Rozprawy doktorskie na temat „Solid-state phase transformation”

In order to achieve progress in Advanced Steels development came more emphasis in solid state phase transformations are received. For achieving the desired mechanical and corrosion resistance properties in Duplex Stainless Steels (DSS), a precise knowledge of the precipitation kinetics of secondary phases, the morphology of the precipitates and effects of the alloying elements on different properties is needed. A complicated chemical composition and the production technology route make each grade of DSS a unique object for a study. Besides, when the market needs to reduce weight and increase product durability by utilizing Advance Strength Steels, a deeper understanding of their transformations is required. The aim of the present work was to study the main features of phase precipitation in diverse Duplex Stainless Steels grades, including Lean Duplex, Standard and Superduplex. Beside analyze the effects of metallurgical features on the properties of DSS and Advanced High Strength Dual Phase (DP) steels. One of the tasks was to study the effects plastic deformation after heat treatment in diverse duplex grades.
Con lo scopo di ottenere progressi industriali nello sviluppo di Advanced Steels, specie quando le necessità di mercato richiedono una riduzione di peso e un aumento della durabilità è fondamentale una più profonda comprensione delle loro trasformazioni di fase allo stato solido. Nel caso di acciai Inossidabili Duplex (DSS), per raggiungere le proprietà meccaniche desiderate e le proprietà di resistenza alla corrosione, è necessaria la precisa conoscenza della cinetica di precipitazione di fasi secondarie, la morfologia dei precipitati e gli effetti degli elementi alleganti su diverse proprietà. La complessa composizione chimica e la tecnologia di produzione rendono ciascuna tipologia di DSS come un caso di studio unico. L’obbiettivo del presente lavoro è stato quello di studiare le principali caratteristiche delle precipitazioni di fasi secondarie in diversi tipi di acciai inossidabili duplex, comprendendo i Lean Duplex, Standard e altamente legati duplex, ed inoltre di analizzare gli effetti delle caratteristiche metallurgiche sulle proprietà degli Acciai Duplex e Advanced High Strength Steels.

This Ph.D. dissertation explores the solid state chemistry of the AUO4 family of oxides (A = divalent or trivalent cation), addressing the role uranyl bonding and 5f electron chemistry play in influencing their physicochemical properties using high resolution measurement methods and ab initio calculations. The irreversible phase transformation that occurs between the rhombohedral and orthorhombic variants of SrUO4 is examined and demonstrated to be first order and reconstructive. The transformation is shown to involve a sequential reduction and oxidation process related to reducing the activation energy barrier that can be traced to the respective ability and inability for the rhombohedral and orthorhombic variants to host oxygen defects. The defect inventory in AUO4 rhombohedral structures is shown to be modulated by the size of the A site cation. When isostructural rhombohedral CaUO4, α-Sr0.4Ca0.6UO4 and SrUO4 obtain a critical amount of oxygen defects they can access novel reversible symmetry lowering and defect ordering transformations forming phases denoted δ. The transformations are purely thermodynamic where the origin is proposed to be related to decreasing entropy from defect ordering balanced by increasing electronic entropy with heating. AUO4 oxides that had been previously poorly described were examined at high resolution. This includes elucidation of NiUO4 polymorphs which provide the transformative “missing link" between the Pbcn and Ibmm orthorhombic variants. Consequently a structural hierarchy is developed for the family of AUO4 oxides that can be used for structure prediction for specific A and U cations. High pressure studies of SrUO4 found anomalous U-O bond lengthening to occur with increasing pressure related to electron delocalisation. This demonstrates the inapplicability of Badger’s rule to all uranyl bearing compounds. With the structural topology of rhombohedral SrUO4, this lengthening process produces bulk moduli comparable to diamond

Steepest-entropy-ascent quantum thermodynamics (SEAQT) is a mathematical and theoretical framework for intrinsic quantum thermodynamics (IQT), a unified theory of quantum mechanics and thermodynamics. In the theoretical framework, entropy is viewed as a measure of energy load sharing among available energy eigenlevels, and a unique relaxation path of a system from an initial non-equilibrium state to a stable equilibrium is determined from the greatest entropy generation viewpoint. The SEAQT modeling has seen a great development recently. However, the applications have mainly focused on gas phases, where a simple energy eigenstructure (a set of energy eigenlevels) can be constructed from appropriate quantum models by assuming that gas-particles behave independently. The focus of this research is to extend the applicability to solid phases, where interactions between constituent particles play a definitive role in their properties so that an energy eigenstructure becomes quite complicated and intractable from quantum models. To cope with the problem, a highly simplified energy eigenstructure (so-called ``pseudo-eigenstructure") of a condensed matter is constructed using a reduced-order method, where quantum models are replaced by typical solid-state models. The details of the approach are given and the method is applied to make kinetic predictions in various solid-state phenomena: the thermal expansion of silver, the magnetization of iron, and the continuous/discontinuous phase separation and ordering in binary alloys where a pseudo-eigenstructure is constructed using atomic/spin coupled oscillators or a mean-field approximation. In each application, the reliability of the approach is confirmed and the time-evolution processes are tracked from different initial states under varying conditions (including interactions with a heat reservoir and external magnetic field) using the SEAQT equation of motion derived for each specific application. Specifically, the SEAQT framework with a pseudo-eigenstructure successfully predicts: (i) lattice relaxations in any temperature range while accounting explicitly for anharmonic effects, (ii) low-temperature spin relaxations with fundamental descriptions of non-equilibrium temperature and magnetic field strength, and (iii) continuous and discontinuous mechanisms as well as concurrent ordering and phase separation mechanisms during the decomposition of solid-solutions.
Ph. D.
Many engineering materials have physical and chemical properties that change with time. The tendency of materials to change is quantified by the field of thermodynamics. The first and second laws of thermodynamics establish conditions under which a material has no tendency to change; these conditions are called equilibrium states. When a material is not in an equilibrium state, it is able to change spontaneously. Classical thermodynamics reliably identifies whether a material is susceptible to change, but it is incapable of predicting how change will take place or how fast it will occur. These are kinetic questions that fall outside the purview of thermodynamics. A relatively new theoretical treatment developed by Hatsopoulos, Gyftopoulos, Beretta and others over the past forty years extends classical thermodynamics into the kinetic realm. This framework, called steepest-entropy-ascent quantum thermodynamics (SEAQT), combines the tools of thermodynamics with quantum mechanics through a postulated equation of motion. Solving the equation of motion provides a kinetic description of the path a material will take as it changes from a non-equilibrium state to stable equilibrium. To date, the SEAQT framework has been applied primarily to systems of gases. In this dissertation, solid-state models are employed to extend the SEAQT approach to solid materials. The SEAQT framework is used to predict the thermal expansion of silver, the magnetization of iron, and the kinetics of atomic clustering and ordering in binary solid-solutions as a function of time or temperature. The model makes it possible to predict a unique kinetic path from any arbitrary, non-equilibrium, initial state to a stable equilibrium state. In each application, the approach is tested against experimental data. In addition to reproducing the qualitative kinetic trends in the cases considered, the SEAQT framework shows promise for modeling the behavior of materials far from equilibrium.

