No description available.

[pt] Este trabalho tem como objetivo estudar a expansão térmica extrínseca e intrínseca do Al2-xInxW3O12, suas transições de fase e higroscopicidade para as fases: x = 0,2; 0,4; 0,7 e 1. Os pós foram obtidos pelo método de co-precipitação. Esta técnica permite a produção de materiais cerâmicos avançados por meio de reações químicas suaves em temperaturas relativamente baixas usando em solução aquosa. A família Al2-xInxW3O12 faz parte do que se pode classificar como cerâmicas termomióticas (do grego thermo para calor e mio para contração) e pertence à família A2M3O12 (A = cátion trivalente, M = cátion hexavalente), com expansão térmica negativa ou quase zero. Este fato torna esta cerâmica uma candidata potencial em aplicações que requerem materiais com alta resistência ao choque térmico. Na literatura, encontramos poucos estudos sistemáticos que relatam parâmetros de interesse no sistema Al2-xInxW3O12, como os coeficientes de expansão térmica (CET) e suas transições de fase. Portanto, o presente trabalho tem como objetivo determinar os coeficientes de expansão intrínsecos (determinados por difração de raios X que é relativa às variações nos parâmetros de rede do material) e o coeficiente de expansão extrínseco (obtido por dilatometria que leva em consideração a variação intrínseca e também extrínseca, dimensões do material, estas últimas relacionadas a defeitos microestruturais) do sistema Al2-xInxW3O12, temperaturas de transição de fase (monoclínica e ortorrômbica) na faixa de x = 0,2 a x = 1. Além disso, este estudo pretende relatar a higroscopicidade deste sistema (usando termogravimetria). Os resultados mostraram que o Al2-xInxW3O12 adotou uma estrutura ortorrômbica em temperatura ambiente para as composições x = 0,2; 0,4; 0,7 e uma estrutura monoclínica para a composição x = 1. Na fase x = 1, uma transição de fase monoclínica para ortorrômbica ocorreu perto de 200 oC. Finalmente, o sistema Al2-xInxW3O12 apresentou baixa higroscopicidade nas quatro fases estudadas. / [en] The Al2-xInxW3O12 family is part of thermomiotic ceramics (from the Greek thermo for heat and mio for contraction) and belongs to the A2M3O12 family (A = trivalent cation, M = hexavalent cation), wich can show negative or near zero thermal expansion. This fact makes this ceramic a potential candidate in applications that require materials with high resistance to thermal shock. In the literature, we found few systematic studies that report parameters of interest in Al2-xInxW3O12 system such as the coefficients of thermal expansion (CTE) and its phase transitions. Therefore, the present work aims to determine the intrinsic coefficients of expansion (determined by X-ray diffraction that is relative to variations in the material s lattice parameters) and the extrinsic coefficient of expansion (obtained by dilatometry which takes into account intrinsic and also extrinsic variations in dimension, these later related to microstructural defects) of Al2-xInxW3O12, phase transition temperatures (monoclinic to orthorhombic) in the range between x = 0.2 to x = 1. In addition, this study intends to report hygroscopicity of this system (using thermogravimetry). The results showed that Al2-xInxW3O12 adopted an orthorhombic structure at room temperature (RT) for x = 0.2; 0.4; 0.7 compositions and monoclinic structure for x = 1 composition. In x = 1 phase, a monoclinic to orthorhombic phase transition occurred close to 200 oC. Finally, the Al2-xInxW3O12 system presented low hygroscopicity in all four studied phases.

Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator (MI) transition at TMI = 357K, followed by a well-separated antiferromagnetic order at TN = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts TMI and induces exotic magnetic behavior below TN. Moreover, M doping for Ru produces negative thermal expansion in Ca2Ru1-xMxO4 (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio reaching as high as 1%. The onset of the negative thermal expansion closely tracks TMI and TN, sharply contrasting classic negative thermal expansion that shows no relevance to electronic properties. In addition, the observed negative thermal expansion occurs near room temperature and extends over a wide temperature interval. These findings underscores new physics driven by a complex interplay between orbital, spin and lattice degrees of freedom. These materials constitute a new class of Negative Thermal Expansion (NTE) materials with novel electronic and magnetic functions.

No description available.

