The simple cubic ReO₃-type framework has all of the key features required for negative thermal expansion (NTE) arising from the transverse thermal motion of bridging atoms and rotation of rigid polyhedra. Although ReO₃ itself only displays low NTE below ambient temperature, there is a potentially large family of isostructural fluorides and oxyfluorides that could display NTE. However, the coefficients of thermal expansion (CTE) of ReO₃-type materials range from strongly positive to strongly negative. Through extensive use of in situ synchrotron diffraction, this thesis examines the thermal expansion of several ReO₃-type fluorides and oxyfluorides, demonstrating the effects on CTE and related properties of both cation and anion substitution and the disorder produced by these structural changes.

The work presented in this thesis detail the measurement of the thermal expansion coefficient of three magnetic spin materials. Thermal expansion coefficient values were measured by capacitive dilatometry in several key low (T < 250 K) temperature regions specific to each material. This thesis is separated into several key parts. The first part establishes the theory behind observing phase transitions through the thermal expansion coefficient. Beginning with the classical definitions of the specific heat, compressibility and thermal expansion coefficient, the three properties are related using a property known as the Grüneisen parameter. To first order, the parameter allows phase transitions to be observed by the thermal expansion coefficient. The second part introduces capacitive dilatometry; a technique used to measure the thermal expansion coefficient. Three capacitive dilatometer devices are presented in this section. The silver compact dilatometer, the fused quartz dilatometer and the copper dilatometer. Each device discusses merits and weaknesses to their designs. Particular focus is made on the fused quartz dilatometer which was built during the duration of this thesis. The third part presents research on three magnetic spin materials; LiHoF4, Tb2Ti2O7 and Ba3NbFe3Si2O14. These materials are studied individually focusing on specific aspects. LiHoF4, a candidate material for the transverse field Ising model, provides insight to quantum phase transitions. Thermal expansion coefficient and magnetostriction along the c-axis for T ≈ 1.3-1.8 K and transverse field Ht ≈ 0-4 T were measured extracting critical points for a Ht-T phase diagram. Existing thermal expansion coefficient measurements had evidence of possible re-entrant behaviour. With a high density of low transverse field critical points it was established that LiHoF4 showed no evidence of re-entrant behaviour. The highly debated material Tb2Ti2O7 has a rich, controversial low temperature behaviour. Originally believed to be a spin liquid, specific heat results propose a scenario involving a sample composition dependent ordered state. Still under considerably attention, thermal expansion coefficient measurements were performed for T < 1 K. The results are interpreted to either fit into the proposed scenario or provide evidence for an alternate scenario. The material Ba3NbFe3Si2O14 exhibits a magnetoelectric multiferroic phase below TN ≈ 27 K; a phase where magnetic and electric order simultaneously exist. The formation of this phase is believed to have a similar structural shift observed in hexagonal perovskite multiferroic materials. The ferroelectric ordering in those materials are brought about through a centrosymmetric to non-centrosymmetric structural shift. The thermal expansion and thermal expansion coefficient coefficient along the a and c axis are measured for T > TN searching for a displacive structural phase transition.

In this work, a 3-terminal capacitance dilatometer was set up and used for measurements of the thermal expansion and magnetostriction of novel superconducting iron pinictides and related materials. In particular, \re~with R\,=\,La, Ce, Pr, Sm, Gd, \laf~and Ca(Fe$_{1-x}$Co$_x$)$_2$As$_2$ have been investigated. The data on polycrystalline \laf~are the first published thermal expansion data on this material. The lattice effects at the structural and the magnetic phase transition have been investigated and the phase diagram upon F-doping has been studied. A main result is the observation of a previously unknown fluctuation regime for the doping level $\mathnormal{x}\leqslant$ 0.04 over a large $T$ range above the structural transition temperature \ts. The absence of any structural anomalies in the normal state of the superconducting \laf~samples with $\mathnormal{x}\geqslant$ 0.05 corroborates the discontinuous character of the phase boundary not only for the magnetism but also for the structural degrees of freedom. Similarly, the presence of high-temperature fluctuations is found for all \re~undoped materials under study. The discussion of the probable origin of the fluctuations as well as the definition of the structural transition temperature \ts~are done. The low temperature features shown by the thermal expansion data for \re~are caused by the onset of long range magnetic order of the $4f$-moments and their different configurations. In particular, \pr, which has a very pronounced anomaly associated with Pr-ordering exhibits a large magnetostriction at low temperatures. By discussing this effect along with the magnetization, resistivity and other measurements, it is found that this large magneto-elastic effect may originate from the correlations between the momentum from Fe$^{3+}$ and Pr$^{3+}$. Last, the thermal expansion of Ca(Fe$_{1-x}$Co$_x$)$_2$As$_2$ 122 single crystals is investigated. Ca(Fe$_{1-x}$Co$_x$)$_2$As$_2$ is one of the first materials where single crystals are available. The thermal expansion results on the undoped compound with $x=0$ show a large anomaly at the combined magnetic and structural transition which is far sharper than that for polycrystalline systems. Upon doping, both transitions are suppressed and their splitting is visible in the thermal expansion data. The high precision thermal expansion and magnetostriction results presented in this work are among the first data on the novel family of iron-based superconductors. A valuable insight in the respective ordering phenomena and the thermodynamic properties is provided.