O presente trabalho teve como objetivo o estudo do estado sólido do ganciclovir (GCV) e suas diferentes formas polimórficas. O GCV é um fármaco antiviral útil no tratamento de infecções por citomegalovírus (CMV). Embora seja um fármaco amplamente usado, poucos estudos têm sido realizados sobre seu estado sólido. Atualmente, o GCV é conhecido por apresentar quatro formas cristalinas, duas anidras (Forma I e II) e duas hidratas (III e IV). Neste trabalho, nós reportamos a solução da estrutura cristalográfica da Forma I do GCV, que foi encontrado durante o screening de cristalização do fármaco, em que nove ensaios de cristalização (GCV-1, GCV-A, GCV-B, GCV-C, GCV-D, GCV-E, GCV-F, GCV-G e GCV-H) foram realizados e os materiais resultantes foram caracterizados por Difratometria de raios X (DRX), análise térmica (DTA/TG) e Hot Stage Microscopy. De todas as cristalizações realizadas foram obtidas quatro formas sólidas, denominadas como Forma I (GCV-1, GCV-B e GCV-H), Forma III (GCV-C, GCV-D, GCV-F e GCV-G), Forma IV (GCV-A) e Forma V (GCV-E). Esta última está sendo descrita pela primeira vez na literatura e indica a presença de outra forma hidratada de GCV. As Formas I, III e IV corresponderam a forma anidra e as duas formas hidratadas do fármaco, respectivamente. Além disso, foi evidenciado por experimentos de conversão de slurry e análise térmica que o cristalizado de GCV-1 (Forma I) foi o mais estável entre os materiais obtidos, e este deu origem ao monocristal da Forma I de GCV, estrutura cristalina anidra do fármaco. Neste trabalho, pela primeira vez, a estrutura cristalina deste composto foi definida por cristalografia de raios X de monocristal. A análise estrutural mostrou que a Forma I do fármaco cristaliza no grupo espacial monoclínico P21/c e está composta por quatro moléculas de GCV na sua unidade assimétrica. Cada molécula está unida intermolecularmente por ligações de hidrogênio, que dão lugar à formação de cadeias infinitas e estas por sua vez se arranjam de maneira a formar uma estrutura tridimensional.
This presented work aims to study the solid state of ganciclovir (GCV) and its different polymorphic forms. GCV is an antiviral drug useful in the treatment of cytomegalovirus (CMV) infections. Although it is a widely-used drug, few studies have been conducted on its solid state. Currently, GCV is known to have four crystalline forms, two anhydrous (Form I and II) and two hydrates (III and IV). In this investigation, we report a successful preparation of GCV Form I and its crystallographic structure, which was found during the crystallization of the drug, in which nine crystallization tests (GCV-1, GCV-A, GCV-B, GCV- D, GCV-E, GCV-F, GCV-G and GCV-H) were performed and the resulting materials were characterized by X-ray diffractometry (XRD), thermal analysis (DTA/TG) and Hot Stage Microscopy. Of all the crystallizations performed, four solid forms were obtained, denoted as Form I (GCV-1, GCV-B and GCV- H), Form III (GCV-C, GCV-D, GCV-F and GCV-G), Form IV (GCV-A) and Form V (GCV-E). The latter is being described for the first time in the literature and indicates the presence of another hydrated form of GCV. Forms I, III and IV corresponded to the anhydrous form and the two hydrated forms of the drug, respectively. In addition, it was evident by both the slurry conversion and the thermal analysis methods that the GCV-1 crystallized (Form I) was indeed the most stable amongst the materials obtained. This gave rise to GCV Form I monocrystal, anhydrous crystalline structure of the drug. The compound was characterized by monocrystal X-ray crystallography. The structural analysis showed that Form I of the drug crystallized in the monoclinic system space group P21/c is composed of four molecules of GCV in its asymmetric unit. Each molecule is linked intermolecularly by hydrogen bonds, which give rise to the formation of infinite chains arranged in a way that form a three-dimensional structure.