O presente trabalho, realizado junto ao Grupo de Novos Materiais e Dispositivos (GNMD), no Laboratório de Microeletrônica do Departamento de Sistemas Eletrônicos da Escola Politécnica da USP, visou determinar algumas das propriedades termo-mecânicas de materiais depositados pela técnica de plasma enhanced chemical vapor deposition (PECVD) que são importantes para o desenvolvimento de sistemas microeletromecânicos (MEMS). O módulo de elasticidade, a tensão mecânica residual, o coeficiente de expansão térmica e a condutividade térmica de filmes finos de carbeto de silício amorfo hidrogenado (a-SiC:H) e de oxinitreto de silício (SiOxNy) foram estudados. Medidas de nanoindentação e ressonância de cantilevers foram utilizadas para a obtenção do módulo de elasticidade e os resultados obtidos foram similares (75 e 91 GPa) pelos dois métodos e compatíveis com valores encontrados na literatura. Além disso, obteve-se o módulo de elasticidade de filmes de cromo (285 GPa). A tensão mecânica residual dos filmes utilizados neste trabalho foi medida através da curvatura do substrato induzida pela deposição dos filmes e pela deformação de cantilevers. O valor médio da tensão mecânica, obtido pela curvatura do substrato, variou de -69 MPa até -1750 MPa, mostrando grande dependência das condições de deposição dos filmes. O método que utiliza a deformação de cantilevers possibilitou a obtenção do gradiente de tensão mecânica, que também mostrou uma dependência das condições de deposição, sendo sempre o a-SiC:H quase estequiométrico o menos tensionado. O coeficiente de expansão térmica foi medido utilizando a técnica do gradiente de temperatura e o valor obtido foi similar a valores reportados na literatura para o carbeto de silício cristalino. Para um a-SiC:H quase estequiométrico foi obtido um coeficiente de expansão térmica de 3,41 m/oC, enquanto para um a-SiC:H rico em carbono o valor foi de 4,36 m/oC. Também foi verificado que a variação da resistência do cromo em função da temperatura é pequena, não permitindo sua utilização como sensor de temperatura e inviabilizando a obtenção da condutividade térmica dos filmes estudados. Além disso, foram apresentados trabalhos promissores, mostrando o potencial dos materiais estudados para o desenvolvimento de MEMS. Nesses trabalhos, demonstrou-se a viabilidade de integrar microestruturas atuadas termicamente e guias de onda ópticos, utilizando os materiais estudados neste trabalho. Foram fabricados chaves ópticas, portas lógicas ópticas, fontes de luz integradas e acoplamento das fontes de luz com guias de onda. / This work, realized at the New Materials and Devices Group (GNMD) at the Microelectronics Laboratory of the Department of Electronic Systems of the Polytechnic School of the University of São Paulo, focused at the determination of thermo-mechanical properties of materials deposited by plasma enhanced chemical vapor deposition (PECVD) that are important for the development of microelectromechanical systems (MEMS). The Youngs modulus, the residual stress, the coefficient of thermal expansion and the thermal conductivity of amorphous hydrogenated silicon carbide (a-SiC:H) and silicon oxynitride (SiOxNy) thin films were studied. Nanoindentation and the resonance of cantilevers were used to obtain the Youngs modulus. The results were similar (75 and 91 GPa) with both methods and compatible with literature values. Further, the Youngs modulus of chromium films was also obtained (285 GPa). The residual stress of thin films was obtained through the substrate curvature induced by the film deposition and through the deformation of cantilever beams. The residual stress, obtained through the substrate curvature, varied between -69 MPa and -1750 MPa, showing great dependence on the deposition conditions of these materials. The deformation of cantilevers allowed the determination of the stress gradient and it was also affected by the deposition conditions. In all stress measurements the near stoichiometry a-SiC:H film was less stressed. The coefficient of thermal expansion was measured using the temperature gradient technique and the obtain values were similar to those reported in the literature for crystalline silicon carbide. For a near stoichiometry a-SiC:H film, a value of 3.41 m/oC was obtained, while a carbon rich film showed a thermal expansion coefficient of 4.36 m/oC. It was also verified that the variation of the chromium resistance as a function of temperature is small. This did not allow the utilization of chromium as a temperature sensor, which prevented the obtention of the thermal conductivity of the studied films. Also, some promising works were presented, showing potential applications of the studied materials for the development of MEMS. In these works, the viability of integration of thermal actuated microstructures and optical waveguides was demonstrated. In these works, optical switches, optical logic gates, integrated light sources and coupling of integrated light sources with optical waveguides were presented.