The research presented in this thesis focuses on the structural studies and the high pressure behavior of oxide negative thermal expansion (NTE) materials that can be classified as framework materials. First two chapters were devoted to TaO2F which adopts the ReO3-type cubic structure. Our studies under pressure revealed a rather complicated high pressure behavior for this deceivingly simple compound. The diffraction measurements at variable temperature and high pressure indicated that pressure had a significant effect on the linear coefficient of thermal expansion of TaO2F. In the remainder of the thesis, compounds that belong to the Sc2W3O12 family were examined. High-pressure in-situ powder diffraction studies were conducted on Zr2WO4(PO4)2, Zr2MoO4(PO4)2, Hf2WO4(PO4)2, and Sc2W3O12 in order to investigate the effects of pressure on the coefficients of thermal expansion, existence of phase transitions, phase transition pressures and structural changes occurring upon phase transitions.

Orientador: Antonio Carlos Artur / Banca: Antenor Braga Paraguassú / Banca: José Eduardo Rodrigues / Banca: Maria Heloisa Barros de Oliveira Frascá / Banca: Peter Christian Hackspacher / Resumo: Considerando um conjunto de 21 tipos de rochas utilizadas como revestimento e subdivididas em quatro conjuntos por afinidade da composição mineral (rochas carbonáticas, quartzosas, feldspáticas e quartzo-feldspáticas) foram realizados ensaios tecnológicos para a determinação do coeficiente de dilatação térmica linear e da resistência à compressão uniaxial, bem como a anisotropia dessas propriedades. Os dados tecnológicos obtidos foram correlacionados com informações petrográficas qualitativas e quantitativas referentes à composição mineral, variações texturais e estruturais determinadas em seções ortogonais entre si a partir de um sistema de referência (xyz) baseado na foliação e lineação macroscopicamente visíveis. A análise integrada dos dados utilizando estatística convencional e multivariada procurou apontar as variáveis petrográficas mais relevantes para as duas propriedades tecnológicas enfocadas e suas respectivas anisotropias. A dilatação térmica e sua anisotropia são influenciadas principalmente pela composição mineral e pela orientação preferencial dos minerais embora as microfissuras desempenhem papel importante em alguns casos. A tensão de compressão mostra sua variabilidade e anisotropia influenciadas pela granulação média, tipos de contatos minerais predominantes e padrões de microfissuras mais ou menos definidos por influência da foliação presente. Constatou-se que no conjunto analisado a presença da foliação não implica necessariamente em anisotropia das duas propriedades estudadas. / Abstract: The anisotropy of thermal expansion coefficient and compressive tensile strength were determined for 21 commercially used stones gathered in four set according the main mineral composition named carbonatic, quartz-rich, feldspar-rich and quartz-feldspar-rich rocks. Using a coordinate reference system (xyz) based on the macroscopic visible foliation and lineation the samples were submitted to normalized laboratorial analyses for determination of the both technological properties and the petrographical features such as mineral composition, texture and fabric. Additionally was carried out measurements of weathered area and microcrack quantification by image analysis and texture quantification by U-stage methods. In order to understand the relationship between the anisotropy measured and petrographical data it was applied traditional and multivariate statistical analysis. The results pointed to the great significance of mineral composition and the crystallographic preferred orientation for thermal expansion and respective anisotropy, especially to monomineralic and/or foliated rocks, in spite of some cases microcracks play this role. The compressive strength is mainly controlled by a complex interaction between grain size distribution, grain boundary and microcrack patterns related or not to foliation. / Doutor