Non-stoichiometric strontium iron oxide is described by an abbreviated formula SrFeOx (2.5 ≤ x ≤ 3.0) exhibits a variety of interesting physical and chemical properties over a broad range of temperatures and in different gaseous environments. The oxide contains a mixture of iron in the trivalent and the rare tetravalent state. The material at elevated temperature is a mixed oxygen conductor and it, or its derivatives,can have practical applications in oxygen conducting devices such as pressure driven oxygen generators, partial oxidation reactors in electrodes for solid oxide fuel cells (SOFC). ¶ This thesis examines the behaviour of the material at ambient and elevated temperatures using a broad spectrum of solid state experimental techniques such as: x-ray and neutron powder diffraction,thermogravimetric and calorimetric methods,scanning electron microscopy and Mossbauer spectroscopy. Changes in the oxide were induced using conventional thermal treatment in various atmospheres as well as mechanical energy (ball milling). The first experimental chapter examines the formation of the ferrite from a mixture of reactants.It describes the chemical reactions and phase transitions that lead to the formation of the oxide. Ball milling of the reactants prior to annealing was found to eliminate transient phases from the reaction route and to increase the kinetics of the reaction at lower temperatures. Examination of the thermodynamics of iron oxide (hematite) used for the reactions led to a new route of synthesis of the ferrite frommagnetite and strontium carbonate.This chapter also explores the possibility of synthesis of the material at room temperature using ball milling. ¶ The ferrite strongly interacts with the gas phase so its behaviour was studied under different pressures of oxygen and in carbon dioxide.The changes in ferrite composition have an equilibrium character and depend on temperature and oxygen concentration in the atmosphere. Variations of the oxygen content x were described as a function of temperature and oxygen partial pressure, the results were used to plot an equilibrium composition diagram. The heat of oxidation was also measured as a function of temperature and oxygen partial pressure. ¶ Interaction of the ferrite with carbon dioxide below a critical temperature causes decomposition of the material to strontium carbonate and SrFe12O19 . The critical temperature depends on the partial pressure of CO2 and above the critical temperature the carbonate and SrFe12O19 are converted back into the ferrite.The resulting SrFe12O19 is very resistant towards carbonation and the thermal carbonation reaction does not lead to a complete decomposition of SrFeOx to hematite and strontium carbonate. ¶ The thermally induced oxidation and carbonation reactions cease at room temperature due to sluggish kinetics however,they can be carried out at ambient temperature using ball milling.The reaction routes for these processes are different from the thermal routes.The mechanical oxidation induces two or more concurrent reactions which lead to samples containing two or more phases. The mechanical carbonation on the other hand produces an unknown metastable iron carbonate and leads a complete decomposition of the ferrite to strontiumcarbonate and hematite. ¶ Thermally and mechanically oxidized samples were studied using Mossbauer spectroscopy. The author proposes a new interpretation of the Sr4Fe4O11 (x=2.75) and Sr8Fe8O23 (x=2.875)spectra.The interpretation is based on the chemistry of the compounds and provides a simpler explanation of the observed absorption lines.The Mossbauer results froma range of compositions revealed the roomtemperature phase behaviour of the ferrite also examined using x-ray diffraction. ¶ The high-temperature crystal structure of the ferrite was examined using neutron powder diffraction.The measurements were done at temperatures up to 1273K in argon and air atmospheres.The former atmosphere protects Sr2Fe2O5 (x=2.5) against oxidation and the measurements in air allowed variation of the composition of the oxide in the range 2.56 ≤ x ≤ 2.81. Sr2Fe2O5 is an antiferromagnet and undergoes phase transitions to the paramagnetic state at 692K and from the orthorhombic to the cubic structure around 1140K.The oxidized formof the ferrite also undergoes a transition to the high-temperature cubic form.The author proposes a new structural model for the cubic phase based on a unit cell with the Fm3c symmetry. The new model allows a description of the high-temperature cubic form of the ferrite as a solid solution of the composition end members.The results were used to draw a phase diagramfor the SrFeOx system. ¶ The last chapter summarizes the findings and suggests directions for further research.

The main purposes of this study were; (i) to apply the theory of martensite crystallography to martensitic transformations in low-symmetry materials, (ii) to investigate, using the computer simulation method, the microscopic structure of complex interphase boundaries which are not yet fully understood in terms of the martensitic mechanism. Although the unique symmetry of a twin boundary makes it a rather exceptional kind of interface, it is clearly a particularly appropriate starting point especially due to the role which twinning plays in martensitic transformations. The accuracy of twinning modes is vital for their use as lattice-invariant shears in theories of martensite crystallography. Potential twinning modes for zirconia were determined using the analysis due to Bilby and Crocker (1965) and the associated atomic shuffling was also considered. Twinning orientation relationships involving a screw axis and a glide plane have been established. The theory of martensite crystallography (Acton et al. 1970) was then applied to the tetragonal to monoclinic martensitic transformation in zirconia. The predictions for the habit plane, shape strain and the direction of the shape deformation were obtained and compared with available experimental observations. The application of the theory was also extended to the face-centred cubic to monocline martensitic transformation in plutonium alloys. The predictions of the crystallographic features for this transformation are reported. The computer simulation method was applied to investigate the relaxed atomic structure and energies of the complex interphase boundaries. The (100)b//(100)f and the (011)b /(111)f interphase boundaries were investigated using interatomic potential. Special consideration was given to the misfit dislocations at the interface which can accomplish the lattice-invariant shear of the phenomenological theories of martensite crystallography. A new equilibrium interatomic potential for iron was developed to study the relaxed structure of the (225)f b. c. c. /f. c. c. interphase boundary. These results are also compared with experimental information. Finally the general results of the thesis are discussed and main conclusions summarized.

Thèse Ecole polytechnique fédérale de Lausanne EPFL, no 4336 (2009), Faculté des sciences et techniques de l'ingénieur STI, Programme doctoral Sciences et Génie des matériaux, Institut des matériaux IMX (Laboratoire de simulation des matériaux LSMX). Dir.: Alain Jacot.

Interpretation de l'abaissement de la pression de fusion lorsque la fusion est plus rapide que le temps de relaxation de la polarisation de **(3)he d'apres l'etude theorique de la morphologie de l'interface liquide-solide lors de la fusion de **(3)he solide polarise. Tendance au metamagnetisme de **(3)he liquide pour une polarisation de equiv. A 20 %, a 0,1 k, et absence d'anomalie dans la vitesse du son mesuree a ce taux de polarisation. Possibilite de refroidir le liquide polarise au-dessus de 0,1 k en un temps tres court compare a celui de la relaxation de polarisation. Etude experimentale des proprietes magnetoelastiques de composes a deux fermions lourds et analyse phenomenologique pour prevoir la magnetostriction, la vitesse du son sous champ magnetique de ces composes pesentant une forte tendance au metamagnetisme, et, aux frequences grandes comparees au taux de relaxation de la polarisation, la vitesse du son

Mise en évidence par mesures de conductivité électrique des transformations structurelles à caractère relaxationnel induites par traitement thermique. Etude des variations de la bande interdite optique. Etude du rôle privilégié de certains centres dans les phénomènes de transport

