cations. Since Ni2+ and Cr3+ ion in tetrahedral coordination exhibits Jahn-Teller distortion, an entropy corresponding to randomization of the distortion in the cubic phase has been incorporated in the cation distribution model. The thermodynamic mixing properties of stoichiometric spinel solid solution NiAl2O4-NiCr2O4 in terms of one mole of mixing species were computed at 1373 K. The strain energy caused by size mismatch was added as a separate term to the Gibbs energy of mixing using empirical relationship between enthalpy of mixing for a pair of ions and the difference in their ionic volumes. Madelung constant and electrostatic contribution of energy of mixing of the spinel solid solution have also been computed. Comparison of Gibbs energy of mixing calculated using the cation mixing model for the stoichiometric spinel solid solution NiAl2O4-NiCr2O4 with that of the experimental tie-line data for nonstoichiometric spinel solid solution NiAl2+2xO4+3x-NiCr2O4 were included in this chapter. The thermodynamic mixing properties obtained in this study would be helpful in understanding the formation of complex spinel protective layers on alloys containing nickel, aluminium and chromium in high-temperature applications. The summary of the important finding and the conclusions arrived at on the basis of results obtained from the present investigations are presented in Chapter 5.

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