Existe atualmente uma tendência de se utilizar em revestimento das fachadas de grandes edificações placas cada vez maiores, separadas por juntas de dilatação com dimensões menores possíveis, a fim de proporcionar efeitos arquitetônicos agradáveis e ao mesmo tempo dificultar a infiltração de agentes deterioradores na estrutura das edificações. Desta forma, há a necessidade de se dimensionar precisamente estas juntas, cuja função é absorver as variações do comprimento de placas produzidas pela dilatação térmica linear (&#946) de rochas graníticas e gnáissicas extraídas nos Estados de São Paulo, Mato Grosso e Espírito Santo, usadas comercialmente na forma de placas para revestimento de edificações. Os coeficientes de dilatação térmica linear (&#946) foram determinados em dilatômetro de quartzo fundido e correlacionadas com o conteúdo em quartzo, granulação, porosidade aparente e estrutura das rochas estudadas. Conclui-se que, nas rochas gnáissicas, os valores de &#946 são muito maiores quando determinados paralelo à gnaissificação. Nas graníticas, o &#946 aumenta com o conteúdo em quartzo e diminui com os aumentos da porosidade aparente e do tamanho dos grãos minerais. / There is a great tendency of using larger plaques of rocks on the covering of the faces of buildings, separated by expansion joints of very small dimensions as possible, in order to provide agreeable architectural effects and at the same time to make difficult the infiltration in the building structure of deterioration agents. Therefore, there is a great need of dimensioning precisely these joints whose function is to absorb the plates length variation produced by thermal expansion. This research presents values of plates length variation produced by thermal expansion. This research presents values of thermal linear expansion coefficient (&#946) of granite and gneiss rocks extracted from São Paulo, Mato Grosso and Espírito Santo states, used commercially in plate shapes for covering of buildings. The thermal linear expansion coefficients (&#946) were determined by cast quartz dilatometer and correlated with the quartz content, granulation, apparent porosity, and the studied rock structures. It can be concluded that, in gneiss rocks, the &#946 values are much bigger when determined in parallel with the structure. On the granite rocks, the &#946 value increases with the quartz content and it decreases with the increases of apparent porosity and the size of mineral grains.

Submitted by MARCIA ROVADOSCHI (marciar@unifra.br) on 2018-08-14T12:51:06Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_RenatoCalegari.pdf: 2585701 bytes, checksum: 505e7f34f4ef08cc40206d7faccfadbb (MD5) / Made available in DSpace on 2018-08-14T12:51:06Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Dissertacao_RenatoCalegari.pdf: 2585701 bytes, checksum: 505e7f34f4ef08cc40206d7faccfadbb (MD5) Previous issue date: 2010-01-21 / The work presented here describes the construction of an educational hypermedia application for the content of Linear Thermal Expansion in teaching physics in high school. The hypermedia application was created in flash that allows light to be run on any machine and have a look capable of holding the attention of the student. Through the use of hypermedia application the teacher can make a coaching activity that the student is developing through the feedback procedure. Thus, allows the teacher to remotely monitor the activity done by the students, analyzing the construction of their knowledge and can intervene when necessary, allowing learning to be more significant. Is the Theory of Meaningful Learning of Ausubel which is the foundation of this work. This work is also given a questionnaire that can be applied to students before using the hypermedia application, in order to obtain student information through the use of new technologies in the classroom and in their daily lives. This application is directed to education, since it addresses only the construction of a hypermedia application and not its application. Through the feedback procedure the teacher follows the construction of knowledge that the student will have by using this feature, showing that a material which, when used by the student will be able to bring significant contributions to physics teaching in the content of linear thermal expansion in high school . / O trabalho aqui apresentado descreve a construção de um aplicativo hipermídia educacional para o conteúdo de Dilatação Térmica Linear no ensino de Física no ensino médio. O aplicativo hipermídia foi criado em flash que permite ser leve para rodar em qualquer máquina e tem um visual capaz de prender a atenção do aluno. Mediante o uso do aplicativo hipermídia o professor pode fazer um acompanhamento individual da atividade que o aluno está desenvolvendo através do feedback processual. Assim, permite ao professor acompanhar remotamente a atividade feita pelo aluno, analisando a construção de seu conhecimento e quando necessário pode intervir, possibilitando a aprendizagem ser mais significativa. É na Teoria da Aprendizagem Significativa de Ausubel que está o fundamento deste trabalho. Neste trabalho também é apresentado um questionário que pode ser aplicado aos alunos antes do uso do aplicativo hipermídia, para assim obter informações dos alunos mediante a utilização das novas tecnologias em sala de aula e em seu dia-a-dia. Este aplicativo é voltado ao ensino, uma vez que aborda somente a construção de um aplicativo hipermídia e não sua aplicação. Através do feedback processual o professor acompanha a construção do conhecimento que o aluno terá mediante o uso deste recurso, mostrando ser um material que, quando utilizado pelo aluno será capaz de trazer significativas contribuições ao ensino de física no conteúdo de dilatação térmica linear no ensino médio.