Ultra cold quantum gas is a convenient system to study fundamental questions of modern physics, such as phase transitions and critical phenomena. This master thesis is devoted to experimental investigation of the thermodynamics susceptibilities, such as the isothermal compressibility and the thermal expansion coefficient of a trapped Bose-Einstein condensate (BEC) of 87Rb atoms. The critical phenomena and the critical exponents across the transition can explain the behavior of the isothermal compressibility and the thermal expansion coefficient near the critical temperature TC. By employing the developed formalism of global thermodynamics variables, we carry out a statistical treatment of Bose gas in a 3D harmonic potential. After that, comparison of obtained results reveals the most appropriate state variables describing the system, namely volume and pressure parameter V and Π respectively. The both are related with the confining frequencies and BEC density distribution. We apply this approach to define the set of new thermodynamic variables of BEC, and also to construct the isobaric phase diagram V T. Its allows us to extract the compressibility κT and the thermal expansion coefficient βΠ. The behavior of the isothermal compressibility corresponds to the second-order phase transition, while the thermal expansion coefficient around the critical point behaves as β ∼ tr-α, where tr is reduced temperature of the system and α is the critical exponent on the basic of these. Results we have obtained the critical exponent α = 0.15±0.09, which allows us to determine the system dimensionality by means of the scaling theory, relating the critical exponents with the dimensionality. As a result, we found out that the dimensionality of the system to be d ∼ 3, one is in agreement with the real dimension of the system. / Amostras atômicas ultrafrias de um gás de Bose são convenientes para estudar questões fundamentais da física moderna, como as transições de fase e fenômenos críticos em condensados de Bose-Einstein (BEC). A minha dissertação dedica se à investigação das susceptibilidades termodinâmicas como a compressibilidade isotérmica e o coeficiente de expansão térmica de a traves da transição de um BEC de 87Rb. Os fenômenos críticos e os exponentes críticos a traves da transição podem explicar o comportamento da compressibilidade isotérmica e do coeficiente de expansão térmica perto da temperatura crítica TC. Ao empregar o desenvolvido formalismo das variáveis termodinâmicas globais, levamos a cabo o tratamento estatístico de um gás de Bose num potencial harmônico 3D. Depois da comparação dos resultados obtidos, revelam as mais apropriadas variáveis de estado descrevendo o sistema, chamadas parâmetro de volume e pressão, V e Π respectivamente. As duas estão relacionadas com as frequências de confinamento e a distribuição de densidade do BEC. Nós aplicamos esta abordagem para definir um conjunto de novas variáveis termodinâmicas do BEC, e também para construir o diagrama de fase isobárico V T. O anterior nós permite extrair a compressibilidade κT e o coeficiente de expansão termina βΠ. O comportamento da compressibilidade isotérmica corresponde a uma transição de fase de segunda ordem enquanto que o coeficiente de expansão térmica ao redor do ponto crítico comporta se como β ∼ tr-α, onde tr é a temperatura reduzida do sistema, e α o exponente crítico. Deste resultado nós obtemos um exponente critico, α = 0.15 ± 0.09, que permite determinar a dimensionalidade do sistema a traves da teoria de escala, relacionando os exponentes críticos com a dimensionalidade. Como resultado, encontramos que a dimensionalidade do sistema é d ∼ 3 que está de acordo como a dimensão real do sistema.

Ultra cold quantum gas is a convenient system to study fundamental questions of modern physics, such as phase transitions and critical phenomena. This master thesis is devoted to experimental investigation of the thermodynamics susceptibilities, such as the isothermal compressibility and the thermal expansion coefficient of a trapped Bose-Einstein condensate (BEC) of 87Rb atoms. The critical phenomena and the critical exponents across the transition can explain the behavior of the isothermal compressibility and the thermal expansion coefficient near the critical temperature TC. By employing the developed formalism of global thermodynamics variables, we carry out a statistical treatment of Bose gas in a 3D harmonic potential. After that, comparison of obtained results reveals the most appropriate state variables describing the system, namely volume and pressure parameter V and Π respectively. The both are related with the confining frequencies and BEC density distribution. We apply this approach to define the set of new thermodynamic variables of BEC, and also to construct the isobaric phase diagram V T. Its allows us to extract the compressibility κT and the thermal expansion coefficient βΠ. The behavior of the isothermal compressibility corresponds to the second-order phase transition, while the thermal expansion coefficient around the critical point behaves as β ∼ tr-α, where tr is reduced temperature of the system and α is the critical exponent on the basic of these. Results we have obtained the critical exponent α = 0.15±0.09, which allows us to determine the system dimensionality by means of the scaling theory, relating the critical exponents with the dimensionality. As a result, we found out that the dimensionality of the system to be d ∼ 3, one is in agreement with the real dimension of the system. / Amostras atômicas ultrafrias de um gás de Bose são convenientes para estudar questões fundamentais da física moderna, como as transições de fase e fenômenos críticos em condensados de Bose-Einstein (BEC). A minha dissertação dedica se à investigação das susceptibilidades termodinâmicas como a compressibilidade isotérmica e o coeficiente de expansão térmica de a traves da transição de um BEC de 87Rb. Os fenômenos críticos e os exponentes críticos a traves da transição podem explicar o comportamento da compressibilidade isotérmica e do coeficiente de expansão térmica perto da temperatura crítica TC. Ao empregar o desenvolvido formalismo das variáveis termodinâmicas globais, levamos a cabo o tratamento estatístico de um gás de Bose num potencial harmônico 3D. Depois da comparação dos resultados obtidos, revelam as mais apropriadas variáveis de estado descrevendo o sistema, chamadas parâmetro de volume e pressão, V e Π respectivamente. As duas estão relacionadas com as frequências de confinamento e a distribuição de densidade do BEC. Nós aplicamos esta abordagem para definir um conjunto de novas variáveis termodinâmicas do BEC, e também para construir o diagrama de fase isobárico V T. O anterior nós permite extrair a compressibilidade κT e o coeficiente de expansão termina βΠ. O comportamento da compressibilidade isotérmica corresponde a uma transição de fase de segunda ordem enquanto que o coeficiente de expansão térmica ao redor do ponto crítico comporta se como β ∼ tr-α, onde tr é a temperatura reduzida do sistema, e α o exponente crítico. Deste resultado nós obtemos um exponente critico, α = 0.15 ± 0.09, que permite determinar a dimensionalidade do sistema a traves da teoria de escala, relacionando os exponentes críticos com a dimensionalidade. Como resultado, encontramos que a dimensionalidade do sistema é d ∼ 3 que está de acordo como a dimensão real do sistema.