Solid state materials are candidates to exhibit a large field-driven thermal response in the vicinity of first-order transitions. The strong sensitivity of the transition temperature with the applied field and the latent heat associated with the change of phase can give rise to the giant magneto-, electro-, baro-, and elastocaloric effects. Furthermore, the coupling between structural, magnetic and electronic degrees of freedom at the transition regime enables the thermal response to be driven by multiple fields and, thus, giving rise to the multicaloric effect. In the last years, the interest in understanding and tailoring novel caloric materials has exceptionally grown in view of their potential application to alternative cooling technologies for large scale industry. The present thesis reports the giant caloric effects encompassing the Fe49Rh51 magnetovolumic transition, the magnetostructural martensitic transformation in Ni-Mn based Heusler alloys, and the ferroelectric perovskites BaTiO3 and Pb(Sc0.5Ta0.5)O3. The physical conditions for the optimization of the thermal response which yield to an enlarged magnitude and operation range are explored, as well as the corresponding reproducibility upon field cycling and the potential multicaloric character. This evaluation is achieved by means of a complete caloric characterization in which the calorimetric experimental techniques which have been developed in purpose are crucial.
Els materials d'estat sòlid són susceptibles de mostrar una gran resposta tèrmica induïda per un camp extern a l'entorn de transicions de fase de primer ordre. La forta sensitivitat de la temperatura de transició amb el camp aplicat i la calor latent associada amb el canvi de fase poden donar lloc als efectes magneto-, electro-, baro- i elastocalòric gegants. A més, l'acoblament entre els graus de llibertat estructurals, magnètics i electrònics en el règim de transició possibilita que la resposta tèrmica sigui induïda per múltiples camps, originant així l'efecte multicalòric. En els darrers anys, l'interès en entendre i elaborar materials calòrics ha crescut excepcionalment, amb l'ull posat en les aplicacions potencials en tecnologies de refrigeració alternatives per a la indústria a gran escala. La present tesi reporta els efectes calòrics gegants que acompanyen la transició magnetovolúmica del Fe49Rh51, la transformació martensítica en aliatges Heusler amb base de Ni-Mn, i les perovskites ferroelèctriques de BaTiO3 i de Pb(Sc0.5Ta0.5)O3. S'exploren les condicions físiques propícies per a una optimització de la resposta tèrmica que resulten amb un eixamplament en magnitud i en rang d'operació, així com també la reproducibilitat corresponent sota ciclatge i el potencial caràcter multicalòric. Aquesta avaluació s'aconsegueix per mitjà d'una caracterització calòrica completa en què les tècniques experimentals calorimètriques que s'han desenvolupat amb aquest propòsit són crucials

The surge of interest in multifunctional materials over the past 15 years has been driven by their fascinating physical properties and huge potential for technological applications such as sensors, microwave devices, energy harvesting, photovoltaic technologies, solid-state refrigeration, and data storage recording technologies. Among the others, magnetoelectric multiferroic composites are a special class of advanced solid-state compounds with coupled ferromagnetic and ferroelectric ferroic orders which allow to perform more than one task by combining electronic, magnetic and mechanical properties into a single device component. The production and characterization of lead zirconate titanate (PZT)- cobalt ferrite composites was the main topic of the thesis. During the PhD activity different ceramic processing and characterization technologies were studied and involved in order to optimize the produced materials as a function of the final microstructural and functional properties. The synthesis of cobalt ferrite (CF) and niobium-doped lead zirconate titanate (PZTN) powders by solid state reaction method and sol-gel technique, to control the particle size distributions and their microstructural and functional properties through calcination and milling treatments has been addressed first, followed by the mixing of the PZT and CF powders to produce particulate composites. The dispersion of PZT and CF in a liquid media, to produce layered composites by depositing the particles by electrophoretic deposition was an objective of the work as well. Key issues such as the lead loss during the sintering of PZTN-CF composites and the reaction between CF and titania have been addressed and have resulted in improvements in the sintering and characterization techniques leading to the production of fully dense PZTN-CF dual-particulate composites. In particular, the optimized sintering parameters have configured a new paradigm of ceramic sintering, which has been called quite-fast sintering, in respect to the traditional one, and the study of the PbO loss has led to propose an equation to calculate the PbO loss through XRD analysis. Further important achieved results were: the production of nanocobalt ferrite particles by multi-step milling, the correlation between the spin-canting angle with the microstrain and the average crystallite size of nanocobalt ferrite particles, the understanding of the CF growth mechanisms, the extension of the Globus model from small ferromagnetic grains “having no defect inside” to multiparallel-twinned overgrown ones, the understanding of heating rate effect on the interface nucleation onset of the anatase-to-rutile transformation and the anatase particle size, and the reaction products between CF and rutile at 1200 °C at the variation of CF/rutile ratio.

