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Minimality, input-output equivalence and identifiability of LPV systems in state-space and linear fractional representations / Minimalité, équivalence entrée-sortie et identifiabilité des systèmes LPV sous forme d’état et sous forme de représentations linéaires fractionairesAlkhoury, Ziad 09 November 2017 (has links)
Dans cette thèse, plusieurs concepts importants liés à la théorie de la réalisation des modèles linéaires à paramètres variants (LPV) sont étudiés.Tout d’abord, nous abordons le problème de l’identifiabilité des modèles LPV affines (ALPV). Une nouvelle condition suffisante et nécessaire est introduite afin de garantir l’identifiabilité structurelle pour les paramétrages ALPV. L’identifiabilité de cette classe de paramétrages est liée à l’absence d’isomorphismes liant deux représentations d’état LPV lorsque deux modèles LPV correspondant à différentes valeurs des variables de séquencement sont considérés. Nous présentons ainsi une condition suffisante et nécessaire pour l’identifiabilité structurelle locale, et une condition suffisante pour l’identifiabilité structurelle (globale) qui sont toutes deux fonction du rang d’une matrice définie par l’utilisateur. Ces dernières conditions permettent la vérification de l’identifiabilité structurelle des modèles ALPV.Ensuite, étant donné que les techniques d’identification dites locales sont parfois inévitables, nous fournissons une expression analytique de la borne supérieure de l’erreur de comportements entrées-sorties de deux modèles LPV équivalents localement. Cette erreur se révèle être une fonction de (i) la vitesse de changement du signal de séquencement et (ii) l’écart entre les bases cohérentes de deux modèles LPV. En particulier, la différence entre les sorties des deux modèles peut être arbitrairement réduite en choisissant un signal de séquencement qui varie assez lentement.Enfin, nous présentons et étudions des propriétés importantes de la transformation des représentations d’état ALPV en Représentations Linéaires Fractionnelles (LFR). Plus précisément, nous montrons que (i) les représentations ALPV minimales conduisent à des LFR minimales, et vice versa, (ii) le comportement entrée-sortie de la représentation ALPV détermine de manière unique le comportement entrée-sortie de la LFR résultante, (iii) les modèles ALPV structurellement identifiables fournissent des LFRs structurellement identifiables et vice versa. Nous caractérisons ensuite les LFRs qui correspondent á des modèles ALPV équivalents basés sur leurs applications entrées-sorties. Comme illustré tout au long du manuscrit, ces résultats ont des conséquences importantes pour l’identification et la commande des systèmes LPV. / In this thesis, important concepts related to the identification of Linear Parameter-Varying (LPV) systems are studied.First, we tackle the problem of identifiability of Affine-LPV (ALPV) state-space parametrizations. A new sufficient and necessary condition is introduced in order to guarantee the structural identifiability for ALPV parameterizations. The identifiability of this class of parameterizations is related to the lack of state-space isomorphisms between any two models corresponding to different scheduling parameter values. In addition, we present a sufficient and necessary condition for local structural identifiability, and a sufficient condition for (global) structural identifiability which are both based on the rank of a model-based matrix. These latter conditions allow systematic verification of structural identifiability of ALPV models. Moreover, since local identification techniques are inevitable in certain applications, it is thus a priority to study the discrepancy between different LPV models obtained using different local techniques. We provide an analytic error bound on the difference between the input-output behaviors of any two LPV models which are frozen equivalent. This error bound turns out to be a function of both (i) the speed of the change of the scheduling signal and (ii) the discrepancy between the coherent bases of the two LPV models. In particular, the difference between the outputs of the two models can be made arbitrarily small by choosing a scheduling signal which changes slowly enough.Finally, we introduce and study important properties of the transformation of ALPV statespace representations into Linear Fractional Representations (LFRs). More precisely, we show that (i) state minimal ALPV representations yield minimal LFRs, and vice versa, (ii) the inputoutput behavior of the ALPV representation determines uniquely the input-output behavior of theresulting LFR, (iii) structurally identifiable ALPV models yield structurally identifiable LFRs, and vice versa. We then characterize LFRs which correspond to equivalent ALPV models based on their input-output maps. As illustrated all along the manuscript, these results have important consequences for identification and control of LPV systems.
