<p>  </p> <p>The fundamental theory of the glass transition and the glassy state does not exist. Instead, over the years of research there have accumulated a vast number of experimental observations and phenomenological models developed in order to rationalize these observations. A case in point is the stress-strain behavior of a polymer glass during large constant strain rate deformation; for every feature of the stress-strain curve, such as yield, post-yield softening and post-yield hardening, a new mechanism is postulated. But do these mechanisms have a physical basis or are they merely curve-fits? The experiments included in this dissertation are purposefully designed to challenge the prevailing model assumptions. Four specific areas have been chosen: (1) the linear viscoelastic behavior above the glass transition temperature, Tg, (2) the effect of physical aging on the relaxation response of the glassy polymers well below Tg, (3) the behavior of the glassy polymers during a multi-step non-linear deformation, and (4) the effect of the large deformation of the glassy polymer on the enthalpy relaxation as measured by the DSC.</p> <p>(1) Linear viscoelastic isotherms were analyzed by performing dynamic mechanical analysis on a thermoset epoxy, EPON1009F-MDA (Tg: 102.5°C). Storage and loss moduli for the material were investigated for isotherms ranging from 90°C (Tg-12°C) to 180°C (Tg+78°C) for frequencies ranging from 10-2 Hz to 101.7 Hz. This linear viscoelastic dataset was augmented by performing stress relaxation experiments on the same material for temperatures ranging from 90°C (Tg-12°C) to 112.5°C (Tg+10.5°C). The transient results from the stress relaxation (SR) were converted to frequency domain. The resulting augmented dataset spanned 6 order of magnitude in frequency. The wide frequency window showed that the material is thermo-rheologically complex, precluding the creation of a master curve via horizontal shifting of the isotherms. This renders impossible the use of time-temperature superposition, and thus highlights the need for reevaluating its prominent use in glass studies.</p> <p>(2) Existing beliefs on the diminishing effects of physical aging at low temperatures were studied. Linear viscoelastic isotherms of EPON825-MDA (Tg: 182°C) that have been annealed for 2 to 600 hours at temperature ranging from -100°C (Tg-282°C) to 185°C (Tg+3°C) were investigated. At temperatures near Tg, no tangible effects of annealing were identified. At the lowest temperature of -100°C, no differences could be identified between 2 hour and 6 hour annealed specimens; however, annealing effects could possibly be observed at longer aging times based on the results of other isotherms. For all other isotherms between -50°C to 170°C, clear differences could be observed between 2 hour and 6 hour annealed specimens, where the storage moduli increased while the loss moduli decreased. In addition, the effects of annealing were unidentifiable when the material went through a temperature up-jump, but persisted when the material went through a temperature down-jump. The results of this study show that contrary to popular belief, annealing effects are not frozen and persist deep in the glass state and is observable even within experimental limits. Additionally, deep glass aging is fundamentally different from physical aging in that no master curve can be achieved via horizontal shifting along the frequency axis unlike physical aging, due to the change in shape and magnitude of the isotherms.</p> <p>(3) Many constitutive models that target prediction of mechanical behaviors are drawn from the results of single step deformation experiments. Multi-step non-linear deformation experiments were performed on a copolymer of PBMA and PMMA, to challenge the existing models, where the last step is a constant-strain-rate loading step that shows the effects of previous deformation histories on the stress overshoot. Various multi-step deformation histories were investigated, one being a sequence of constrain-strain-rate-loading/unload/creep/constant-strain-rate-loading. Contrary to previous literature reports, the results showed a dependence on the creep stress level of the last overshoot, which initially increased in peak magnitude with creep stress, reached a maximum, and decreased for further increase in creep stress. These results are not qualitatively predicted by any of the existing constitutive models, illustrating the need to rethink how the mechanisms behind stress-strain behaviors are approached. A new toy model is also discussed that can qualitatively predict these results as well as the results of other multi-step deformation histories that are discussed.</p> <p>(4) A new methodology for analysis of the differential scanning calorimetry (DSC) traces was proposed. The DSC trace is known to be sensitive to the thermo-mechanical history a material is subjected to prior to the DSC test; but, the true effects are convoluted with the experimental scatter. The conventional method consists in shifting of the data obtained for different thermo-mechanical histories to the same glassy asymptote, but this has no physical basis. In fact, we argue that this misses the actual effects. We propose that the shifting must be to match the liquid, i.e., equilibrium, asymptote as it is in the equilibrium state which is independent of the history. The new methodology was used to confirm literature reports on the effects of aging. DSC scans of deformed specimens were also studied, where the results showed a systematic effect in the heat capacity traces of deformed specimens, where an endothermic peak followed by an exothermic peak is observed. The peaks are not present in the case of an undeformed material, where a larger degree of strain led to a larger endothermic peak. The results indicate the possibility of a systematic effect where the magnitudes of the additional endothermic and exothermic peaks are controlled by the amount of mechanical work performed during the deformation.</p>