A dilatação térmica é um problema com o qual os engenheiros de tubulação frequentemente precisam lidar, já que parte do papel destes prossionais é controlar as dilatações lineares totais e minimizar tensões e forças associadas a este fenômeno físico. O projeto de sistemas de tubulação é guiado por normas, sendo a ASME B31.3 (2010) certamente a mais utilizada no Brasil e nos Estados Unidos. Para a referida norma o sistema de tubulação, do ponto de vista térmico, é avaliado com base em uma temperatura de projeto constante e uniforme denida pelos critérios desta norma, temperatura esta normalmente estabelecida com base na temperatura de regime permanente. Estes critérios são sucientes para garantir a integridade estrutural da tubulação em virtude da forma como as tensões admissíveis e atuantes estão estabelecidas, contudo, a norma é omissa em relação ao transiente térmico e a dilatação linear da tubulação durante esse período. Tal dilatação poderá estar associada a forças transmitidas pela tubulação a equipamentos e estruturas, forças essas negligenciadas pela ASME B.31.3 e a literatura em geral. Esse trabalho apresenta as equações envolvidas no problema do transiente térmico de tubulações e, baseando-se nos resultados de simulações numéricas e na mecânica classicamente adotada pela Engenharia de Tubulação para computar forças, faz uma discussão a respeito das forças associadas à dilatação no período do transiente térmico. Vericou-se que quanto maior a velocidade do escoamento, maior o número de Nusselt e maior a difusividade térmica do material do tubo, maior será a taxa de aquecimento da tubulação e que, quanto maior essa taxa de aquecimento e o coeciente de dilatação, maior será a taxa de dilatação linear do tubo. Além disso, a força associada à dilatação linear passa a ser transmitida ao ponto xo (ancoragem ou trava) de forma abrupta e aumenta de forma intermitente até o seu máximo valor, para então cair ao seu mínimo valor de forma extremamente abrupta, sendo este valor mínimo o obtido nas análises usuais de sistemas de tubulação. / Thermal expansion is a problem the pipe engineers often have to deal with, since it is important to control the total linear thermal expansion and minimize stresses and forces associated with this physical phenomenon. The design of pipe systems is guided by standards, being ASME B31.3 (2010) certainly the most used in Brazil and the United States. For this standard the pipe system, from the thermal standpoint, is evaluated based on a constant and uniform design temperature, being this normally referenced by the steady state value. These criteria are sucient to ensure the pipe structural integrity due to the way the admissible and acting stresses are established; however, the standard is silent regarding the thermal transient and the pipe linear thermal expansion during this period. Such thermal expansion may be associated with forces transmitted by the pipe to equipment and structures, neglected by ASME B.31.3 and the literature. This work presents the equations involved in the pipe thermal transient problem. Based on the results of numerical simulations and the procedures normally used by Pipeline Engineering to compute forces, a discussion is made about the forces associated with the thermal expansion in the period of the thermal transient. It was found that the higher the ow velocity, the Nusselt number and the thermal diusivity of the pipe material, the higher the pipe heating rate. Besides, it was found that the higher the heating rate and the thermal expansion coecient, the higher the linear thermal expansion rate of the pipe. Moreover, the force associated with the linear thermal expansion starts to be transmitted to the pipe xed point (anchor or stop) in an abrupt way and increases intermittently until its maximum value, then falls to its minimum value in an extremely abrupt way, being this minimum value the load obtained in the usual pipe load analysis.

