Rozprawy doktorskie na temat „Phase transformation interfaces”

Au cours de cette thèse deux problèmes majeurs pour l’eau ont été étudiés : la transition liquide-liquide et la nucléation homogène de la glace. Pour cela nous avons utilisé l'état de l'art des méthodes d’échantillonnage amélioré, couplé avec une nouvelle variable qui contient les informations topologiques pertinentes des systèmes étudiés, le PIV. En calculant des profils d'énergie libre pour différentes conditions de pression et de température, nous avons pu montrer rigoureusement l’absence de barrière d’énergie libre et de second point critique pour la transition liquide-liquide avec le modèle TIP4P/2005. En échantillonnant l'ensemble des chemins de transition grâce à un nouvel algorithme TPS, nous avons aussi pu étudier précisément le mécanisme de nucléation homogène de l’eau avec le modèle TIP4P/Ice, montrant que la structure optimale des noyaux critiques est un empilement désordonné, les noyaux critiques purement cubique ou hexagonaux évoluant spontanément vers cette structure. De plus, nous avons pu montrer que la glace hexagonale s’agrégeait majoritairement en deux étapes, là où la glace cubique s’agrégeait en une étape. Finalement nous avons quantifié rigoureusement la qualité de notre métrique topologique PIV comme coordonnée de réaction pour étudier la nucléation : une analyse réalisée avec la méthode d'optimisation de la vraisemblance maximale basée sur la fonction de réalisation, indique que cette coordonnée surpasse un large éventail de coordonnées utilisées précédemment pour étudier ce problème
During this thesis two major problems were studied : the liquid-liquid transition and the homogeneous nucleation of ice in water. To achieve this, we used state-of-the-art enhanced sampling methods, coupled with a new collective variable which store the relevant topological information of a system, the PIV. By rigorous calculation of free energy profile for various conditions of pressure and temperature, we have been able to show the lack of free energy barrier and thereof a second critical point for the liquid-liquid transition, with the TIP4P/2005 model of water. By sampling the transition path ensemble with a new TPS algorithm, we have been able to precisely study the homogeneous nucleation of ice in water with the TIP4P/Ice model, showing that critical nuclei arrange themselves optimaly in stacking disorder ice, with purely hexagonal or cubic nuclei spontaneously evolving toward this structure. The insight we obtained includes a two-step mechanism for the aggregation of new hexagonal ice molecules to the critical nucleus, compared to a one-step process for the addition of cubic ice molecules. Finally we performed a quantitative assessment of the quality of the PIV topological metric as reaction coordinate for nucleation : analysis by means of a rigorous likelihood optimization technique based on committor information, indicates that this coordinate outperforms a large set of previously considered coordinates

Notre travail porte sur la fusion dite solutale survenant lorsque l'on met deux métaux en contact à une température comprise entre leurs températures de fusion respectives. L'interface solide/liquide se retrouve initialement fortement hors-équilibre et la cinétique propre à son retour à l'équilibre semble mettre en défaut les modèles généralement employés pour décrire la solidification et la fusion. Pour progresser dans la compréhension du processus, nous avons abordé le problème sous trois angles complémentaires. Dans un premier temps, nous avons réalisé des expériences in-situ de fusion solutale du système Au-Ag en utilisant la tomographie par rayons X. L'analyse critique des résultats semble montrer que l'interface solide-liquide reste hors équilibre pendant la fusion solutale, avec la persistance inattendue de gradients de concentration à la fin des expériences. Dans un deuxième temps, dans le but de mieux comprendre les expériences, nous avons mis en œuvre un modèle reposant sur la thermodynamique des processus irréversibles appliquée aux échanges d'espèces chimiques à travers une interface solide/liquide abrupte. Une paramétrisation des coefficients de transfert interfaciaux permet au modèle de reproduire qualitativement les comportements observés dans les expériences. Enfin, nous avons cherché à justifier les paramètres cinétiques du modèle thermodynamique en utilisant la dynamique moléculaire (DM) dans le système Cu-Ni. Nous avons ainsi démontré que les coefficients interfaciaux dépendent des concentrations à l'interface, en accord avec la paramétrisation du modèle thermodynamique
Our work focuses on solutal melting, which occurs when two metals are brought into contact at a temperature between their respective melting temperatures. The solid/liquid interface is initially far from equilibrium, and the kinetics governing its return to equilibrium appear to challenge the models commonly used to describe solidification and melting. To advance our understanding of the process, we approached the problem from three complementary angles. First, we conducted in-situ experiments on the solutal melting of the Au-Ag system using X-ray tomography. Critical analysis of the results appears to indicate that the solid-liquid interface remains out of equilibrium during solutal melting, with the unexpected persistence of concentration gradients at the end of the experiments. Second, in an effort to better understand the experiments, we developed a model based on the thermodynamics of irreversible processes applied to the exchange of chemical species across a sharp solid/liquid interface. Parametrization of interfacial transfer coefficients enables the model to qualitatively reproduce the behaviors observed in the experiments. Finally, we sought to justify the kinetic parameters of the thermodynamic model using molecular dynamics (MD) in the Cu-Ni system. We thus demonstrated that the interfacial coefficients depend on the concentrations at the interface, consistent with the parametrization of the thermodynamic model