Neste trabalho consideramos o modelo de Potts na árvore de Cayley submetida a um campo magnético. Esse campo pode ser representado pela interação dos spins da árvore com um spin adicional, denominado spin fantasma. Essa nova rede passa a ser chamada de árvore de Cayley fechada e assimétrica. Sendo uma rede hierárquica, ela representa soluções exatas que são obtidas quando as técnicas do grupo de renormalização no espaço real são aplicadas. Subtraindo os efeitos de superfície e considerando somente o interior da árvore (rede de Bethe), esses resultados reproduzem os resultados da aproximação de campo médio de Bethe-Peierls. Com a finalidade de estudar a função de correlação do modelo de Potts na rede de Bethe, consideramos primeiramente uma cadeia de Potts interagindo com um spin fantasma. Através das regras de composição em série e paralelo e do método da quebra e colapso para as trasmissividades térmicas (função de correlação) obtemos uma fórmula de recorrência para a função de correlação entre quaisquer dois spins na cadeia. Mostramos então que pela invariança translacional da rede de Bethe qualquer par de spins pode ser mapeado no sistema anterior. A seguir consideramos o modelo de Potts de um estado na árvore de Cayley fechada e assimétrica. Decimando os spins interiores da unidade geradora da rede, obtemos um mapa polinomial quadrático para a transformação do grupo de renormalização (mapa de Bethe-Peierls). O diagrama de fase desse sistema é então obtido do conjunto de Mandelbrot através de uma transformação de Mobius. O mapa de Bethe-Peierls apresenta dois pontos fixos, que são relacionados com as fases ferro e paramagnética e o regime caótico é identificado com a fase vidro de spin. Esse sistema revela ser o exemplo mais simples de vidro de spin de McKay-Berker-Kirkpatrick. Na rede de Bethe e a campo nulo esse sistema apresenta transições de fase de segunda ordem. Analisando o comportamento crítico da função de correlação e de suas derivadas, vemos que se identificarmos a função de correlação entre o spin fantasma e qualquer spin da rede com a magnetização (por spin) e a função de correlação entre dois spins primeiros vizinhos com a energia interna do sistema, cinco expoentes críticos ((&#948, &#946, &#947 &#8217, &#945, &#945 &#8217) são calculados e satisfazem as relações de escala. Para ilustrar o procedimento recursivo apresentado para calcular a função de correlação entre dois spins separados por ligações m na rede de Bethe, consideramos os spins de Potts de um estado. Obtemos então de forma explícita as correlações para m=1, 2 e 3.0 / In this work we consider the Potts model on the Cayley tree subjected to a magnetic Field. This field can be represented by the interaction of the tree spins with an additional one, denominated ghost spin. This new lattice is then called closed-asymmetric Cayley tree. Being a hierarchical lattice it comes to have exact solutions which are obtained when the real-space renormalization group techniques are applied. Subtracting the surface effects and considering only the tree interior (Bethe lattice), these results reproduce the results of Bethe-Peierls mean-field approximation. With the objective of studying the pair-correlation function of the Potts model on the Bethe lattice, we at first consider a Potts chain interacting with a ghost spin. Throughout the series-parallel composition rules and the break-collapse method for the thermal transmissivities (pair-correlation function) we obtain a recursive relation for the correlation function between any two spins on the chain. We then show, due to the translational invariance of the Bethe lattice, that any pair of spins can be mapped into the latter system. Next we consider the one-state Potts model on the closed asymmetric tree. Decimating the inner spins of the generating unit for the lattice, we obtain a quadratic polynomial map for the renormalization group transformation (Bethe-Peierls map). The phase diagram of this system is obtained from the Mandelbrot set throughout a Mobius transformation. The Bethe-Peierls map has two stable fixed points which are related to the ferro and paramagnetic phases and the chaotic regime is identified with the spin-glass phase. This system turns out to be the simplest example of a McKay-Berker-Kirkpatrick spin glass. On the Bethe lattice with vanishing field this system presents second-order phase transitions. Analyzing the critical behavior of the pair-correlation function and of this derivatives, we see that if we identify the correlation function between the ghost spin and any spin on the lattice with the magnetization (per spin), and the correlation function between two nearest-neighbor spins with the internal energy of the system, five critical exponents (&#948, &#946, &#947 &#8217, &#945, &#945 &#8217) are calculated and they satisfy the scaling relations. In order to illustrate the recursive procedure presented to calculate the pair-correlation function between spins m bonds apart on the Bethe lattice, we consider the one-state Potts spins. We obtain explicitly the correlation for m=1, 2 and 3.