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Síntese e caracterização de filmes finos do sistema Y2O3-Er2O3-Al2O3-B2O3 para aplicação como amplificadores ópticos planares. / Thin films preparation and characterization of the Y2O3-Er2O3-Al2O3-B2O3.Maia, Lauro June Queiroz 18 October 2006 (has links)
Esse trabalho de tese descreve a síntese e a caracterização de materiais amorfos e cristalinos na forma de pó e de filmes finos pertencentes ao sistema Er2O3-Y2O3-Al2O3-B2O3. O principal objetivo do trabalho foi o de obter filmes finos amorfos contendo íons Er3+ próximo à composição YAI3(BO3)4 (YAB), visando sua aplicação como amplificador em dispositivos ópticos integrados. Na síntese das amostras foi empregado o método dos precursores poliméricos e o método sol-gel. Uma vez estabelecida às condições de síntese das resinas e de sóis estáveis, diferentes parâmetros foram otimizados visando à deposição de filmes relativamente espessos e amorfos. As propriedades térmicas, estruturais e ópticas de amostras cristalinas ou amorfas, na forma de pó e na forma de filmes finos, foram caracterizadas através das técnicas de análise termogravimétrica, calorimetria exploratória diferencial, difração de raios X, espectroscopia vibracional na região do infravermelho com transformada de Fourier, espectroscopia Raman e microscopia eletrônica de varredura de alta resolução, microscopia de força atômica, espectroscopia \"m-line\", medidas de espectros de luminescência. Baseado na análise térmica e estrutural das amostras na forma de pó, foi possível realizar a síntese de amostras na forma de filmes finos de composição Y1-xErxAl3(BO3)4 que apresentaram características estruturais, microestruturais e ópticas adequadas à aplicação desejada. Através do estudo das propriedades térmicas e estruturais, foi observado que as amostras preparadas através do método dos precursores poliméricos e do método sol-gel apresentam respectivamente uma temperatura de transição vítrea (Tg) à 723 °C e à 746 °C e uma temperatura de cristalização (Tc) à 814 °C e à 830°C. O tratamento térmico à aproximadamente 1150 °C da amostra amorfa na forma de pó de composição Y0,9Er0,1Al3(BO3)4 contendo boro em excesso levou a obtenção de uma solução sólida cristalina de composição Y0,9Er0,1Al3(BO3)4. No que se refere às propriedades dos filmes finos, as melhores condições de densificação, homogeneidade, eficiência de guiamento, emissão luminescente e tempo de vida foram observadas quando os filmes de composição Y0,9Er0,1Al3(BO3)4 foram tratados entre as temperaturas de Tg e Tc. Os filmes amorfos de composição Y0,9Er0,1Al3(BO3)4 se comportam como guias monomodos, apresentando alta emissão luminescente e um tempo de vida comparável a outros sistemas amorfos a base de boro. Esse comportamento mostra a viabilidade de aplicação desses filmes amorfos como amplificadores ópticos planares. / This work specifies the synthesis and the characterization of amorphous and crystalline powder and thin films materials belonging to the Er2O3-Y2O3-Al2O3-B2O3 system. The main objective of this work was to develop amorphous thin film samples near the YAI3(BO3)4 composition with yttrium partially substituted by erbium Y1-xErxAl3(BO3)4 with the aim of applying these thin films as waveguide amplifiers in integrated optical systems. The polymeric precursor and the sol-gel methods were applied in order to produce such thin films. After the first step where the conditions to obtain very stable resins and sols was established, different parameters were adjusted aiming the deposition of thick and stable thin films. To well define the best conditions to obtain amorphous and dense thin films, the powder samples of the same compositions were first characterized by thermal analysis techniques, X-ray diffraction, IR and Raman spectroscopies, high resolution electron microscopy and atomic force microscopy. From thermal analysis and structural results, it was observed that the samples prepared from the polymeric precursor and sol-gel methods exhibit glass transition temperatures, Tg, at 723 and 746 °C and cristallisation temperatures, Tc, at 814 and 830 °C, respectively. The heat treatment at around 1150 °C of Y0,9Er0,1Al3(BO3)44 powder sample containing a smaller amount of boron in excess produced by both methods lead to the formation of a crystalline solid solution of the same composition without the presence of secondary phases. These results show that dense, free of cracks, thick and homogeneous thin films could be obtained when they were submitted at a heat treatment in temperatures between Tg and Tc. From the \"m-line\" spectroscopy technique and luminescence measurements we observed that the Y0,9Er0,1Al3(BO3)4 amorphous thin films can be considered as monomode waveguides showing a high luminescence intensities and a lifetime similar to other amorphous borate systems. These results show the potentiality to apply such amorphous thin films as optical planar amplifiers.
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The relation between the deposition process and the structural, electronic, and transport properties of magnetron sputtered doped ZnO and Zn1-xMgxO filmsBikowski, Andre 03 July 2014 (has links)
In dieser Dissertation wurde die Beziehung zwischen den strukturellen, optischen und Ladungstransporteigenschaften von dotierten ZnO- und Zn1-xMgxO-Schichten eingehend untersucht. Das Ziel war es, die oben genannten Zusammenhänge weiter aufzuklären, wodurch sich anschließend Ansätze für eine zielgerichtete Verbesserung der Schichteigenschaften ableiten lassen. Zunächst konzentriert sich die Arbeit auf das Wachstum der ZnO-Schichten, um wichtige strukturelle Parameter, wie zum Beispiel Korngrößen und Defektdichten, mittels Röntgendiffraktometrie und Transmissionselektronenmikroskopie zu bestimmen. Diese strukturellen Parameter wurden dann als Modellparameter für die theoretische Modellierung des Transports der freien Ladungsträger verwendet. Temperaturabhängige Hall-, Leitfähigkeits- und Seebeck-Koeffizient-Messungen zeigten, dass der elektrische Transport hauptsächlich durch die Streuung der Ladungsträger an ionisierten Störstellen und Korngrenzen limitiert wird. Im Rahmen dieser Arbeit wurde die theoretische Beschreibung der Streuung an Korngrenzen auf entartet dotierte Halbleiter erweitert. Diese Ergebnisse wurden dann genutzt, um ein qualitatives Modell zu formulieren, welches den Zusammenhang zwischen dem Magnetron-Sputter-Abscheidungsprozess und den strukturellen und elektrischen Eigenschaften der Schichten herstellt. Gemäß diesem Modell sind die Schichteigenschaften bei niedrigen Abscheidungstemperaturen hauptsächlich durch die Bildung akzeptoratiger Sauerstoffzwischengitterdefekte bestimmt, die einen Teil der extrinsischen Dotanden kompensieren. Diese Defekte werden durch ein Bombardement der wachsenden Schicht mit hochenergetischen negativen Sauerstoffionen verursacht. Bei höheren Abscheidungstemperaturen dominiert die Bildung von sekundären Phasen oder Defektkomplexen, in denen der Dotant elektrisch inaktiv ist. / In this thesis, the relation between the structural, optical, and charge carrier transport properties of magnetron sputtered doped ZnO and Zn1-xMgxO films has been investigated in detail. The objective was to clarify the above mentioned relations, which allows to derive solutions for a deliberate improvement of the layer properties. The work first focusses on the growth of the ZnO layers to determine important structural properties like grain sizes and defect densities via X-ray diffraction and transmission electron microscopy investigations. These structural properties were then used as model parameters for the theoretical modelling of the charge carrier transport. The temperature dependent Hall, conductivity and Seebeck coefficient measurements show that the transport is mainly limited by grain boundary scattering and ionized impurity scattering. The theoretical description of the grain boundary scattering has been extended in this work to also include degenerate semiconductors. Based on the results on the structural and electronic properties, in a next step a qualitative model was developed which explains the correlation between the magnetron sputtering deposition process and the structural and electronic properties of the films. According to this model, the properties of the films are mainly influenced by the formation of electrically active acceptor-like oxygen interstitial defects at low deposition temperatures, which lead to a partial compensation of the extrinsic donors. These defects are caused by a bombardment of the growing film by high-energetic negative oxygen ions. At higher deposition temperatures, the formation of secondary phases or defect complexes, in which the dopant is electrically inactive, prevails.