Dans ce travail, nous etudions certaines transitions de phase dans les lignes et interfaces. Le texte est concu en trois chapitres assez distincts. Dans le premier chapitre, les transitions de phase entre parois de bloch et ising dans un modele xy anisotrope sont etudiees. Nous generalisons la notion de parois de domaines aux systemes dynamiques ou une excitation parametrique joue le role de l'anisotropie. Le phenomene nouveau qui apparait alors est le mouvement des parois de bloch, avec une vitesse proportionnelle a leurs chiralites. Au deuxieme chapitre, nous etudions le role de la surface d'un cristal lors d'une transition de phase structurale, et nous comparons cette derniere a une transition de mouillage classique. Dans le cadre de notre modele, nous mettons en evidence une transition de phase de surface, comparable a une transition de premouillage, qui survient avant la transition de phase structurale du volume. Le troisieme chapitre etudie l'interaction entre deux chaines de polymeres, et la transition de localisation qui peut survenir dans ce systeme. Nous etudions plus particulierement la relation qui existe entre cette transition et l'enroulement mutuel des deux chaines. L'interaction entre les deux chaines qui a courte portee, peut comporter dans notre modele des termes qui favorisent l'enroulement

Cette thèse applique l'approche des Quasiparticles (QA) pour étudier les mécanismes à l'échelle atomique qui conduisent à la transformation de phase CFC à CC dans le fer. Dans un premier temps, cette étude se concentre sur le fer pur, fournissant des résulats détaillés sur la nature et le rôle des dislocations à l'interface CFC-CC. Il a été montré que l'interface CFC-CC est semi-cohérente, avec des marches, et contient deux réseaux de dislocations de transformations. L'approche des Quasiparticles a permis de révéler l'influence de la relation d'orientation sur les caractéristiques de l'interface. Bien que les relations d'orientation étudiées ont montré diférentes structures d'interface, il a été démontré que toutes suivent le même chemin de transformation atomique, dû au glissement des dislocations de transformation à l'interface. Il a été conclu que la transformation complète de CFC à CC implique le mécanisme de transformation de Kurdjumov-Sachs (KS) en deux variantes le long des lignes de dislocations, avec le mécanisme de transformation de Kurdjumov-Sachs-Nishiyama (KSN) qui émerge comme la moyenne de l'action des deux mécanismes KS. Cette description détaillée a servi de base pour l'étude des systèmes Fe-C, où la ségrégation du carbone à l'interface a été observée. De plus, il a été montré que les profils de concentration de carbone sont cohérents avec des conditions d'équilibre local à l'interface
This thesis applies the Quasiparticle Approach (QA) to investigate the atomic scale mechanisms driving the phase transformation from FCC to BCC structures in iron. Initially, the study focuses on pure iron, providing detailed results into the nature and role of dislocations, at the FCC-BCC interface. It was shown that the FCC-BCC interface is semi-coherent and stepped, with two sets of transformations dislocations at the interface. The QA framework reveals how each orientation relationship (OR) influences the interface characteristics. Although the ORs displayed different interface structures, all were ultimately found to follow the same atomic transformation path, driven by the glide of transformation dislocations at the interface. It was concluded that the complete FCC to BCC phase transformation involves the action of the Kurdjumov-Sachs (KS) transformation mechanism in two variants along the two sets of dislocations, with the Kurdjumov-Sachs-Nishiyama (KSN) mechanism emerging as the average of the two KS mechanisms. This detailed description served as a basis for the study of Fe-C systems, where carbon segregation at the interface was observed. Moreover, it was shown that the carbon concentration profiles were consistent with local equilibrium conditions at the interface