Neste trabalho consideramos o modelo de Potts na árvore de Cayley submetida a um campo magnético. Esse campo pode ser representado pela interação dos spins da árvore com um spin adicional, denominado spin fantasma. Essa nova rede passa a ser chamada de árvore de Cayley fechada e assimétrica. Sendo uma rede hierárquica, ela representa soluções exatas que são obtidas quando as técnicas do grupo de renormalização no espaço real são aplicadas. Subtraindo os efeitos de superfície e considerando somente o interior da árvore (rede de Bethe), esses resultados reproduzem os resultados da aproximação de campo médio de Bethe-Peierls. Com a finalidade de estudar a função de correlação do modelo de Potts na rede de Bethe, consideramos primeiramente uma cadeia de Potts interagindo com um spin fantasma. Através das regras de composição em série e paralelo e do método da quebra e colapso para as trasmissividades térmicas (função de correlação) obtemos uma fórmula de recorrência para a função de correlação entre quaisquer dois spins na cadeia. Mostramos então que pela invariança translacional da rede de Bethe qualquer par de spins pode ser mapeado no sistema anterior. A seguir consideramos o modelo de Potts de um estado na árvore de Cayley fechada e assimétrica. Decimando os spins interiores da unidade geradora da rede, obtemos um mapa polinomial quadrático para a transformação do grupo de renormalização (mapa de Bethe-Peierls). O diagrama de fase desse sistema é então obtido do conjunto de Mandelbrot através de uma transformação de Mobius. O mapa de Bethe-Peierls apresenta dois pontos fixos, que são relacionados com as fases ferro e paramagnética e o regime caótico é identificado com a fase vidro de spin. Esse sistema revela ser o exemplo mais simples de vidro de spin de McKay-Berker-Kirkpatrick. Na rede de Bethe e a campo nulo esse sistema apresenta transições de fase de segunda ordem. Analisando o comportamento crítico da função de correlação e de suas derivadas, vemos que se identificarmos a função de correlação entre o spin fantasma e qualquer spin da rede com a magnetização (por spin) e a função de correlação entre dois spins primeiros vizinhos com a energia interna do sistema, cinco expoentes críticos ((&#948, &#946, &#947 &#8217, &#945, &#945 &#8217) são calculados e satisfazem as relações de escala. Para ilustrar o procedimento recursivo apresentado para calcular a função de correlação entre dois spins separados por ligações m na rede de Bethe, consideramos os spins de Potts de um estado. Obtemos então de forma explícita as correlações para m=1, 2 e 3.0 / In this work we consider the Potts model on the Cayley tree subjected to a magnetic Field. This field can be represented by the interaction of the tree spins with an additional one, denominated ghost spin. This new lattice is then called closed-asymmetric Cayley tree. Being a hierarchical lattice it comes to have exact solutions which are obtained when the real-space renormalization group techniques are applied. Subtracting the surface effects and considering only the tree interior (Bethe lattice), these results reproduce the results of Bethe-Peierls mean-field approximation. With the objective of studying the pair-correlation function of the Potts model on the Bethe lattice, we at first consider a Potts chain interacting with a ghost spin. Throughout the series-parallel composition rules and the break-collapse method for the thermal transmissivities (pair-correlation function) we obtain a recursive relation for the correlation function between any two spins on the chain. We then show, due to the translational invariance of the Bethe lattice, that any pair of spins can be mapped into the latter system. Next we consider the one-state Potts model on the closed asymmetric tree. Decimating the inner spins of the generating unit for the lattice, we obtain a quadratic polynomial map for the renormalization group transformation (Bethe-Peierls map). The phase diagram of this system is obtained from the Mandelbrot set throughout a Mobius transformation. The Bethe-Peierls map has two stable fixed points which are related to the ferro and paramagnetic phases and the chaotic regime is identified with the spin-glass phase. This system turns out to be the simplest example of a McKay-Berker-Kirkpatrick spin glass. On the Bethe lattice with vanishing field this system presents second-order phase transitions. Analyzing the critical behavior of the pair-correlation function and of this derivatives, we see that if we identify the correlation function between the ghost spin and any spin on the lattice with the magnetization (per spin), and the correlation function between two nearest-neighbor spins with the internal energy of the system, five critical exponents (&#948, &#946, &#947 &#8217, &#945, &#945 &#8217) are calculated and they satisfy the scaling relations. In order to illustrate the recursive procedure presented to calculate the pair-correlation function between spins m bonds apart on the Bethe lattice, we consider the one-state Potts spins. We obtain explicitly the correlation for m=1, 2 and 3.