The aim of this thesis was to find anomalies of elastic properties induced by topological changes of the Fermi surface. The latter are called "Lifshitz transitions". Lifshitz transitions are an interesting subject to study because a topological change of the Fermi surface results in a van Hove singularity of the density of states at the Fermi energy, which again induces an anomaly in the free energy and therefore yield anomalies of observable physical quantities. In all cases the question arose, if the corresponding van Hove singularities are large enough to cause anomalies in the elastic properties, which are measurable by nowadays experimental techniques and computable within the accuracy reachable in nowadays computer calculations. The calculations have been done with the Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure code FPLO. To shift the van Hove singularities through the Fermi energy we used hydrostatic pressure, which is mimicked in the computations by decreasing the volume of the unit cell. The materials under consideration had been YCo5 and LaCo5 as examples for magnetic compounds and the element Osmium as an example for a non-magnetic material. All these materials exhibit hexagonal symmetry. In the case of YCo5 our calculations yield a first order Lifshitz transition. Here, an extraordinarily large peak in the spin-up part of the DOS, which is caused by a nearly dispersionless band in the hexagonal plane, crosses the Fermi level under a pressure of about 21 GPa. Thus, the spin-up 3d states become partly depopulated, which results in a drop of the total magnetic moment of 35%. Therefore the transition can be regarded as a transition from strong to weak ferromagnetism. Further, the transition results in a volume collapse of 1.4%. Though the volume collapse is isomorphic, it exhibits the following anisotropy: while the lattice constant in the hexagonal plane is almost smoothly contracting with increasing pressure, the lattice constant in c-direction collapses at the transition-pressure. This volume collapse has been verified in experiment. Analogous calculations have been performed for the compound LaCo5, which is isoelectronic to YCo5. Here as well we predict a first order Lifshitz transition, taking place at a pressure of about 23 GPa. The mechanism of the transition is the same than in YCo5. Again we find a volume collapse under pressure together with a decrease of the magnetic moment. The relative volume change amounts to 1.3%. Like in YCo5, the unit cell dimensions in the hexagonal plane are decreasing almost smoothly with pressure while in c-direction the lattice constant collapses at the transition-pressure. For LaCo5 there are no such experiments done so far to the best of our knowledge. For Osmium we found, that LDA reproduces the ground state volume very well. Furthermore, we could detect three Lifshitz transitions taking place at very high pressures of about 72 GPa, 81 GPa, and 122 GPa. At first, a hole ellipsoid appears at the Gamma-point (V=24.6Å^3, P=72 GPa), then a neck is created at the symmetry-line LH (V=24.2Å^3, P=81 GPa), and finally a hole ellipsoid appears at the L-point (V=23.2 Å^3, P=122 GPa). Due to a degeneracy in the band structure, the hole ellipsoid at the L-point appears at the same pressure when the necks, situated at the symmetry-lines LH merge at L. The corresponding van Hove singularities in the DOS are very tiny and thus no anomalies in the elastic properties could be detected. Furthermore, we showed that the kink in c/a at 25 GPa and at 27 GPa found by Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] and Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)], respectively, is not statistically significant and that (c/a)(P) can be fitted equally well by a smooth function as by piece-wise linear functions as proposed in these references
Das Ziel dieser Arbeit war es, Anomalien in den elastischen Eigenschaften zu finden, die durch topologische Änderungen der Fermifläche - genannt "Lifschitz Übergänge" - hervorgerufen werden. Lifschitz Übergänge sind ein interessantes Forschungsgebiet, denn die topologische Änderung der Fermifläche führt zu einer van Hove Singularität in der Zustandsdichte, die an der Fermienergie liegt und eine Anomalie in der freien Energie hervorruft und deswegen zu Anomalien in beobachtbaren physikalischen Größen führt. In allen Fällen kam die Frage auf, ob die entsprechenden van Hove Singularitäten groß genug sind, um mit heutigen Methoden meßbare und berechenbare Anomalien in den elastischen Eigenschaften zu verursachen. Die Daten wurden mit dem Computerprogramm FPLO (Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure scheme) berechnet. Um die van Hove Singularitäten durch die Fermienergie zu schieben, verkleinerten wir das Volumen der Einheitszelle, um hydrostatischen Druck zu simulieren. Als zu untersuchende Stoffe wurden YCo5 und LaCo5 als Beispiele für magnetische Verbindungen gewählt und Osmium als Beispiel für ein nicht magnetisches Element. Im Falle von YCo5 fanden wir einen Lifschitz Übergang erster Ordnung. Hier springt ein besonders großer Peak im Spin-auf Teil der Zustandsdichte unter einem Druck von ca. 21 GPa über die Fermienergie. Dadurch werden die Spin-auf 3d Zustände teilweise unbesetzt und das magnetische Moment verringert sich um 35%. Deswegen kann man den Übergang als einen Übergang von starkem Ferromagnetismus zu schwachem Ferromagnetismus bezeichnen. Das Volumen verkleinert sich hierbei um 1.4%. Obwohl dieser Volumenkollaps isomorph ist, zeigt er folgende Anisotropie: während die Gitterkonstante in der hexagonalen Ebene mit zunehmendem Druck mehr oder weniger glatt kontrahiert, kollabiert am Übergangsdruck die Gitterkonstante in c-Richtung. Dieser Volumenkollaps wurde vom Experiment verifiziert. Analoge Rechnungen wurden für die Verbindung LaCo5, die isoelektronisch zu YCo5 ist, durchgeführt. Auch hier sagen wir einen Lifschitz Übergang erster Ordnung voraus, der bei einem Druck von ca. 23 GPa stattfinden wird. Der Mechanismus dieses Übergangs ist der selbe wie in YCo5. Wiederum finden wir einen Volumenkollaps unter Druck zusammen mit einer Verringerung des magnetischen Moments. Die relative Volumenänderung beträgt hier 1.3%. Wie in YCo5 verläuft hier die Kontraktion der Gitterkonstante in der hexagonalen Ebene mehr oder weniger glatt, während die Gitterkonstante in c-Richtung am Übergang kollabiert. Für LaCo5 existieren unseres Wissens hierzu noch keine Experimente. Im Falle von Osmium fanden wir drei Lifschitz Übergänge bei sehr hohen Drücken von ca. 72 GPa, 81 GPa, und 122 GPa. Zuerst bildet sich ein Lochellipsoid am Gamma-Punkt (V=24.6Å^3, P=72 GPa), dann bildet sich ein Hals an der Symmetrielinie LH (V=24.2Å^3, P=81 GPa), und zum Schluß erscheint ein Lochellipsoid am L-Punkt (V=23.2 Å^3, P=122 GPa). Auf Grund einer Entartung in der Bandstruktur taucht das Lochellipsoid am L-Punkt an dem Druck auf, an dem sich auch die Hälse auf der Symmetrielinie LH bei L verbinden. Die entsprechenden van Hove Singularitäten in der Zustandsdichte sind jedoch extrem klein und deswegen können keine Anomalien in den elastischen Eigenschaften detektiert werden. Desweiteren zeigten wir, daß der Knick in c/a, den Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] bei 25 GPa und Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)] bei 27 GPa fanden, statistisch nicht relevant ist und daß (c/a)(P) genauso gut von einer glatten Funktion gefittet wird als von stückweise linearen Funktionen