In der vorliegenden Arbeit wird die Einkristallzüchtung nach dem Czochralskiverfahren von GdCa4O(BO3)3 (GdCOB) beschrieben. Aus insgesamt 18 Zuchtversuchen, bei denen auch die Ziehgeschwindigkeit zwischen 1 und 3mm/h variiert wurde, wurden erfolgreich nahezu perfekte Einkristalle gewonnen. In einigen Kristallen traten jedoch auch Risse oder Einschlüsse auf. Diese enthielten neben Iridium vom Tiegelmaterial auch andere Phasen des Gd2O3–B2O3–CaO-Systems, sowie P und Yb, deren Herkunft unklar ist. Als Hauptziehrichtung wurde die kristallographische b-Achse gewählt, ergänzt durch einige Experimente in der c-Richtung. In den drei kristallographischen Hauptrichtungen wurden die thermischen Ausdehnungskoeffizienten von GdCOB bestimmt. Diese können in zwei nahezu lineare Bereiche unterteilt werden: von Zimmertemperatur bis etwa 850° C und von 850 bis 1200° C, wobei die Koeffizienten im Hochtemperaturbereich deutlich höher sind (unter 850° C: alpha_a=11.1, alpha_b=8.6, alpha_c=13.3 10^-6/K, oberhalb 850° C: alpha_a=14.1, alpha_b=11.7, alpha_c=17.8 10^-6/K). Daraus ergibt sich, dass ein Phasenübergang höherer Ordnung vorliegen muss. Als mögliche Ursache wurde mittels HT-Raman Spektroskopie ein Ordnungs-Unordnungs-Übergang identifiziert, während dessen die BO3-Gruppen in der Struktur leicht rotieren. Weitere Untersuchungen mittels thermodynamischer Methoden führten zu schwachen, aber eindeutigen Signalen, die diesem Effekt ebenfalls zuzuordnen sind. Obwohl das Material ein vielversprechender Kandidat für piezoelektrische Anwendungen im Hochtemperaturbereich ist, wurde dieser Effekt bisher unzureichend beschrieben. Dieses Verhalten, kombiniert mit den anisotropen thermischen Ausdehnungskoeffizienten, könnte eine der Ursachen für das Vorkommen von Rissen in den Kristallen während der Synthese darstellen. Spektroskopische Untersuchungen ergaben einen großen Transparenzbereich von 340 bis 2500nm (29 400–4000 cm^-1), was für optische Anwendungen von großer Bedeutung ist. / In a series of 18 growth experiments, GdCa4O(BO3)3 (GdCOB) single crystals were successfully grown by the Czochralski method. They have a well-ordered structure, as revealed by single crystal structure analysis. Although the main growth direction was along the crystallographic b-axis, some experiments were conducted using the cdirection. Pulling velocities were varied between 1 and 3mm/h. Except for a few crystals with cracks or elongated "silk-like" inclusions consisting of multiphase impurities, most of the obtained crystals are of good quality. Those inclusions contain iridium, deriving from the crucible, P and Yb with unclear source, and other phases from the system Gd2O3–B2O3–CaO. Thermal expansion coefficients of GdCOB were determined in the directions of the crystallographic axes and found to be approximately linear in two temperature ranges: from 25° C to around 850° C, and from 850 to 1200° C, with the latter range showing significantly higher coefficients (below 850° C: alpha_a=11.1, alpha_b=8.6, alpha_c=13.3 10^-6/K, and above 850° C: alpha_a=14.1, alpha_b=11.7, alpha_c=17.8 x10^-6/K). This sudden increase of thermal expansion coefficients indicates a phase transition of higher order. An order-disorder transition in form of the rotation of BO3-triangles in the structure was made tentatively responsible for this transition, as revealed by HT-Raman spectroscopy. This transition was also detected by DSC-methods but appeared to result in very weak effects. Although the material is thought to represent a promising candidate for high temperature piezoelectric applications (noncentrosymmetric space group Cm), this effect of change in specification has not been described and it is unknown whether it has influence on the piezoelectric properties. Furthermore, this characteristic behaviour in combination with anisotropic coefficients may be the reason for the development of cracks during cooling of crystals, making the growth difficult. Spectroscopic investigation revealed a wide transparency range from 340 to 2500nm (29 400–4000 cm^-1) of GdCOB, which is a very important property for optical applications.