Beaucoup de personnes voient la chimie comme un sujet abstrait et difficile parce qu’elle concerne l’´étude d’éléments invisibles à l’oeil nu. Mais, en y réfléchissant, la chimie est partout ! Des processus chimiques se déroulent tout autour de nous et aussi en nous tous les jours : dans le corps humain où les protéines jouent un grand rôle, dans les bouteilles de shampoing, dans le dentifrice, dans le ciment utilisé pour bâtir les maisons... Cela ne devrait donc être une surprise pour personne qu’autant d’efforts soient employés dans l'étude des processus chimiques.Qu’elles sont ces espèces invisibles avec lesquelles la chimie fonctionne ? Je pense pouvoir affirmer avec peu de doutes que vous avez tous entendu parler des atomes et des molécules (qui sont un assemblage d’atomes). Atomes et molécules ne sont pas toujours des espèces neutres, c’est-`a-dire, elles peuvent porter une charge électrique (dans ce cas, les atomes sont appelés desions). Cette transformation d’une espèce chargée à une espèce neutre peut se dérouler lorsque la particule est plongée dans un solvant (comme l’eau).C’est le cas par exemple lorsque l’on met du sel dans l’eau et que des ions sont formés. Les exemples de particules qui deviennent chargées dans unsolvant sont nombreux: protéines, virus, polyélectrolytes ... Mais pourquoi cette charge électrique est elle si importante ? Comme pour les aimants, où lepôle positif attire le négatif, les espèces vont commencer à interagir selon leur charge. Parmi d’autres facteurs, tel que la forme de la particule, le rôle joué par les charges dans les processus chimiques est primordial. La physico-chimie se concentre sur la compréhension du comportement de telles petites particules (appelées particules colloïdales) lorsqu’elles sont immergées dans une solution. Néanmoins, à cette échelle, l’étude expérimentale des dispersions colloïdales n’est pas triviale. Dans ce contexte, les simulations informatiques se trouvent être très utile. Elles ont pour but, par l’emploi de modèles physiques et mathématiques, d’essayer de reproduire les résultats obtenus expérimentalement et d’accéder à des valeurs qu’aucunes autres techniques ne peuvent procurer. Elles sont donc complémentaires aux expériences. Cette thèse traite de simulations moléculaires, réalisées `a l’aide de l’algorithme de Metropolis, de particules minérales en forme de disques. Dans un premier projet, l’évolution du nombre de charges sur une particule en fonction de la concentration en sel est étudiée. Dans un second temps, l’influence de la charge portée par les particules sur la formation des phases de gels et de cristaux liquides est examinée. Un des résultats les plus marquant est la découverte de nouvelles phases de cristaux liquides qui pourraient permettre le développement de nouveaux matériaux. Enfin, la croissance de nanoparticules et leurs interactions sont étudiées dans des conditions similaires à celles rencontrées dans les pâtes de ciment. [résumé simplifié] / A considerable amount of mineral particles are found to have a plate-like shape. The work in this thesis concerns theoretical investigations, using a Monte Carlo method, of the properties of such particles in aqueous solutions. The objectives were first to create a model that could capture the essential physics of clay suspensions and also to understand the role of thermodynamics in certain chemical processes. For all investigations, the results are related to experimental studies. The acid-base behavior of clays have been studied, using the primitive model, and an excellent agreement between simulated and experimental results was found. The formation of gel phases as a function of the charge anisotropy have also been investigated. Liquid-gel and sol-gel transitions are found to occur for high and moderate charge anisotropy, respectively. These transitions were also found to be size and salt dependent. In absence of charge anisotropy, a liquid-glass transition is reported. The formation of smectic and columnar liquid crystals phases with plate-like particles has been found to be favored by a strong charge anisotropy, in opposition to what was observed for nematic phases. New liquid-crystal phases were also reported. The stability and growth of nanoplatelets is discussed. It was found that the internal Coulombic repulsion could be the cause of the limited growth of C-S-H platelets. The influence of thermodynamics on the agregation mode of such platelets was also investigated / De flesta