The aim of this thesis was to find anomalies of elastic properties induced by topological changes of the Fermi surface. The latter are called "Lifshitz transitions". Lifshitz transitions are an interesting subject to study because a topological change of the Fermi surface results in a van Hove singularity of the density of states at the Fermi energy, which again induces an anomaly in the free energy and therefore yield anomalies of observable physical quantities. In all cases the question arose, if the corresponding van Hove singularities are large enough to cause anomalies in the elastic properties, which are measurable by nowadays experimental techniques and computable within the accuracy reachable in nowadays computer calculations. The calculations have been done with the Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure code FPLO. To shift the van Hove singularities through the Fermi energy we used hydrostatic pressure, which is mimicked in the computations by decreasing the volume of the unit cell. The materials under consideration had been YCo5 and LaCo5 as examples for magnetic compounds and the element Osmium as an example for a non-magnetic material. All these materials exhibit hexagonal symmetry. In the case of YCo5 our calculations yield a first order Lifshitz transition. Here, an extraordinarily large peak in the spin-up part of the DOS, which is caused by a nearly dispersionless band in the hexagonal plane, crosses the Fermi level under a pressure of about 21 GPa. Thus, the spin-up 3d states become partly depopulated, which results in a drop of the total magnetic moment of 35%. Therefore the transition can be regarded as a transition from strong to weak ferromagnetism. Further, the transition results in a volume collapse of 1.4%. Though the volume collapse is isomorphic, it exhibits the following anisotropy: while the lattice constant in the hexagonal plane is almost smoothly contracting with increasing pressure, the lattice constant in c-direction collapses at the transition-pressure. This volume collapse has been verified in experiment. Analogous calculations have been performed for the compound LaCo5, which is isoelectronic to YCo5. Here as well we predict a first order Lifshitz transition, taking place at a pressure of about 23 GPa. The mechanism of the transition is the same than in YCo5. Again we find a volume collapse under pressure together with a decrease of the magnetic moment. The relative volume change amounts to 1.3%. Like in YCo5, the unit cell dimensions in the hexagonal plane are decreasing almost smoothly with pressure while in c-direction the lattice constant collapses at the transition-pressure. For LaCo5 there are no such experiments done so far to the best of our knowledge. For Osmium we found, that LDA reproduces the ground state volume very well. Furthermore, we could detect three Lifshitz transitions taking place at very high pressures of about 72 GPa, 81 GPa, and 122 GPa. At first, a hole ellipsoid appears at the Gamma-point (V=24.6Å^3, P=72 GPa), then a neck is created at the symmetry-line LH (V=24.2Å^3, P=81 GPa), and finally a hole ellipsoid appears at the L-point (V=23.2 Å^3, P=122 GPa). Due to a degeneracy in the band structure, the hole ellipsoid at the L-point appears at the same pressure when the necks, situated at the symmetry-lines LH merge at L. The corresponding van Hove singularities in the DOS are very tiny and thus no anomalies in the elastic properties could be detected. Furthermore, we showed that the kink in c/a at 25 GPa and at 27 GPa found by Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] and Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)], respectively, is not statistically significant and that (c/a)(P) can be fitted equally well by a smooth function as by piece-wise linear functions as proposed in these references.
Das Ziel dieser Arbeit war es, Anomalien in den elastischen Eigenschaften zu finden, die durch topologische Änderungen der Fermifläche - genannt "Lifschitz Übergänge" - hervorgerufen werden. Lifschitz Übergänge sind ein interessantes Forschungsgebiet, denn die topologische Änderung der Fermifläche führt zu einer van Hove Singularität in der Zustandsdichte, die an der Fermienergie liegt und eine Anomalie in der freien Energie hervorruft und deswegen zu Anomalien in beobachtbaren physikalischen Größen führt. In allen Fällen kam die Frage auf, ob die entsprechenden van Hove Singularitäten groß genug sind, um mit heutigen Methoden meßbare und berechenbare Anomalien in den elastischen Eigenschaften zu verursachen. Die Daten wurden mit dem Computerprogramm FPLO (Full-Potential nonorthogonal Local-Orbital minimum-basis band-structure scheme) berechnet. Um die van Hove Singularitäten durch die Fermienergie zu schieben, verkleinerten wir das Volumen der Einheitszelle, um hydrostatischen Druck zu simulieren. Als zu untersuchende Stoffe wurden YCo5 und LaCo5 als Beispiele für magnetische Verbindungen gewählt und Osmium als Beispiel für ein nicht magnetisches Element. Im Falle von YCo5 fanden wir einen Lifschitz Übergang erster Ordnung. Hier springt ein besonders großer Peak im Spin-auf Teil der Zustandsdichte unter einem Druck von ca. 21 GPa über die Fermienergie. Dadurch werden die Spin-auf 3d Zustände teilweise unbesetzt und das magnetische Moment verringert sich um 35%. Deswegen kann man den Übergang als einen Übergang von starkem Ferromagnetismus zu schwachem Ferromagnetismus bezeichnen. Das Volumen verkleinert sich hierbei um 1.4%. Obwohl dieser Volumenkollaps isomorph ist, zeigt er folgende Anisotropie: während die Gitterkonstante in der hexagonalen Ebene mit zunehmendem Druck mehr oder weniger glatt kontrahiert, kollabiert am Übergangsdruck die Gitterkonstante in c-Richtung. Dieser Volumenkollaps wurde vom Experiment verifiziert. Analoge Rechnungen wurden für die Verbindung LaCo5, die isoelektronisch zu YCo5 ist, durchgeführt. Auch hier sagen wir einen Lifschitz Übergang erster Ordnung voraus, der bei einem Druck von ca. 23 GPa stattfinden wird. Der Mechanismus dieses Übergangs ist der selbe wie in YCo5. Wiederum finden wir einen Volumenkollaps unter Druck zusammen mit einer Verringerung des magnetischen Moments. Die relative Volumenänderung beträgt hier 1.3%. Wie in YCo5 verläuft hier die Kontraktion der Gitterkonstante in der hexagonalen Ebene mehr oder weniger glatt, während die Gitterkonstante in c-Richtung am Übergang kollabiert. Für LaCo5 existieren unseres Wissens hierzu noch keine Experimente. Im Falle von Osmium fanden wir drei Lifschitz Übergänge bei sehr hohen Drücken von ca. 72 GPa, 81 GPa, und 122 GPa. Zuerst bildet sich ein Lochellipsoid am Gamma-Punkt (V=24.6Å^3, P=72 GPa), dann bildet sich ein Hals an der Symmetrielinie LH (V=24.2Å^3, P=81 GPa), und zum Schluß erscheint ein Lochellipsoid am L-Punkt (V=23.2 Å^3, P=122 GPa). Auf Grund einer Entartung in der Bandstruktur taucht das Lochellipsoid am L-Punkt an dem Druck auf, an dem sich auch die Hälse auf der Symmetrielinie LH bei L verbinden. Die entsprechenden van Hove Singularitäten in der Zustandsdichte sind jedoch extrem klein und deswegen können keine Anomalien in den elastischen Eigenschaften detektiert werden. Desweiteren zeigten wir, daß der Knick in c/a, den Occelli et al. [Occelli et al., Phys. Rev. Lett. 93, 095502 (2004)] bei 25 GPa und Ma et al. [Ma et al., Phys. Rev. B 72, 174103 (2005)] bei 27 GPa fanden, statistisch nicht relevant ist und daß (c/a)(P) genauso gut von einer glatten Funktion gefittet wird als von stückweise linearen Funktionen.