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Efeito de metais de transição sobre a polarização espontânea na estrutura cristalina de nanopós da família tungstênio bronzeLima, Alan Rogério Ferreira 28 February 2011 (has links)
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Previous issue date: 2011-02-28 / This work aimed the study of the effect of transition metals (Ni, Fe, Co) on the spontaneous polarization of the ferroelectric oxides of tetragonal tungsten bronze (TTB)-type structure of potassium strontium niobate (KSr2Nb5O15) and of the KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d and KSr2(CoNb4)O15-d solid solutions. All systems investigated were prepared by mechanical mixture of oxide/carbonates by high-energy ball milling. The calcination temperature was performed to obtain nanoparticles and the nanostructured particles were evaluated. The evolution of mass loss, chemical bonds, crystalline structure and the electrical behavior were
evaluated using the thermal analysis (thermogravimetric Analysis (TGA) and Differential Scanning Calorimeter (DSC), infrared absorption spectroscopy (FTIR), X-ray diffraction
(XRD) and impedance spectroscopy, respectively. From the impedance spectroscopy technique were studied the dielectric properties of the nanoparticles and the dielectric
permittivity of the KSr2Nb5O15, KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d and KSr2(CoNb4)O15-d systems was determined. The highest permittivity value was obtained for KSr2(FeNb4)O15-d. The determination of crystallographic parameters of nanopowders was performed using the
Rietveld method. From the crystallographic parameters was simulated the crystalline structure and determined the spontaneous polarization for KSr2Nb5O15, KSr2(FeNb4)O15-d,
KSr2(NiNb4)O15-d and KSr2(CoNb4)O15-d systems based on the atomic displacement (Dz) of Nb (niobium) atom, in the z plane, from the central position of the [NbO6] octahedron. The
variation of spontaneous polarization of the nanoparticles with the addition of transition metals in the KSr2Nb5O15 host structure confirmed the existence of ferroelectricity in the
systems investigated. / O objetivo deste trabalho foi estudar o efeito de metais de transição (Ni, Fe, Co), sobre a
polarização espontânea, dos óxidos ferroelétricos de estrutura tungstênio bronze (TB) de
niobato de potássio e estrôncio (KSr2Nb5O15) e das soluções sólidas de KSr2(FeNb4)O15-d,
KSr2(NiNb4)O15-d e KSr2(CoNb4)O15-d. Todos os sistemas investigados foram preparados por
mistura de óxidos/carbonatos pelo do método de ativação mecânica por moagem de alta
energia. A temperatura de calcinação necessária à obtenção de nanopartículas foi otimizada e
as partículas nanoestruturadas foram avaliadas. A evolução dos parâmetros de perda de
massa, ligações químicas, estrutura cristalina e o comportamento elétrico, foram avaliados
utilizando as técnicas de análise térmicas (análise termogravimétrica (ATG) e calorimetria
diferencial exploratória (DSC), espectroscopia de absorção na região do infravermelho,
difração de raios X e espectroscopia de impedância, respectivamente. A partir da técnica de
espectroscopia de impedância foram estudadas as propriedades dielétricas das nanopartículas
em suspensão, determinando a permissividade dielétrica dos sistemas KSr2Nb5O15,
KSr2(FeNb4)O15-d, KSr2(NiNb4)O15-d e KSr2(CoNb4)O15-d. O maior valor de permissividade
foi obtido para o KSr2(FeNb4)O15-d. A determinação dos parâmetros cristalográficos dos
nanopós foi realizada utilizando o método de Rietveld de refinamento e/ou ajuste de estrutura
cristalina. A partir dos parâmetros cristalográficos foi simulada a estrutura cristalina e
determinada a polarização espontânea para os sistemas KSr2Nb5O15, KSr2(FeNb4)O15-d,
KSr2(NiNb4)O15-d e KSr2(CoNb4)O15-d com base no deslocamento atômico (Dz) do átomo de
Nb (nióbio), no plano z, da posição central do octaedro [NbO6]. A variação da polarização
espontânea das nanopartículas, com a adição de metais de transição na estrutura hospedeira do
KSr2Nb5O15, confirmou a existência de ferroeletricidade nos sistemas investigados.