ser nog kemi som ett abstrakt och komplicerat ämne mestadels föratt det behandlar byggstenar så små att de inte kan ses med blotta ögat. Menom man tänker på det så finns kemi överallt ! Kemiska processer sker runtomoch inuti oss oavbrutet : i våra kroppar där proteiners kemi spelar en stor roll,i produkter som schampo och tandkräm, i cement som används för att byggavåra hus etc. Det borde därför inte komma som någon stor överraskning attenormt mycket resurser läggs på att förstå olika kemiska processer.Så vad är då dessa osynliga beständsdelar som kemi handlar om? Jag trormig våga påstå att alla någon gång hört talas om atomer och molekyler(varav de senare utgörs av en grupp sammanlänkade atomer). Atomer ochmolekyler är inte alltid neutrala, d.v.s., dom kan bära en elektrisk laddning.Övergången från en neutral till en elektriskt laddad enhet kan exempelvis skenär atomer eller molekyler kommer i kontakt med ett lösningsmedel, vilketär fallet när ett salt löses upp i vatten och blir till fria joner. Fler exempelpå molekyler som blir laddade i vatten är proteiner, virus, polyelektrolyteretc. Liksom magneters positiva och negativa poler attraherar varandra, kommerden erhållna elektriska laddningen i molekyler spela en viktig roll förhur dessa interagerar. Bland många andra faktorer såsom tex partikelgeometrin,spelar laddningen en primär roll i kemiska processer. Fysikaliskkemi fokuserar på att förstå de processer som äger rum när så kallade kolloidalapartiklar interagerar i en lösning under olika förhållanden. Att utföraexperiment med partiklar i storleksordningen 1-1000 nanometer är inte trivialt.Här kommer beräkningskemin in som en kraftfullt komplement. Genomatt använda matematiska och fysikaliska modeller, så eftersträvar man attsimulera de experimentellt erhållna resultaten och samtidigt förstå de underliggandemekanismerna och drivkrafterna på en nivå som ej är möjlig pånågot annat sätt.Den här avhandlingen behandlar Monte Carlo-simuleringar av diskformademineralpartiklar. I första projektet undersöktes hur antalet laddningar på diskformad mineralpartikel varierar som funktion av pH i en saltlösning avolika koncentrationer. Därefter studerades hur denna laddningsfördelningpåverkar bildandet av geler och flytande kristallina faser. Genom dennastudie upptäcktes nya termodynamiskt stabila faser vilket kan leda till utvecklandetav nya material. Slutligen så studerades tillväxten av diskformadenanopartiklar och deras interaktioner under förhållande jämförbara med deförekommande i en cementblandning [populärvetenskaplig sammanfattning på svenska]

In this PhD research the liquid-liquid phase separation phenomena in Gd-based alloys was investigated in terms of phase equilibria, microstructure formation upon quenching the melt and corresponding magnetic properties of phase-separated metallic glasses. The phase diagrams of the binary subsystems Gd-Zr and Gd-Ti were experimentally reassessed. Especially the phase equilibria with the liquid phase could be determined directly by combining in situ high energy synchrotron X-ray diffraction with electrostatic levitation of the melt. The Gd-Zr system is of eutectic type with a metastable miscibility gap. The eutectic composition at 18 ± 2 at.% Zr, the liquidus line and the coexistence of bcc-Zr and bcc-Gd at elevated temperature could be determined. The Gd-Ti system is a monotectic system. The experimental observations in this work led to improved new Gd-Zr and Gd-Ti phase diagrams. The phase equilibria of the ternary Gd-Ti-Co system were analyzed for two alloy compositions. The XRD patterns for molten Gd35Ti35Co30 gave direct evidence for the coexistence of two liquid phases formed by liquid-liquid phase separation. The first experimental and thermodynamic assessment of the ternary Gd–Ti–Co system revealed that the stable miscibility gap of binary Gd–Ti extends into the ternary Gd–Ti–Co system (up to about 30 at.