Uranium-10wt% zirconium (U-10Zr) alloy nuclear fuels have been used for decades and new variations are under consideration ranging from U-5Zr to U-50Zr. As a precursor to understanding the fission gas behavior in U-Zr alloys using ion implantation, a basic study on the U-Zr metallurgy was completed using EPMA, DSC, XRD, Optical microscopy, and TEM with a focus on solid state phase transformations in alloys containing 2, 5, 10, 20, 30, and 50wt% zirconium. Alloys were cast by crucible melting using high temperature furnace under argon atmosphere in yttrium oxide crucibles and various thermal profiles were used to study phase transformations in these alloys. Using TEM, XRD, and DSC data, it was ascertained that athermal-ω, along with martensitic α1, formed in all alloys quenched from γ phase. XRD could detect the presence of athermal-ω only in U-20, 30 and 50wt%Zr alloys. BSE images for as-cast alloys of 2, 5, 10, 20, and 30wt%Zr had lamellar microstructure with lamellae rich in zirconium. All alloy samples clearly showed a heating transformation pertaining to δ → γ in DSC data while XRD could only confirm the presence of δ phase in U-20, 30, and 50wt%Zr alloys. An explanation is offered for the absence of δ phase peaks in uranium-rich alloys based on its formation mechanism. Alloy samples of U-2, 5, and 10wt%Zr were step-cooled from γ phase by annealing in the (α + δ) phase field before cooling to room temperature revealed broad peaks for δ phase indicating incomplete collapse of {111}γ planes. Both as cast and γ- quenched alloys were annealed at 600degreeC, in the (α + δ) phase field for 1, 3, 7, and 30 days. Microstructures of the samples in both cases contained uranium-rich matrix and zirconium-rich precipitates and WDS analyses were consistent with their being α-U and δ phase respectively. However, XRD data for annealed alloys never showed peaks for δ phase even though it’s area fraction was within the detection limits. Moreover, the peaks which were present in U-20wt%Zr vanished after annealing for 7 days. Based on the data obtained, it is suggested that it is more appropriate to consider the presence of metastable diffusional-ω instead of a stable δ in the as-cast alloys and that it is not stable at 600degreeC.

Non-stoichiometric strontium iron oxide is described by an abbreviated formula SrFeOx (2.5 ≤ x ≤ 3.0) exhibits a variety of interesting physical and chemical properties over a broad range of temperatures and in different gaseous environments. The oxide contains a mixture of iron in the trivalent and the rare tetravalent state. The material at elevated temperature is a mixed oxygen conductor and it, or its derivatives,can have practical applications in oxygen conducting devices such as pressure driven oxygen generators, partial oxidation reactors in electrodes for solid oxide fuel cells (SOFC). ¶ This thesis examines the behaviour of the material at ambient and elevated temperatures using a broad spectrum of solid state experimental techniques such as: x-ray and neutron powder diffraction,thermogravimetric and calorimetric methods,scanning electron microscopy and Mossbauer spectroscopy. Changes in the oxide were induced using conventional thermal treatment in various atmospheres as well as mechanical energy (ball milling). ¶ ...