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Avaliação de filmes à base de quitosana combinado com goma xantana e hidrolisado proteico de corvina (Micropogonias furnieri)Lima, Maria de Morais 10 March 2017 (has links)
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Previous issue date: 2017-03-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Os filmes biodegradáveis vêm despertando o interesse da comunidade científica por
apresentarem potencialidade como materiais de embalagens. Eles melhoram a
qualidade e reduzem perdas de alimentos, além de cooperarem com a preservação
do meio ambiente. Nesse sentido, o objetivo geral desta pesquisa foi avaliar filmes à
base de quitosana combinados com goma xantana e hidrolisado de corvina
(Micropogonias furnieri). Desta forma, este trabalho contempla quatro capítulos. No
primeiro estudo, avaliou-se hidrolisados enzimáticos de corvina (Micropogonias
furnieri) através da composição proximal, grau de hidrólise, atividade antioxidante,
perfil de distribuição da massa molar e composição de aminoácidos. Filés de corvina
foram hidrolisados com a enzima Alcalase 2.4L variando apenas o tempo, assim,
foram obtidos hidrolisados com 2, 4 e 8 h de reação. Os teores de proteínas dos
hidrolisados variaram de 78,28 a 82,30%, onde o hidrolisado com maior tempo de
reação mostrou maior grau de hidrólise (32,1%) e maior poder de inibição da
oxidação pelos métodos ABTS e DPPH (98,35% e 54,11%, respectivamente). No
segundo estudo foram elaborados filmes à base de quitosana e goma xantana. Os
filmes foram avaliados por seus grupos funcionais, propriedades estruturais,
térmicas, morfológicas, físicas, mecânicas, ópticas e de barreira. Todos os filmes
apresentaram picos endotérmicos no intervalo de 122 e 175 °C e picos exotérmicos
largos acima de 200 °C, que foram atribuídos à temperatura de fusão e à
decomposição térmica, respectivamente. Estes resultados demonstraram que os
filmes com goma xantana têm o Tm e o ΔmH mais elevados. Os filmes que contêm
maior teor de goma xantana mostram também maior resistência à tração e a menor
elongação. A adição de goma xantana não afetou a permeabilidade ao vapor de
água, solubilidade em água e umidade dos filmes. No terceiro estudo, filmes à base
de quitosana, goma xantana e hidrolisado proteico de corvina (Micropogonias
furnieri) foram elaborados com o objetivo de avaliar suas propriedades antioxidantes,
mecânicas, físicas, estruturais, morfológicas, térmicas e de barreira. A mistura de
goma xantana e hidrolisado promoveram algumas alterações nos filmes de
quitosana. A adição de goma xantana aumentou a resistência a tração e alterou os
parâmetros de cor dos filmes. A adição de hidrolisado proteico de corvina propiciou
significativa atividade antioxidante aos filmes, no entanto, maiores concentrações
tendem aumentar a umidade e diminuir a resistência dos mesmos. Todos os filmes
apresentaram uma estrutura homogênea, sem separação de fases e livres de
fissuras. Não foram observadas diferenças significativas quanto à solubilidade e à
permeabilidade ao vapor de água nos filmes estudados. Já no quarto estudo
objetivou-se avaliar a eficiência de filmes à base de quitosana e goma xantana na
conservação de filés de corvina mantidos sob refrigeração durante 9 dias. Avaliou-se
a composição proximal, perda de massa, cor, pH, N-BVT (Bases Voláteis Totais) e
perfil microbiológico. Os resultados demonstraram que a combinação de quitosana e
goma xantana proporcionaram melhorias na qualidade do pescado refrigerado, uma
vez que reduziu as N-BVT, inibiu o crescimento de Staphylococcus coagulase
positiva, Salmonella spp e coliformes a 45 °C. / Biodegradable films have aroused the interest of the scientific community for
presenting potential as packaging materials. They improve quality and reduce food
waste, as well as cooperate with the preservation of the environment. In this sense,
the general objective of this research was to evaluate chitosan based films combined
with xanthan gum and enzymatic protein from croaker (Micropogonias furnieri). Thus,
this work contemplates four chapters. In the first study, enzymatic hydrolysates of
croaker (Micropogonias furnieri) were evaluated through the proximal composition,
degree of hydrolysis, antioxidant activity, molar mass distribution profile and amino
acid composition. Croaker fillets were hydrolyzed with the enzyme Alcalase 2.4L
varying only the time, thus, hydrolysates with 2, 4 and 8 h of reaction were obtained.
The hydrolyzate protein content varied from 78.28-82.30%, the hydrolyzate with the
highest hydrolysis time showed a higher degree of hydrolysis (32.1%) and a higher
oxidation inhibition power by the ABTS and DPPH methods (98.35% and 54.11%,
respectively). In the second study, films based on chitosan and xanthan gum were
elaborated. The films were evaluated by their functional groups, structural, thermal,
morphological, physical, mechanical, optical and barrier properties. All films showed
endothermic peaks in the range of 122-175 °C and wide exothermic peaks above
200 °C, which were attributed to melt in temperature and thermal decomposition,
respectively. These results demonstrated that films with xanthan gum have the
highest Tm and ΔmH. Films containing higher xanthan gum content also show higher
tensile strength and lower elongation. The addition of xanthan gum did not affect the
water vapor permeability, water solubility and moisture of the films. In the third study,
films based on chitosan, xanthan gum and protein hydrolysate of croaker
(Micropogonias furnieri) were elaborated with the objective of evaluating its
antioxidant, mechanical, physical, structural, morphological, thermal, optical and
barrier properties. The mixture of xanthan gum and hydrolyzate promoted some
changes in the chitosan films. The addition of xanthan gum increased the tensile
strength and altered the color parameters of the films. Croaker protein hydrolyzate
addition gave significant antioxidant activity to the films, however, higher
concentrations tend to increase humidity and decrease their resistance. All the films
presented a homogeneous structure, without separation of phases and free of
cracks. No significant differences were observed regarding the solubility and
permeability to water vapor in the studied films. The fourth study aimed to evaluate
the efficiency of chitosan and xanthan gum films in the conservation of croaker
steaks kept under refrigeration for 9 days. Proximal composition, loss of mass, color,
pH, N-BVT (Total Volatile Bases) and microbiological profile were evaluated. The
results demonstrated that the combination of chitosan and xanthan gum provided
improvements in the quality of refrigerated fish as it reduced N-BVT, inhibited growth
of coagulase-positive Staphylococcus, Salmonella spp and coliforms at 45 °C.