This thesis concerns the mathematical modelling of phase transformations with a special emphasis on martensitic phase transformations and their application to the modelling of steels. In Chapter 1, we develop a framework that determines the optimal transformation strain between any two Bravais lattices and use it to give a rigorous proof of a conjecture by E.C. Bain in 1924 on the optimality of the so-called Bain strain. In Chapter 2, we review the Ball-James model and related concepts. We present some simplification of existing results. In Chapter 3, we pose a conjecture for the explicit form of the quasiconvex hull of the three tetragonal wells, known as the three-well problem. We present a new approach to finding inner and outer bounds. In Chapter 4, we focus on highly compatible, so called self-accommodating, martensitic structures and present new results on their fine properties such as estimates on their minimum complexity and bounds on the relative proportion of each martensitic variant in them. In Chapter 5, we investigate the contrary situation when self-accommodating microstructures do not exist. We determine, whether in this situation, it is still energetically favourable to nucleate martensite within austenite. By constructing different types of inclusions, we find that the optimal shape of an inclusion is flat and thin which is in agreement with experimental observation. In Chapter 6, we introduce a mechanism that identifies transformation strains with orientation relationships. This mechanism allows us to develop a simpler, strain-based approach to phase transformation models in steels. One novelty of this approach is the derivation of an explicit dependence of the orientation relationships on the ratio of tetragonality of the product phase. In Chapter 7, we establish a correspondence between common phenomenological models for steels and the Ball-James model. This correspondence is then used to develop a new theory for the (5 5 7) lath transformation in low-carbon steels. Compared to existing theories, this new approach requires a significantly smaller number of input parameters. Furthermore, it predicts a microstructure morphology which differs from what is conventionally believed.

La thèse porte sur la modélisation de la transformation de l'austénite en ferrite dans les aciers en mettant l'accent sur les conditions thermodynamiques et cinétiques aux interfaces alpha/gamma en cours de croissance de la ferrite. Dans une première partie, la thèse se concentre sur la description des équilibres thermodynamiques entre alpha et gamma à l'aide de la méthode CalPhad. Nous avons développé un nouvel algorithme hybride combinant la construction d'une enveloppe convexe avec la méthode classique de Newton-Raphson. Nous montrons ses possibilités pour des aciers ternaire Fe-C-Cr et quaternaire Fe-C-Cr-Mo dans des cas particulièrement difficiles. Dans un second chapitre, un modèle à interface épaisse a été développé. Il permet de prédire l'ensemble du spectre des conditions à l'interface alpha/gamma au cours de la croissance de la ferrite, de l'équilibre complet au paraéquilibre avec des cas intermédiaires des plus intéressants. Nous montrons que de nombreux régimes cinétiques particuliers dans les systèmes Fe-C-X peuvent être prévus avec un minimum de paramètres d'ajustement, principalement le rapport entre les diffusivités de l'élément substitutionnel dans l'interface épaisse et dans le volume d'austénite. Le troisième chapitre porte sur l'étude d'un modèle de champ de phase. Une analyse approfondie des conditions à l'interface données par le modèle est réalisée en utilisant la technique des développements asymptotiques. En utilisant les connaissances fournies par cette analyse, le rôle de la mobilité intrinsèque d'interface sur la cinétique et les régimes de croissance est étudié, à la fois dans le cas simple d'alliages binaires Fe-C et dans le cas plus complexe d'alliages Fe-C-Mn
Transformation in steels focusing on the thermodynamic and kinetics conditions at the alpha/gamma interfaces during the ferrite growth. The first chapter deals with the determination of thermodynamic equilibria between alpha and gamma with CalPhad thermodynamic description. We have developed a new hybrid algorithm combining the construction of a convex hull to the more classical Newton-Raphson method to compute two phase equilibria in multicomponent alloys with two sublattices. Its capabilities are demonstrated on ternary Fe-C-Cr and quaternary Fe-C-Cr-Mo steels. In the second chapter, we present a thick interface model aiming to predict the whole spectrum of conditions at an alpha/gamma interface during ferrite growth, from full equilibrium to paraequilibrium with intermediate cases as the most interesting feature. The model, despite its numerous simplifying assumptions to facilitate its numerical implementation, allows to predict some peculiar kinetics in Fe-C-X systems with a minimum of fitting parameters, mainly the ratio between the diffusivities of the substitutional element inside the thick interface and in bulk austenite. The third chapter deals with the phase field model of austenite to ferrite transformation in steels. A thorough analysis on the conditions at the interface has been performed using the technique of matched asymptotic expansions. Special attention is given to clarify the role of the interface mobility on the growth regimes both in simple Fe-C alloys and in more complex Fe-C-Mn alloys

Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2007.
Martha A. Gallivan, Committee Member ; Andrei G. Fedorov, Committee Member ; Christopher Summers, Committee Member ; Thomas H. Sanders, Jr., Committee Member ; Mo Li, Committee Chair.

Ce travail concerne la microstructure des phases de frank-kasper, en particulier, les interfaces. Les proprietes de ces phases cristallines et leurs liens avec les quasicristaux sont rappeles dans le premier chapitre, ces deux types de structures possedant le meme ordre local icosaedrique ou derive de l'icosaedre. Le deuxieme chapitre est consacre aux interfaces entre phases de frank-kasper et cristal simple. Ce travail est preliminaire a l'etude des interfaces entre quasicristal et cristal simple. Il est montre que les approches traditionnelles des interfaces basees sur la comparaison de deux cristaux simples ne sont pas adaptees aux phases de frank-kasper. Une nouvelle approche geometrique est alors proposee. Sa validite est testee sur des interfaces entre precipites de phases de frank-kasper et des matrices simples etudiees par microscopie electronique. L'approche proposee rend bien compte des plans d'interfaces et des relations d'orientation observes. Le troisieme chapitre est consacre aux transformations des phases de frank-kasper (ici une isostructure de alpha-manganese) vers un ordre quasiperiodique et au role des defauts dans ces transformations. Une sequence continue de phases quasiperiodiques du systeme mgal dont l'originalite est de posseder une symetrie cubique est presentee. La derniere etape de cette sequence possede en outre la symetrie d'inflation en 2+3. La decouverte des phases cubiques quasiperiodiques est issue d'un travail preliminaire sur des particules d'une isostructure de alpha-manganese du systeme fecrmo dont les diagrammes de diffraction etaient globalement aperiodiques et cristallins a petite echelle. L'analyse de cette microstructure montre que la structure alpha-manganese peut generer une frustration geometrique pouvant conduire a l'apparition d'un ordre quasiperiodique dans un systeme de symetrie cubique. Ceci est en accord avec l'observation des phases quasiperiodiques dans le systeme mgal

L’epaisseur instantanée d'un film annulaire soumis ou non à un écoulement de gaz est analysée grâce à des méthodes statistiques, à la théorie du chaos et à l'aide de la transformée en ondelettes. Ces méthodes appliquées aux mesures, réalisées à l'aide de sondes conductimétriques à fils parallèles en 5 positions de la section d'essai de 40,6 mm de diamètre et de 2,2 m de longueur, ont permis d'obtenir de nombreux résultats sur l'évolution longitudinale et la dynamique du film. Citons : * l'existence d'un nombre de Reynolds de liquide global critique, situé autour de 3000. Le comportement en moyenne et dynamique du film est bien distinct en deca et au delà de cette limite. Par exemple : - l'amplification des vagues et l'augmentation de l'épaisseur du film et de la célérité moyenne moins fortes dans la première zone. - l'épaisseur du substrat et la fréquence prépondérante qui sont quasi constantes quand le nombre de Reynolds global est supérieur à 3000. - la dimension de corrélation qui est quasi indépendante du débit de liquide quand l'écoulement est turbulent (Re_L > 3000) alors que dans la zone laminaire, son évolution est fonction de la distance. * la dépendance de la structure de l'interface du film en fonction de la distance. Par exemple, quand la distance augmente, l'amplitude et la célérité des vagues croissent alors que la fréquence prépondérante et la dimension fractale diminuent. * la célérité des vagues indépendante de la fréquence. * une relation linéaire entre la célérité moyenne et l'amplitude maximale des vagues. * l'influence de l'interaction liquide-gaz diminue quand le débit de liquide augmente. La célérité des vagues et la dimension fractale chutent à l'approche du point de flooding. * une possibilité de filtrage des signaux par la transformée en ondelettes.