Cette thèse avait pour objectif d’étudier les relations existant entre la microstructure de réfractaires alumine-carbone utilisés en coulée continue dans l’industrie sidérurgique et leurs propriétés thermomécaniques. Le travail réalisé ici s’inscrit dans une logique composite, en déterminant les propriétés thermomécaniques des constituants séparément et en analysant ensuite les propriétés des matériaux multiphasiques. Différents systèmes de matériaux modèles ont été étudiés en s’intéressant à deux échelles : agrégats et matrice. Ces matériaux sont constitués d’une part, d’un squelette de graphite et d’agrégats d’alumine et d’autre part d’une matrice carbonée chargée en petits grains d’alumine. La liaison carbone de ces matériaux résultant de la pyrolyse d’une résine phénolique, les propriétés thermomécaniques des matériaux modèles élaborés ont été analysées à la fois pendant et après le traitement thermique de pyrolyse. L’évolution des propriétés au cours de la pyrolyse des échantillons réticulés a mis en évidence l’apparition d’un léger endommagement en fin de montée en température, et un endommagement plus prononcé lors du refroidissement. Cet endommagement résulte d’un différentiel de dilatation thermique entre les grains d'alumine et la liaison carbone. L'influence de ces effets microstructuraux sur le comportement mécanique des matériaux pyrolysés a été étudiée grâce à des essais de traction, mettant en évidence un comportement non-linéaire assez marqué. Des relations entre la fraction volumique et les propriétés physiques clés des matériaux ont pu être établies. Par ailleurs, les résultats obtenus ont montré qu’un changement de composition relativement peu important peut modifier radicalement les propriétés thermomécaniques de ces matériaux. Cette étude sur des matériaux modèles a permis de dégager des pistes pour une amélioration des compositions industrielles. / The present thesis aimed at investigating the relationships existing between the microstructure of alumina-carbon refractories used in steel continuous casting and their thermomechanical properties. The work realized here fall within a composite approach, by determining thermomechanical properties of the single constituents of the materials and analyzing then the properties of the heterogeneous composites. Different systems of double scale model materials, constituted of graphite and alumina aggregates in one hand, and of carbon matrix loaded with fine alumina grains on the other hand were studied here. The carbon bond of these materials resulting from pyrolysis of phenolic resin, the thermomechanical properties of the elaborated model materials were analyzed both during and after the pyrolysis heating treatment. The properties evolutions of the cured samples during the pyrolysis highlighted a slight damage during the end of heating and important damage during cooling, due to a thermal expansion mismatch between the alumina grains and the resin/carbon bond. The influence of the thermal damage has been investigated thanks to tensile tests on the pyrolyzed materials, which exhibit a rather strong non-linear behavior. Relationships between volume fraction and physical key-properties of the materials have been established. Besides, the obtained results highlighted that a small change in composition can drastically change the thermomechanical properties of these materials. This overall study on model materials allowed to develop some ideas in order to improve industrial compositions.

Turbine components operate under severe loading conditions and at high and varying temperatures that result in thermal stresses in the presence of temperature gradients created by hot gases and cooling air. Moreover, static and cyclic loads as well as the motion of rotating components create mechanical stresses. The combined effect of complex thermo-mechanical stresses promote nucleation and propagation of cracks that give rise to fatigue and creep failure of the turbine components. Therefore, the relationship between thermo-mechanical stresses, chemical composition, heat treatment, resulting microstructure, operating temperature, material damage, and potential failure modes, i.e. fatigue and/or creep, needs to be well understood and studied. Artificial neural networks are promising candidate tools for such studies. They are fast, flexible, efficient, and accurate tools to model highly non-linear multi-dimensional relationships and reduce the need for experimental work and time-consuming regression analysis. Therefore, separate neural network models for γ’ precipitate strengthened Ni based superalloys have been developed for predicting the γ’ precipitate size, thermal expansion coefficient, fatigue life, and hysteresis energy. The accumulated fatigue damage is then estimated as the product of hysteresis energy and fatigue life. The models for γ’ precipitate size, thermal expansion coefficient, and hysteresis energy converge very well and match experimental data accurately. The fatigue life proved to be the most challenging aspect to predict, and fracture mechanics proved to potentially be a necessary supplement to neural networks. The model for fatigue life converges well, but relatively large errors are observed partly due to the generally large statistical variations inherent to fatigue life. The deformation mechanism map for 1.23Cr-1.2Mo-0.26V rotor steel has been constructed using dislocation glide, grain boundary sliding, and power law creep rate equations. The constructed map is verified with experimental data points and neural network results. Although the existing set of experimental data points for neural network modeling is limited, there is an excellent match with boundaries constructed using rate equations which validates the deformation mechanism map.