% Co). New phase-separated metallic glasses were synthesized in Gd-TM-Co-Al (TM = Hf, Ti or Zr) alloys. The microstructure was characterized in terms of composition and cooling rate dependence of phase separation. Due to large positive enthalpy of mixing between Gd on the one side and Hf, Ti or Zr on the other side, the alloys undergo liquid-liquid phase separation during rapid quenching the melt. The parameters determining the microstructure development during phase separation are the thermodynamic properties of the liquid phase, kinetic parameters and quenching conditions. By controlling these parameters and conditions the microstructure can be tailored both at microscopic and macroscopic length scales. This includes either droplet-like or interconnected microstructures at the microscopic level and glass-glass or glass-crystalline composites at the macroscopic level. Essential parameter for the quenched in microstructure is the temperature dependence of liquid-liquid phase separation, which is determined by the chemical composition of the alloy: on the one hand, earlier and/or later stages of spinodal decomposition or almost homogeneous glassy states are obtained if the critical temperature of miscibility gap Tc is close to the glass transition temperature Tg; and on the one hand, coarsening and secondary precipitations of the liquids are obtained if Tc is much higher than Tg. Finally, the influence of the microstructure developed by phase separation on their magnetic properties had been investigated. The saturation magnetization σS depends on the overall amount of Gd atoms in the alloys and is not remarkably affected by phase separation processes. The Curie temperature TCurie of the magnetic transition is influenced by the changed chemical composition of the Gd-rich glassy phases compared to that of monolithic Gd-Co-Al glasses. / In dieser Doktorarbeit wurde die flüssig-flüssig Phasenentmischung von Gd-basierten Legierungen hinsichtlich der Phasengleichgewichte, der Gefügeentwicklung während der Schmelzabschreckung und dazugehöriger magnetischer Eigenschaften, untersucht. Die Zustandsdiagramme der binären Untersysteme Gd-Zr undGd-Ti wurden experimentell ermittelt.. Insbesondere konnten die Phasengleichgewichte mit der flüssigen Phase mittels in-situ Röntgenbeugungsmessunngen an elektrostatisch levitierten Schmelzen direkt, bestimmt werden. Das Gd-Zr System stellt ein ein eutektisches Phasendiagram dar und besitzt eine metastabile Mischungslücke. Die eutektische Zusammensetzung wurde mit 18 ± 2 at.%Zr bestimmt und der Verlauf der Liquiduslinie bei erhöhten Temperaturen wurde experimentell ermittelt. Experimentell wurde die Koexistenz von kubisch-raumzentrierten Zr und Gd in einem Bereich bei hohen Temperaturen nachgewiesen. Das Gd-Ti-System ist von monotektischer Art. Die experimentellen Beobachtungen dieser Arbeit trugen wesentlich zur Verbesserung der Beschreibung der Phasendiagaramme Gd-Zr- und Gd-Ti-Phasenbei. Die Phasengleichgewichte des ternären Gd-Ti-Co-Systems wurde anhand zweier Legierungszusammensetzungen untersucht. Die Röntgenbeugungsdiffraktogramme der geschmolzenen Legiereung Gd35Ti35Co30 sind ein direkter Beleg für die Koexistenz zweier flüssiger Phasen, aufgrund der flüssig-flüssig Phasenentmischung. Die erste experimentelle und thermodynamische Auswertung des ternären Gd-Ti-Co-Systems zeigt, dass sich die stabile Mischungslücke des binären Gd-Ti-Systems ins ternäre Gd-Ti-Co-System bis zu ungefähr 30 at.% Co erstreckt. Es wurden neue Gd-TM-Co-Al (TM = Hf, Ti oder Zr)-basierte metallische Gläser, die separierte Phasen besitzen, hergestellt. Ihr Gefüge wurden hinsichtlich Zusammensetzung- und Abkühlratenabhängigkeit der Phasenentmischung charakterisiert. Aufgrund der großen positiven Mischungsenthalpie zwischen Gd auf der einen und Hf, Ti oder Zr auf der anderen Seite, weisen diese Legierungen eine flüssig-flüssig Phasenentmischung während der Abschreckung aus der Schmelze auf. Die Einflussgrößen, die die Gefügeentwicklung während der Phasenentmischung bestimmen, sind die thermodynamischen Eigenschaften der flüssigen Phase, die kinetische Parameter und die Abschreckbedingungen. Indem diese Parameter und Bedingungen kontrolliert werden, kann das Gefüge auf makro- sowie mikroskopischer Längenskala maßgeschneidert werden. Dies beinhaltet entweder tropfenförmige oder miteinander verbundene Gefüge auf einer mikroskopischen Skala und Glas-Glas oder Glas-Kristall Komposite auf einer makroskopischen Längenskala. Ein wesentlicher Parameter für das abgeschreckte Gefüge ist die Temperatur-Abhängigkeit der flüssig-flüssig Phasenentmischung, die durch die chemische Zusammensetzung der Legierung bestimmt wird. Frühere und/oder spätere Stadien der spinodalen Entmischung oder nahezu homogene amorphe Zustände können abhängig von dem Temperaturunterschied zwischen kritischer Temperatur der flüssig-flüssig Phasenentmischung und der Glasübergangstemperatur erhalten werden. Wenn die kritische Temperatur der Mischungslücke, Tc, viel höher ist als die des Glasübergangs, Tg, können makroskopische Vergröberungen der tropfenförmigen Verteilung der flüssigen Phase und sekundäre flüssige oder kristalline Ausscheidungen in den gebildeten amorphen Phasen erhalten werden. Durch die Phasenentmischung und die erhaltenen heterogenen Gefüge werden die magnetischen Eigenschaften beeinflusst.. Die Sättigungsmagnetisierung,σS, hängt von der gesamten Anzahl der Gd-Atome der Legierung ab und wird nicht bemerkenswert vom Phasenentmischungsprozess beeinflusst. Die Curie Temperatur TCurie wird im Vergleich zu monolithischen Gd-Co-Al Gläsern, und abhängig von der chemischen Zusammensetzung der Gd-reichen Phase, verändert.