The present thesis reports computer simulation studies of several phase transition related phenomena in a range of soft-condensed matter systems. A coherent unifying theme of the thesis is the understanding of dynamics of phase transitions through free energy calculations using recently developed efficient non-Boltzmann sampling methods. Based on the system/phenomena of interest, the thesis has been classified into four major parts: I. Isotropic-nematic (IN) phase transition in liquid crystals. II. Nucleation phenomena in gas-liquid transition with particular emphasis on the systems close to the spinodal curve. III. Collapse transition in linear hydrocarbon (n-alkane) chains for a varying range of length, solvent and temperature. IV. Crystallization of unbranched polymer chains in dilute solution, with particular emphasis on the temperature dependent crossover between the rod-like crystalline state and spherical molten globule state. The thesis has been further divided into ten chapters running through the four parts mentioned before. In the following we provide a brief chapter-wise outline of the thesis. Part I deals with the power law relaxation and glassy dynamics in thermotropic liquid crystals close to the IN transition and consists of two chapters. To start with, Chapter I.1 provides an introduction to thermotropic liquid crystals. Here we briefly introduce various liquid crystalline phases, the order parameter used to characterize the IN transition, a few well established theoretical models, and we conclude with describing the recent experimental and computer simulation studies that have motivated the work described in the next chapter. In Chapter I.2, we present our molecular dynamics simulation studies on single particle and collective orientational dynamics across the IN transition for Lebwohl Lasher model, which is a well-known lattice model for thermotropic liquid crystals. Even this simplified model without any translational degrees of freedom successfully captures the short-tointermediate time power law decay recently observed in optical heterodyne detected optical Kerr effect (OHDOKE) measurements near the IN transition. The angular velocity time correlation function also exhibits a rather pronounced power law decay near the IN boundary. In the mean squared angular displacement at comparable time scales, we observe the emergence of a sub-diffusive regime which is followed by a super-diffusive regime before the onset of the longtime diffusive behavior. We observe signature of dynamical heterogeneity through pronounced non-Gaussian behavior in the orientational motion particularly at lower temperatures. Interestingly, this behavior closely resembles what is usually observed in supercooled liquids. We obtain the free energy as a function of orientational order parameter by the use of recently developed transition matrix Monte Carlo (TMMC) method. The free energy surface is flat for the system considered here and the barrier between isotropic and nematic phases is vanishingly small for this weakly first-order transition, hence allowing for large scale, collective, and correlated orientational density fluctuations. We attribute this large scale fluctuations as the reason for the observed power law decay of the orientational time correlation functions. Part II consists of three chapters, where we focus on the age old problem of nucleation and growth, both from the perspective of thermodynamics and kinetics. We account for the rich history of the problem in the introductory Chapter II.1. In this chapter we describe various types and examples of the nucleation phenomena, and a brief account of the major theoretical approaches used so far. We begin with the most successful Classical Nucleation Theory (CNT), and then move on to more recent applications of Density Functional Theory (DFT) and other mean-field types of models. We conclude with a comparison between the experiments, theories and computational studies. In the next chapter (Chapter II.2) we attempt to elucidate the mechanism of nucleation near the gas-liquid spinodal from a microscopic point of view. Here we construct a multidimensional free energy surface of nucleation of the liquid phase from the parent supercooled and supersaturated vapor phase near the gas-liquid spinodal. In particular, we remove the Becker-Doring constraint of having only one growing cluster in the system. The free energy, as a function of the size of the largest cluster, develops a pronounced minimum at a subcritical cluster size close to the spinodal. This signifies a two step nature of the process of nucleation, where the rapid formation of subcritical nuclei is followed by further growth by slower density fluctuations on an uphill free energy surface. An alternative free energy pathway involving the participation of many subcritical clusters is envisaged near the spinodal where the growth of the nucleus is found to be promoted by a coalescence mechanism in contrast to the single particle addition assumption within CNT. The growth of the stable phase becomes progressively collective and spatially diffuse, and the significance of a “critical nucleus” is lost for deeper quenches. In this chapter we present our studies both in 3dimensional Lennard-Jones (LJ) system and Ising model (both 2and 3dimensions). Our general findings seem to be independent of the model chosen. While the previous chapter focuses on relatively well-studied 3-dimensional (3D) LJ system, in Chapter II.3 we present our studies on the characteristics of the nucleation phenomena in 2dimensional (2D) Lennard-Jones fluid. To the best of our knowledge this is the first extensive computer simulation study to check the accuracy of CNT in 2D. Using various Monte Carlo methods, we calculate the free energy barrier for nucleation, line tension, and bulk densities of equilibrium liquid and vapor phases, and also investigate the size and shape of the critical nucleus. The study is carried out at an intermediate level of supersaturation (away from the spinoidal limit). In 2D, a surprisingly large cutoff (rc ≥ 7.0σ where σ is the diameter of LJ particles) in the truncation of the LJ potential is required to obtain converged results. A lower cutoff leads to a substantial error in the values of the line tension, nucleation barrier, and characteristics of the critical cluster. Note that typically 2.5σ is sufficient for 3D LJ fluids. We observe that in 2D system CNT fails to provide a reliable estimate of the free energy barrier. While it is known to slightly overestimate the nucleation barrier in 3D, it underestimates the barrier by as much as 50% at the saturation ratio S = 1.1(defined as S = P/Pc, where Pc is the coexistence pressure) and at the reduced temperature T* = 0.427(defined as T* = KBT/ ε, where ε is the depth of the potential well). The reason for the marked inadequacy of the CNT in 2D can be attributed to the non-circular nature of the critical clusters. Although the shape becomes increasingly circular and the clusters become more compact with increase in cutoff radius, an appreciable non-circular nature remains even without any cutoff to make the simple CNT inaccurate. Part III again consists of three chapters and focuses on the conformational equilibria. Collapse transition and self-organized structures of n-alkanes in solution. In Chapter III.1 we carry out a brief survey of the existing theories of polymer in solution, with particular emphasis on the collapse process in poor solvents. We also introduce the concept of “hydrophobicity” and “hydrophobic collapse”, which is now a subject enormous interest, partly because it my help in understanding the initial processes involved in protein folding. We briefly discuss the subject of formation of beautiful self-organized structures by block copolymers, and also simple homopolymers which is essentially the focus of the work embodied in the next two chapters. In Chapter III.2 we demonstrated a chain length dependent crossover in the structural properties of linear hydrocarbon (n-alkane) chains using detailed atomistic simulations in explicit water. We identify a number of exotic structures o the polymer chain through energy minimization of representative snapshots collected from molecular dynamics trajectory. While the collapsed state is ring-like(circular) for small chains(CnH2n+2; n ≤ 20) and spherical for very long ones( n = 100), we find the emergence of ordered helical structures at intermediate lengths (n ~ 40). We find different types of disordered helices and toroid-like structures at n = 60. We also report a sharp transition in the stability of the collapsed state as a function of the chain length through relevant free energy calculations. While the collapsed state is only marginally metastable for C20H42, a clear bistable free energy surface emerges only when the chain is about 30 monomers long. For n = 30, the polymer exhibits an intermittent oscillation(characterized by well-developed 1/f noise, where f is the frequency ) between the collapsed and the coil structures, characteristic of two stable states separated by a small barrier. This appears to support a weakly first order phase transition between the extended and the collapsed states. Chapter III.3 extends the study of previous chapter to much longer chains (n ≥ 100), which irreversibly collapse in water into globular forms. Even though the collapsed form has a nearly spherical shape, close inspection shows a propensity towards local ordering in the alignment of the polymer segments. This tendency to maintain alignment in order to maximize the number of contacts leads to a core-shell like structure, where the shell is often characterized by a bent rod-like shape consisting of two adjacent segments running in parallel. A key event associated with the initial stage of collapse seems to be the formation of a skewed ring (or loop) that serves as a “nucleation center” for rest of the chain to collapse into. Time evolution of the radial distribution function of water surrounding the polymer, shows that the density of neighboring water decreases by only about 15-20% from that of bulk water. Even though interior of the ting-like structures is fully devoid of water, solvent accessible surface representation shows that these regions are geometrically/spatially inaccessible to water molecules. We suggest that the role of water is to stabilize such ring-like structures once formed by natural conformational fluctuations of the polymer chain. This view is confirmed by observation of spontaneous formation and melting away of such ring-like entities in a polar aprotic solvent(DMSO). We also comment on the role of the flexibility of polymer chains in determining the collapse kinetics. The last part(Part IV) of the thesis consists of two chapters that deal with the crystallization of linear polymer chains from dilute solution. The way long chain polymers crystallize is drastically different from their small molecule counterparts due to their topological connectivity. Linear polymers often crystallize from dilute solution in the form of thin lamellae with well-defined crystallographic features. In Chapter IV.1 we briefly survey the current theoretical understanding and confusions associated with the highly debated field of polymer crystallization. While the last few decades have seen the development of many successful phenomenological theories, the molecular mechanism of formation of such self-organized lamellae is extremely complex and very poorly understood. There are clearly two distinct steps in polymer crystallization. Firstly, the individual linear polymers must self-organize into bundles of somewhat regular structures. These structures then further aggregate to lamellar form and crystallize into a lattice. In this respect , it has marked similarity to the problem of protein crystallization. In chapter IV.2 we present Brownian dynamics simulation studies of a single polythelene chain of length 500. Such systems can reasonably mimic the process of crystallization from dilute solutions. Our simulations could successfully reproduce some of the interesting phenomena observed in experiments and very recent computer simulation studies, including multi-center nucleation of rod-like structures within a single polymer chain, an inverse relation between lamellar thickness and temperature etc. But our primary focus has been to understand the nature of the phase transition as one traverses along the melting temperature and the underlying free energy surface. Near the melting temperature we observe a very intriguing fluctuation between the disordered molten globule state and the ordered rod-like crystalline, where these two forms have highly different shape and structure. These fluctuations have strong signature of 1/f noise or intermittency. This clearly indicates the existence of a weakly first order transition, where two widely different states with large difference in values of order parameter are separated by a rather small free energy barrier. This can be related to the experimentally observed density fluctuations that resemble spinodal decomposition. It is important to note that very similar fluctuations have been observed in our previous studies on liquid crystals (Chapter 1.2) and intermediate sized alkalines in water(Chapter III.2) that signifies a universal underlying energy landscape for these systems. We have discussed the scope of future work at the end of each chapter whenever appropriate.