The present work has been produced as part of an on-going collaboration between the University of Manchester and Amec, with the primary aim of furthering mechanistic understanding of corrosion processes in zirconium alloys out-of-reactor. Zirconium alloys are used as cladding material for nuclear fuel pellets, and correct understanding of the corrosion process in autoclave is essential to predicting material behaviour in-reactor. This EngD thesis is composed of five proposed papers that investigate observations and hypotheses under the theme of mechanical degradation in oxides formed on zirconium alloys in autoclave. First investigations concern observed stress relaxation in zirconium oxide. Finite element analysis is used to capture mechanical aspects of the corrosion process and apply this to stress behaviour determined previously using synchrotron x-ray diffraction. The results indicate that a mechanism other than creep or hydrogen induced lattice strain must be present to account for the observed stress relaxation. One such potential mechanism is crack formation; statistical analysis of scanning electron microscopy images has been used to identify a link between the development of roughness at the metal-oxide interface, crack formation in the oxide and transition points or acceleration in the corrosion kinetics. Parameters such as the median radius of curvature and profile slope (Rdq) have been applied, as these parameters do not require the definition of a periodic wavelength or amplitude. These and other parameters are related to information in literature to indicate that for samples of Zircaloy-4 and ZIRLOTM, which go through transition, the interface roughness changes in a way that would increase localised stress concentrations. The third material is an experimental low tin alloy, which under the same oxidation conditions, and during the same time period, does not appear to go through transition and does not develop an interface roughness in the same way. A critical assessment of finite element analysis applied to oxidising non-planar interfaces shows the significant limitations in the existing mechanism for representing oxidation expansion and stress formation. Autoclave oxidation experiments of artificially roughened samples of Zircaloy-4 were carried out to further understand the impact of out-of-plane stress generation. The results indicate a divergence based on surface roughness after ~86 days oxidation. SEM examination of images in cross section highlighted accelerated oxidation above surface roughness peaks, and an increased crack area in rougher samples. Finally, finite element analysis of the tetragonal to monoclinic phase transformation showed that biaxial compressive stress relaxation, or the tri-axial tensile stress associated with an advancing crack tip, could reduce the transformation strain energy and destabilise the tetragonal phase. The volumetric expansion and shear strain associated with the phase transformation produces stress in the surrounding oxide sufficient to generate nano-scale cracks perpendicular to the metal-oxide interface. This would allow fast ingress routes for oxygen containing species, and therefore acceleration in the corrosion kinetics.

Avec les progres de la modelisation informatique, les siderurgistes ont commence a developper des modeles mathematiques dont l'objectif est de predire l'evolution microstructurale et les proprietes mecaniques finales des aciers en fonction du traitement thermomecanique. Le travail de cette these s'inscrit dans cet effort en ayant pour objet l'etude des cinetiques de la transformation bainitique qui reste a ce jour l'une des plus mal comprises des nombreuses transformations microstructurales dans les aciers. L'approche suivie est avant tout experimentale et laisse une large place a la technique de thermodilatometrie couplee a des analyses microstructurales a differentes echelles. Notre etude s'appuie principalement sur trois nuances d'aciers a 0,5%c dont une nuance au silicium qui permet d'obtenir une bainite sans cementite. L'etude de l'etape de croissance montre que, quel que soit le caractere diffusif ou displacif de la transformation austenite-ferrite, c'est la diffusion du carbone dans l'austenite qui est le facteur limitant. Le modele propose permet decrire convenablement l'effet de la temperature et de la teneur en carbone de l'alliage sur les cinetiques. Nous montrons que le silicium ralentit la croissance en inhibant la precipitation de cementite qui accompagne generalement la transformation. L'effet propre du nickel est mis en evidence et est discute sur la base des modeles de solute-drag que nous avons adapte aux transformations allotropiques. Les vitesses de germination sont deduites pour l'acier industriel xc50 des cinetiques globales et du modele de croissance. Il apparait que c'est la diffusion du carbone dans les joints de grains austenitiques qui controle la dependance en temperature du taux de germination. A partir des equations obtenues pour la croissance et la germination, nous proposons un modele des cinetiques globales en conditions isothermes et en refroidissement continu, ainsi qu'un critere de declenchement de la transformation.