A considerable amount of mineral particles are found to have a plate-like shape. The work in this thesis concerns theoretical investigations, using a Monte Carlo method, of the properties of such particles in aqueous solutions. The objectives were first to create a model that could capture the essential physics of clay suspensions and also to understand the role of thermodynamics in certain chemical processes. For all investigations, the results are related to experimental studies. The acid-base behavior of clays have been studied, using the primitive model, and an excellent agreement between simulated and experimental results was found. The formation of gel phases as a function of the charge anisotropy have also been investigated. Liquid-gel and sol-gel transitions are found to occur for high and moderate charge anisotropy, respectively. These transitions were also found to be size and salt dependent. In absence of charge anisotropy, a liquid-glass transition is reported. The formation of smectic and columnar liquid crystals phases with plate-like particles has been found to be favored by a strong charge anisotropy, in opposition to what was observed for nematic phases. New liquid-crystal phases were also reported. The stability and growth of nanoplatelets is discussed. It was found that the internal Coulombic repulsion could be the cause of the limited growth of C-S-H platelets. The influence of thermodynamics on the agregation mode of such platelets was also investigated

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / A espectroscopia fotoacústica (PAS) é uma técnica não destrutiva e muito utilizada na caracterização óptica e térmica de materiais. Ela é baseada no efeito fotoacústico que consiste, basicamente, na absorção de onda eletromagnética modulada e na geração de calor no interior do material em estudo (amostra), via processo de desexcitação não-radiativa. Dentre as muitas aplicações relacionadas à caracterização de materiais, recentemente, a técnica PAS vem sendo desenvolvida para estudos de transição de fase de segunda ordem. Entretanto, poucos trabalhos são encontrados na literatura com relação à aplicação da técnica PAS ao estudo da transição vítrea. Neste contexto, o objetivo deste trabalho é o de aplicar a técnica PAS na determinação da temperatura de transição vítrea de materiais poliméricos, de uma maneira inovadora com relação à célula fotoacústica e ao sistema de aquecimento. Para isso foi projetada e construída uma célula fotoacústica que possibilita a variação de temperatura da amostra, sem afetar a curva de resposta do microfone. Foi desenvolvido um sistema de aquecimento baseado no efeito Peltier, possibilitando fazer rampas de subida de temperatura, com várias velocidades, da temperatura ambiente até 130 C, de forma linear. Todo o aparato experimental foi testado e aplicado em várias amostras poliméricas: poliamida 6.0 (Nylon); poliestireno (PS-n1921 e PS-n2380); e poli(tereftalato de etileno) (PET). Os resultados obtidos foram: para o Nylon, ; para o PS-n1921, ; para o PS-n2380, ; e para o PET, . Estes resultados estão de acordo com os respectivos valores da temperatura de transição vítrea encontrados na literatura e mostram a potencialidade da técnica PAS ao estudo da transição vítrea de materiais poliméricos. / Photoacoustic spectroscopy (PAS) is a non-destructive technique and it has been largely applied to the thermal and optical characterization of materials. PAS technique is based on the photoacoustic effect which consist, basically, absorption of a modulated electromagnetic radiation and generation of heat inside of the material studied (sample), by a nonradiative deexcitation processes. Nowadays, among many PAS applications, effort are carried out to apply PAS technique for second-order phase transitions. However, only a few works can be found in the literature about glass