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Investigation of structural properties in biomolecular systems using synchrotron-based spectroscopiesKummer, Kurt 11 August 2010 (has links) (PDF)
Solid state approaches to structural properties like diffraction or microscopy techniques often cannot be applied to biomolecular systems, at least not without special postpreparation which often corrupts the desired properties of the pristine systems. In this work the capabilities of synchrotron-based, soft X-ray spectroscopies as an alternative way to unravel structural properties of such systems are tested. To this end, three exemplary systems were investigated each with the focus on another facet and characteristic length scale. The first example are DNA-alkanethiol self-assembled monolayers, also known as DNA microarrays or DNA chips, for which a way to monitor and controllably tune the structural composition on the mesoscopic scale of many thousands of molecules was sought for. The second example focuses on the single-molecule and submolecular scale in metalprotein hybrid compounds with the aim to identify the binding site of metal atoms or ions within protein molecules and the underlying interaction mechanisms. The most fundamental structural scale, the level of single bonds and molecular orbitals, is addressed in the last example where it was tried to elaborate an approach to map the topology of molecular orbitals based upon X-ray absorption properties. This approach was put to the practical test for the characteristic pi*peptide orbitals in protein backbones. For all three investigated examples, spectroscopies using soft X-ray synchrotron radiation were able to extract the desired information, thus confirming that they may grant alternative access to structural properties of soft-matter systems in cases where standard approaches fail. / Klassische Festkörpertechniken zur Strukturuntersuchung, wie Streu- oder Mikroskopiemethoden, können häufig nicht auf Biomolekülsysteme angewandt werden, zumindest nicht ohne spezielle Postpräparation, die die ursprünglichen Eigenschaften dieser Systeme oft verfälscht. In dieser Arbeit soll untersucht werden, inwieweit Röntgenspektroskopien basierend auf Synchrotronstrahlung einen alternativen Zugang zu Struktureigenschaften solcher Systeme bieten. Dazu wurden drei Systeme exemplarisch untersucht, jeweils mit Schwerpunkt auf einen anderen Aspekt und charakteristischen Längenbereich. Für selbstorganisierende DNA-Alkanthiol-Schichten, sogenannte DNA-Chips, wurde nach eine Weg gesucht, ihre strukturelle Zusammensetzung auf der mesoskopischen Ebene vieler tausend Moleküle zu bestimmen und kontrolliert zu modifizieren. Metallisierte Proteinstrukturen wurden auf Einzelmolekül- bzw. submolekularer Ebene untersucht, mit dem Ziel, die Orte der Metallanlagerung innerhalb des Proteins und die zugrundeliegenden Wechselwirkungsmechanismen zu identifizieren. Die unterste strukturelle Ebene, der Bereich einzelne Bindungen und Molekülorbitale, wurde adressiert am Beispiel der pi*peptide Orbitale des Proteinrückrats. Dafür wurde eine Methode zur Kartographierung einzelner Orbitale anhand von Röntgenabsorptionseigentschaften herausgearbeitet und praktisch getestet. In allen drei Fällen konnten Röntgenspektroskopien die nötigen Informationen liefern und damit ihr Potential für Strukturuntersuchungen in weicher Materie unter Beweis stellen.
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Sínteses e caracterizações óptica e estrutural de nanopartículas de LaF3:Yb3+/Ho3+e LaF3:Yb3+/Tm3+ e cerâmicas transparentes de Y2O3:Eu3+e Y2O3:Tm3+ / Syntheses and optical and structural characterizations of nanoparticles of LaF3_Yb3+Ho3+ e LaF3_Yb3+Tm3+ and transparent ceramic of Y2O3_ Eu3+ e Y2O3_Tm3+Nuñez, Patrícia Ysabel Poma 28 August 2015 (has links)
Rare-earth ions co-doped lanthanum fluoride (LaF3) nanoparticles (NPs) were synthesized and the effect of different annealing temperatures investigated. We have also investigated the thermo-optical properties of Tm3+ and Eu3+ doped Y2O3 transparent ceramics. The LaF3:Yb3+/Ho3+ and LaF3:Yb3+/Tm3+ NPs were treated thermally by 3 hs at 300, 500, 700, and 900 °C and then characterized with respect to crystalline structures, sizes, shapes, presence of other crystalline phases and luminescent properties. From the experimental results, optimization of optical and structural properties were obtained for the thermal treatment at 500 °C while maintaining the LaF3 crystalline phase. However, it was observed the formation of lanthanum oxifluoride (LaOF) under thermal annealing at 900 °C, with higher luminescence in the near infrared, which makes this host to deserve further study. It was also synthesized LaF3 NPs varying the Tm3+ and Ho3+ ions concentrations with fixed Yb3+ one and these samples were thermally treated at 500 and 900 °C by 3 hs. The 1.2, 1.47, 1.8, and 2 μm emissions behaviors of Tm3+ and Ho3+ ions were investigated, in order to obtain the best concentrations for these emissions in these two hosts: LaF3 and LaOF. We also synthesized Yb3+/Tm3+ and Yb3+/Ho3+ co-doped LaF3 using nitrate and chloride precursors and these samples were annealed at 500 and 900° C to observe what occurs in the structural, morphological, and optical properties of the LaF3 and LaOF. As a result, no significant difference was observed in their structural and optical properties, thus facilitating the use of nitrate and chloride precursors for further researches using these hosts. Another very interesting and promising material is the yttrium oxide (Y2O3) transparent ceramics. In this case, we investigated using the thermal lens technique, conventional spectroscopy of luminescence and temporal dynamic, the thermal and optical properties of Y2O3:Tm3+ and Y2O3:Eu3+. The thermal properties obtained were: thermal diffusivity =26.06x10-3cm2/s, thermal conductivity =5.8 W/m.K, and the temperature coefficient of the optical path length change ⁄=2.978x10-6K-1. Small values for D and k were obtained in comparison to those of the literature, and this was attributed to the grain size of the investigated ceramics. The luminescence decays along with the thermal lens spectroscopy results were complementary to a complete characterization of the Y2O3:Tm3+ ceramics, enabling obtaining the fluorescence quantum efficiency of the Tm3+ 3F4 level emitting at 1.8 μm, which was estimated at η1=0.84. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nanopartículas (NPs) de fluoreto de lantânio (LaF3) codopadas com íons terras-rara foram sintetizadas e avaliado o efeito de tratamento térmico em diferentes temperaturas. Também investigamos as propriedades termo-ópticas de cerâmicas transparentes de Y2O3 dopadas com os íons Tm3+ e Eu3+. As NPs de LaF3:Yb3+/Ho3+ e LaF3:Yb3+/Tm3+ foram tratadas termicamente por 3 horas nas temperaturas de 300, 500, 700 e 900 °C para então caracterizá-las com relação as suas estruturas cristalinas, tamanhos, formas, presença de outras fases cristalinas e propriedades luminescentes. A partir de resultados experimentais, verificou-se a otimização das propriedades estrutural e óptica no tratamento térmico de 500 °C, mantendo a fase cristalina de LaF3. No entanto, foi observada à formação de óxifluoreto de lantânio (LaOF) no tratamento térmico a 900 °C, resultando em maior luminescência no infravermelho próximo, o que faz essa matriz merecer um estudo mais aprofundado. Também, foram sintetizadas NPs de LaF3, mudando a concentração dos dopantes Tm3+ e Ho3+, mantendo fixa a de Yb3+, e essas amostras foram tratadas termicamente a 500 e 900 °C por 3 horas. Foram investigados os comportamentos das emissões em 1,2; 1,47; 1,8 e 2 μm dos íons Tm3+ e Ho3+, com intuito de se obter as melhores concentrações para essas emissões nessas duas matrizes: LaF3 e LaOF. Sintetizamos também LaF3 codopadas com Yb3+/Tm3+ e Yb3+/Ho3+, usando precursores nitratos e cloretos e as tratamos termicamente a 500 e 900 °C para se observar o que ocorre nas propriedades estruturais, morfológicas e ópticas nas matrizes LaF3 e LaOF. Como resultado, não foram observadas diferenças significativas em suas propriedades estruturais e ópticas, facilitando assim o uso de precursores nitratos e cloretos para futuras pesquisas usando essas matrizes. Outra matriz promissora é a cerâmica transparente de óxido de ítrio (Y2O3). Neste caso, investigamos usando a técnica de lente térmica e espectroscopia convencional de luminescência e dinâmica temporal, as propriedades térmicas e ópticas de Y2O3:Tm3+ e Y2O3:Eu3+. As propriedades termo-ópticas obtidas foram: difusividade térmica =26,06×10-3 cm2/s, condutividade térmica =5,8 W/m.K e o coeficiente de variação do caminho óptico com a temperatura ⁄=2,978×10-6 K-1. Valores pequenos para D e foram obtidos, quando comparados com os da literatura. Tais valores foram atribuídos ao tamanho dos grãos das nossas cerâmicas. Os decaimentos das luminescências, juntamente com os resultados da espectroscopia de lente térmica, foram complementares para uma caracterização completa da cerâmica de Y2O3:Tm3+, possibilitando a obtenção da eficiência quântica de fluorescência do nível 34 do íon Tm3+ emitindo em 1,8 μm, a qual foi estimada em 1=0,84.
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Propriedades estruturais e optoeletr?nicas dos compostos SrSnO3, SrxBa1-xSnO3 e BaSnO3Moreira, Edvan 29 July 2011 (has links)
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Previous issue date: 2011-07-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In this work we present a study for the structural, electronic and optical properties, at
ambient conditions of SrSnO3, SrxBa1?xSnO3 (x = 0:2; 0:4; 0:6; 0:8) and BaSnO3 crystals, all of
them member of perovskite-type earth stannates class, ASnO3. The theoretical model employed
was based on the density functional theory (DFT), considering both the local density and
the generalized gradient approximations, LDA-CAPZ and GGA-PBE (OPIUM), respectively.
For orthorhombic SrSnO3, the electronic band structure, density of states, complex dielectric
function, optical absorption, and the infrared and Raman spectra were computed. Calculated
lattice parameters are closed to the experimental measurements, and an indirect band gap E(S
-> t ?)=1.97 eV (2.27 eV) was obtained within the GGA (LDA) level of calculation. E ective
masses for holes and electrons were estimated, being very anisotropic in comparison with similar
results for orthorhombic CaSnO3. The complex dielectric function and the optical absorption
of SrSnO3 are sensitive to the plane of polarization of the incident light. The infrared spectrum
between 100-600 cm-?1 was obtained, with its main peaks being assigned, and a good agreement
between experimental and theoretical peaks of the Raman spectrum of orthorhombic SrSnO3
was achieved.
For SrxBa1?xSnO3 series, their electronic properties were investigated. The cubic
Sr0:2Ba0:8SnO3 has an indirect band gap, while tetragonal Sr0:4Ba0:6SnO3, orthorhombic Sr0:6Ba0:4
SnO3 and Sr0:8Ba0:2SnO3 exhibit a direct band gap. The Kohn-Sham minimum electronic band
gap oscillates of 2.62 eV (tetragonal Sr0:4Ba0:6SnO3, LDA) to 1.52 eV (orthorhombic Sr0:6Ba0:4Sn
O3, LDA). The effective masses for holes and electrons were estimated, being anisotropic in the series.