Synthesis and Characterization of Some Low and Negative Thermal Expansion Materials Tamas Varga 370 pages Directed by Dr. Angus P. Wilkinson The high-pressure behavior of several negative thermal expansion materials was studied by different methods. In-situ high-pressure x-ray and neutron diffraction studies on several compounds of the orthorhombic Sc2W3O12 structure revealed an unusual bulk modulus collapse at the orthorhombic to monoclinic phase transition. In some members of the A2M3O12 family, a second phase transition and/or pressure-induced amorphization were also seen at higher pressure. The mechanism for volume contraction on compression is different from that on heating. A combined in-situ high pressure x-ray diffraction and absorption spectroscopic study has been carried out for the first time. The pressure-induced amorphization in cubic ZrW2O8 and ZrMo2O8 was studied by following the changes in the local coordination environments of the metals. A significant change in the average tungsten coordination was found in ZrW2O8, and a less pronounced change in the molybdenum coordination in ZrMo2O8 on amorphization. A kinetically frustrated phase transition to a high-pressure crystalline phase or a kinetically hindered decomposition, are likely driving forces of the amorphization. A complementary ex-situ study confirmed the greater distortion of the framework tetrahedra in ZrW2O8, and revealed a similar distortion of the octahedra in both compounds. The possibility of stabilizing the low thermal expansion high-temperature structure in AM2O7 compounds to lower temperatures through stuffing of ZrP2O7 was explored. Although the phase transition temperature was suppressed in MIxZr1-xMIIIxP2O7 compositions, the chemical modification employed was not successful in stabilizing the high-temperature structure to around room temperature. An attempt has been made to control the thermal expansion properties in materials of the (MIII0.5MV0.5)P2O7-type through the choice of the metal cations and through manipulating the ordering of the cations by different heat treatment conditions. Although controlled heat treatment resulted in only short-range cation ordering, the choice of the MIII cation had a marked effect on the thermal expansion behavior of the materials. Different grades of fluorinert were examined as pressure-transmitting media for high-pressure diffraction studies. All of the fluorinerts studied became nonhydrostatic at relatively low pressures (~1 GPa).

Solid oxide fuel cells (SOFC) in a flat-plate configuration require a hermetic seal between the fuel and air sides of the electrodes, and this seal must withstand a variety of thermally-induced stresses over the lifetime of the cell. In this study, quantitative microstructure-property relationships are developed to predict optimum seal structures for mechanical properties and thermal expansion coefficient criteria. These relationships are used to create an inverse approach to characterizing the processing method from the desired microstructure. The main focus of the work concentrates on providing tools to enable macroscopic property predictions from the constituent properties using homogenization techniques based on the individual phase properties and microstructure morphology. The microstructure is represented by two-point correlation functions. Statistical continuum mechanics models were then employed and developed to predict the mechanical and thermal properties of the material. The models enable the prediction of elastic modulus and coefficient of thermal expansion of the multi-phase material. The inelastic mechanical behavior was also studied, indicating microstructure dependence. These models will aid in predicting the a proper seal microstructure (with desired elastic stiffness, coefficient of thermal expansion, and viscoelastic behaviors) based on a desired level of crystallization glass-ceramic materials.