transition studies with PAS technique. In this context, the main goal of this work is to apply PAS technique to determine glass transition temperature of the polymeric materials, based on the new photoacoustic cell configuration and on the new heating system. In this way, a photoacoustic cell was builted up for monitoring temperature variation of the sample, where the performance of the microphone was not affected. A heating system was developed based on the Peltier effect, in such way that it is possible to scan the temperature from the environment one up to 130 C, linearly at several speeds. The experimental apparatus was tested and applied to some polymeric materials: polyamide 6.0 (Nylon); polystyrene (PS-n1921 e PS-n2380); and poli(tereftalato de etileno) (PET). The results obtained were: Nylon, ; PS-n1921, ; PS-n2380, ; and PET, . These results are in a good agreement with the respective values of glass transition temperature found in the literature and show the PAS technique potentiality for glass transition studies in polymeric materials.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / A espectroscopia fotoacústica (PAS) é uma técnica não destrutiva e muito utilizada na caracterização óptica e térmica de materiais. Ela é baseada no efeito fotoacústico que consiste, basicamente, na absorção de onda eletromagnética modulada e na geração de calor no interior do material em estudo (amostra), via processo de desexcitação não-radiativa. Dentre as muitas aplicações relacionadas à caracterização de materiais, recentemente, a técnica PAS vem sendo desenvolvida para estudos de transição de fase de segunda ordem. Entretanto, poucos trabalhos são encontrados na literatura com relação à aplicação da técnica PAS ao estudo da transição vítrea. Neste contexto, o objetivo deste trabalho é o de aplicar a técnica PAS na determinação da temperatura de transição vítrea de materiais poliméricos, de uma maneira inovadora com relação à célula fotoacústica e ao sistema de aquecimento. Para isso foi projetada e construída uma célula fotoacústica que possibilita a variação de temperatura da amostra, sem afetar a curva de resposta do microfone. Foi desenvolvido um sistema de aquecimento baseado no efeito Peltier, possibilitando fazer rampas de subida de temperatura, com várias velocidades, da temperatura ambiente até 130 C, de forma linear. Todo o aparato experimental foi testado e aplicado em várias amostras poliméricas: poliamida 6.0 (Nylon); poliestireno (PS-n1921 e PS-n2380); e poli(tereftalato de etileno) (PET). Os resultados obtidos foram: para o Nylon, ; para o PS-n1921, ; para o PS-n2380, ; e para o PET, . Estes resultados estão de acordo com os respectivos valores da temperatura de transição vítrea encontrados na literatura e mostram a potencialidade da técnica PAS ao estudo da transição vítrea de materiais poliméricos. / Photoacoustic spectroscopy (PAS) is a non-destructive technique and it has been largely applied to the thermal and optical characterization of materials. PAS technique is based on the photoacoustic effect which consist, basically, absorption of a modulated electromagnetic radiation and generation of heat inside of the material studied (sample), by a nonradiative deexcitation processes. Nowadays, among many PAS applications, effort are carried out to apply PAS technique for second-order phase transitions. However, only a few works can be found in the literature about glass transition studies with PAS technique. In this context, the main goal of this work is to apply PAS technique to determine glass transition temperature of the polymeric materials, based on the new photoacoustic cell configuration and on the new heating system. In this way, a photoacoustic cell was builted up for monitoring temperature variation of the sample, where the performance of the microphone was not affected. A heating system was developed based on the Peltier effect, in such way that it is possible to scan the temperature from the environment one up to 130 C, linearly at several speeds. The experimental apparatus was tested and applied to some polymeric materials: polyamide 6.0 (Nylon); polystyrene (PS-n1921 e PS-n2380); and poli(tereftalato de etileno) (PET). The results obtained were: Nylon, ; PS-n1921, ; PS-n2380, ; and PET, . These results are in a good agreement with the respective values of glass transition temperature found in the literature and show the PAS technique potentiality for glass transition studies in polymeric materials.