For cubic BaSnO3, the electronic band structure, density of states, dielectric function and optical absorption were calculated, as well as the infrared absorption spectra after computing
the vibrational modes of the crystal at q = 0. Dielectric optical permittivities and
polarizabilities at w = 0 and w = ?? were also obtained. An indirect band gap E(R -> T?)
of 1.01 eV and 0.74 eV was achieved within the LDA-CAPZ and the GGA-PBE, respectively,
which is smaller than the experimental data ( ?? 3.1 eV). Effective masses of holes and electrons
were estimated by parabolic tting along di erent directions at the valence band maximum
and conduction band minimum, being highly isotropic for electrons and anisotropic for holes,
allowing us to suggest that indirect gap cubic BaSnO3 is a semiconductor with potential for
optoelectronic applications. The optical properties reveal a degree of isotropy for the crystal
with respect to di erent polarization planes of incident light. The infrared spectrum between
100-600 cm?-? was obtained, with its main peaks being assigned / Apresentamos neste trabalho um estudo das propriedades estruturais, eletr?nicas e ?pticas, em temperatura ambiente dos cristais de SrSnO3, SrxBa1xSnO3 (x = 0:2; 0:4; 0:6; 0:8) e BaSnO3, todos eles membros da classe das perovskitas do tipo estanatos terrosos, ASnO3. O nosso modelo te?rico foi baseado na teoria do funcional da densidade (DFT) considerando as aproxima??es da densidade local e do gradiente generalizado, LDA-CAPZ e GGA-PBE (OPIUM), respectivamente. Para o SrSnO3 ortor?mbico, foram calculadas a estrutura de bandas eletr?nica, densidade de estados, fun??o diel?trica complexa, absor??o ?ptica e os espectros infravermelho e Raman. Os par?metros de rede calculados est?o pr?ximos dos resultados experimentais, e um band gap indireto E(S !)=1.97 eV (2.27 eV) foi obtido dentro do n?vel GGA (LDA) de c?lculo. As massas efetivas dos buraco e dos el?trons foram estimadas, sendo elas muito anisotr?picas em compara??o com os resultados similares para o CaSnO3 ortor?mbico. Al?m disso, nossos resultados mostram que a fun??o diel?trica complexa e a absor??o ?ptica do SrSnO3 s?o sens?veis ao plano de polariza??o da luz incidente. O espectro infravermelho entre 100{600 cm1 foi obtido, com seus principais picos sendo assinalados, e uma boa concord?ncia dos resultados experimentais e te?ricos do espectro Raman do SrSnO3 ortor?mbico foram alcan?ados. Para a s?rie SrxBa1xSnO3, as propriedades eletr?nicas foram investigadas. O Sr0:2Ba0:8 SnO3 c?bico possui um band gap indireto, enquanto o Sr0:4Ba0:6SnO3 tetragonal, os ortor?mbicos Sr0:6Ba0:4SnO3 e Sr0:8Ba0:2SnO3 exibem um band gap direto. O band gap eletr?nico m?nimo de Kohn-Sham oscila de 2.62 eV (Sr0:4Ba0:6SnO3 tetragonal, LDA) at? 1.52 eV (Sr0:6Ba0:4SnO3 ortor?mbico, LDA). As massas efetivas de buracos e de el?trons foram estimadas, sendo anisotr?picas nas s?ries. vi Para o BaSnO3 c?bico, foram calculadas a estrutura de bandas eletr?nica, densidade de estados, fun??o diel?trica e absor??o ?ptica, bem como o espectro infravermelho de absor??o ap?s computar os modos de vibra??o do cristal em q = 0. A permissividade ?ptica diel?trica e as polarizabilidades em ! = 0 e ! = 1 foram obtidas. Um band gap indireto E(R !) de 1.01 eV e 0.74 eV foi obtido com o LDA-CAPZ e o GGA-PBE, respectivamente, que ? menor que o dado experimental (3.1 e V). As massas efetivas de buraco e de el?tron foram estimadas atrav?s de um ajuste parab?lico ao longo de diferentes dire??es no m?ximo da banda de val?ncia e no m?nimo da banda de condu??o, sendo muito isotr?pico para el?trons e anisotr?pico para buracos, permitindo-nos sugerir que o BaSnO3 c?bico de gap indireto ? um semicondutor com potencial para aplica??es optoeletr?nicas. As propriedades ?pticas revelaram um grau de isotropia para o cristal com respeito aos diferentes planos de polariza??o de luz incidente. O espectro infravermelho entre 100{600 cm 1 foi obtido, com seus principais picos sendo assinalados
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Síntese e caracterização de filmes finos do sistema Y2O3-Er2O3-Al2O3-B2O3 para aplicação como amplificadores ópticos planares. / Thin films preparation and characterization of the Y2O3-Er2O3-Al2O3-B2O3.Lauro June Queiroz Maia 18 October 2006 (has links)
Esse trabalho de tese descreve a síntese e a caracterização de materiais amorfos e cristalinos na forma de pó e de filmes finos pertencentes ao sistema Er2O3-Y2O3-Al2O3-B2O3. O principal objetivo do trabalho foi o de obter filmes finos amorfos contendo íons Er3+ próximo à composição YAI3(BO3)4 (YAB), visando sua aplicação como amplificador em dispositivos ópticos integrados. Na síntese das amostras foi empregado o método dos precursores poliméricos e o método sol-gel. Uma vez estabelecida às condições de síntese das resinas e de sóis estáveis, diferentes parâmetros foram otimizados visando à deposição de filmes relativamente espessos e amorfos. As propriedades térmicas, estruturais e ópticas de amostras cristalinas ou amorfas, na forma de pó e na forma de filmes finos, foram caracterizadas através das técnicas de análise termogravimétrica, calorimetria exploratória diferencial, difração de raios X, espectroscopia vibracional na região do infravermelho com transformada de Fourier, espectroscopia Raman e microscopia eletrônica de varredura de alta resolução, microscopia de força atômica, espectroscopia \"m-line\", medidas de espectros de luminescência. Baseado na análise térmica e estrutural das amostras na forma de pó, foi possível realizar a síntese de amostras na forma de filmes finos de composição Y1-xErxAl3(BO3)4 que apresentaram características estruturais, microestruturais e ópticas adequadas à aplicação desejada. Através do estudo das propriedades térmicas e estruturais, foi observado que as amostras preparadas através do método dos precursores poliméricos e do método sol-gel apresentam respectivamente uma temperatura de transição vítrea (Tg) à 723 °C e à 746 °C e uma temperatura de cristalização (Tc) à 814 °C e à 830°C. O tratamento térmico à aproximadamente 1150 °C da amostra amorfa na forma de pó de composição Y0,9Er0,1Al3(BO3)4 contendo boro em excesso levou a obtenção de uma solução sólida cristalina de composição Y0,9Er0,1Al3(BO3)4. No que se refere às propriedades dos filmes finos, as melhores condições de densificação, homogeneidade, eficiência de guiamento, emissão luminescente e tempo de vida foram observadas quando os filmes de composição Y0,9Er0,1Al3(BO3)4 foram tratados entre as temperaturas de Tg e Tc. Os filmes amorfos de composição Y0,9Er0,1Al3(BO3)4 se comportam como guias monomodos, apresentando alta emissão luminescente e um tempo de vida comparável a outros sistemas amorfos a base de boro. Esse comportamento mostra a viabilidade de aplicação desses filmes amorfos como amplificadores ópticos planares. / This work specifies the synthesis and the characterization of amorphous and crystalline powder and thin films materials belonging to the Er2O3-Y2O3-Al2O3-B2O3 system. The main objective of this work was to develop amorphous thin film samples near the YAI3(BO3)4 composition with yttrium partially substituted by erbium Y1-xErxAl3(BO3)4 with the aim of applying these thin films as waveguide amplifiers in integrated optical systems. The polymeric precursor and the sol-gel methods were applied in order to produce such thin films. After the first step where the conditions to obtain very stable resins and sols was established, different parameters were adjusted aiming the deposition of thick and stable thin films. To well define the best conditions to obtain amorphous and dense thin films, the powder samples of the same compositions were first characterized by thermal analysis techniques, X-ray diffraction, IR and Raman spectroscopies, high resolution electron microscopy and atomic force microscopy. From thermal analysis and structural results, it was observed that the samples prepared from the polymeric precursor and sol-gel methods exhibit glass transition temperatures, Tg, at 723 and 746 °C and cristallisation temperatures, Tc, at 814 and 830 °C, respectively. The heat treatment at around 1150 °C of Y0,9Er0,1Al3(BO3)44 powder sample containing a smaller amount of boron in excess produced by both methods lead to the formation of a crystalline solid solution of the same composition without the presence of secondary phases. These results show that dense, free of cracks, thick and homogeneous thin films could be obtained when they were submitted at a heat treatment in temperatures between Tg and Tc. From the \"m-line\" spectroscopy technique and luminescence measurements we observed that the Y0,9Er0,1Al3(BO3)4 amorphous thin films can be considered as monomode waveguides showing a high luminescence intensities and a lifetime similar to other amorphous borate systems. These results show the potentiality to apply such amorphous thin films as optical planar amplifiers.
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Contribution to the development of an additive for bulk waterproofing of cement-based materialsMilenkovic, Nenad 02 October 2017 (has links)
For the last 10 years, silicone-based admixtures have been successfully used for bulk waterproofing treatment of cementitious materials. However, a reduction in mechanical properties of treated materials is rather observed and becomes a major problem for the in-situ application. A new concept of a knowledge-based integral water repellent has been designed in such a way that the negative effect on mechanical properties is significantly reduced. The technology comprises the delayed release of the hydrophobic agent (silicone resin) which is achieved by encapsulation of the resin in SiO2 shell. A multidisciplinary research was conducted in order to propose a model of the delayed release and the silica shell reaction mechanism in cement paste. Therefore, a study on the microcapsules reaction in calcium hydroxide solution was conducted by means of FTIR, DSC-TGA, surface tension measurements and chemical analysis by ICP-OES. It was shown that microcapsules flocculate in presence of Ca2+, what appears to be the main factor that contribute to the delayed release of the resin.The influence of the microcapsules on Ordinary Portland (OPC) and Blast furnace slag (BFS) cement hydration process was compared with the emulsion of silane monomer and silicone resin. It was shown that the emulsion delays the setting and influences the early age hydration by prolonging the dormant period and decreasing the hydration heat. Cement microstructure and hydration products development was observed by SEM/ESEM. Quantitative analysis of hydration products was assessed by Rietveld analysis of XRD diffractograms. Emulsion induced a significant delay in the cement paste setting by changing the amount and morphology of ettringite and portlandite at very early age. Differently, microcapsules didn’t show any effect on these properties. Experimental work on relevant mortars is done in order to prove the concept of a delayed release as a solution towards the decrease in mechanical properties. The influence of the new additive on setting, volume change, dynamic E-modulus and the compressive strength was analysed. New analytical techniques (AutoShrink, Ultrasonic Pulse Velocity and ConSensor) in combination with traditional ones (Penetration resistance test and compressive strength on cubes) were used. Microcapsules have successfully lowered the negative impact of silanes on the compressive strength and dynamic Young’s modulus. Moreover, it was showed that the microcapsules slightly influence autogenous deformation by increasing the shrinkage of mortars.Microencapsulation of the silicone resin proved to be a promising solution for the bulk hydrophobic treatment of cementitious materials with no-influence on cement hydration. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished
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