In modern turbine engines for propulsion and energy generation, thermal barrier coating (TBCs) protect hot-section blades and vanes, and play a critical role in enhancing reliability, durability and operation efficiency. In this study, thermal cyclic lifetime and microstructural degradation of electron beam physical vapor deposited (EB-PVD) Yttria Stabilized Zirconia (YSZ) with (Ni,Pt)Al bond coat and Hf- and/or Y- modified CMSX-4 superalloy substrates were examined. Thermal cyclic lifetime of TBCs was measured using a furnace thermal cycle test that consisted of 10-minute heat-up, 50-minute dwell at 1135C, and 10-minute forced-air-quench. TBC lifetime was observed to improve from 600 cycles to over 3200 cycles with appropriated Hf- and/or Y alloying of CMSX-4 superalloys. This significant improvement in TBC lifetime is the highest reported lifetime in literature with similar testing parameters. Beneficial role of reactive element (RE) on the durability of TBCS were systematically investigated in this study. Photostimulated luminescence spectroscopy (PL) was employed to non-destructively measure the residual stress within the TGO scale as a function of thermal cycling. Extensive microstructural analysis with emphasis on the YSZ/TGO interface, TGO scale, TGO/bond coat interface was carried out by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning electron microscopy (STEM) as a funcion of thermal cycling including after the spallation failure. Focused ion beam in-situ lift-out (FIB-INLO) technique was employed to prepare site-specific TEM specimens. X-ray diffraction (XRD) and secondary ion mass spectroscopy (SIMS) were also employed for phase identification and interfacial chemical analysis. While undulation of TGO/bond coat interface (e.g., rumpling and ratcheting) was observed to be the main mechanism of degradation for the TBCs on baseline CMSX-4, the same interface remained relatively flat (e.g., suppressed rumpling and ratcheting) for durable TBCs on Hf- and/or Y-modified CMSX-4. The fracture paths changed from the YSZ/TGO interface to the TGO/bond coat interface when rumpling was suppressed. The geometrical incompatibility between the undulated TGO and EB-PVD YSZ lead to the failure at the YSZ/TGO interface for TBCs with baseline CMSX-4. The magnitude of copressive residual stress within the TGO scale measured by PL gradually decreased as a function of thermal cycling for TBCs with baseline CMSX-4 superalloy substrates. This gradual decrease corrsponds well to the undulation of the TGO scale that may lead to relaxation of the compressive residual stress within the TGO scale. For TBCs with Hf- and/or Y-modified CMSX-4 superalloy substrates, the magnitude of compressive residual stress within the TGO scale remained relatively constant throughout the thermal cycling, although PL corresponding to the stress-relief caused by localized cracks at the TGO/bond coat interface and within the TGO scale was observed frequently starting 50% of lifetime. A slightly smaller parabolic growth constant and grain size of the TGO scale was observed for TBCs with Hf- and/or Y- modified CMSX-4. Small monoclinic HfO2 precipitates were observed to decorate grain boundaries and the triple pointes within the alpha-Al2O3 scale for TBCs with Hf- and/or Y-modified CMSX-4 substrates. Segregation of Hf/Hf4+ at the TGO/bond coat interfaces was also observed for TBCs with Hf- and/or Y-modified CMSX-4 superalloys substrates. Adherent and pore-free YSZ/TGO interface was observed for TBCs with Hf- and/or Y-modified CMSX-4, while a significant amount of decohesion at the YSZ/TGO interface was observed for TBCs with baseline CMSX-4. The beta-NiAl(B2) phase in the (Ni,Pt)Al bond coat was observed to partially transform into gama prime-Ni3Al (L12) phase due to depletion of Al in the bond coat during oxidation. More importantly, the remaining beta-NiAl phase transformed into L10 martensitic phase upon cooling even though there was no significant difference in these phase transformations for all TBCs. Results from these microstructural observations are documented to elucidate mechanisms that suppress the rumpling of the TGO/bond coat interface, which is responsible for superior performance of EB-PVD TBCs with (Ni,Pt)Al bond coat and Hf- and/or Y-modified CMXS-4 superalloy.
Ph.D.
Department of Mechanical, Materials and Aerospace Engineering
Engineering and Computer Science
Materials Science & Engr PhD

The level set method offers a simple and robust approach to modeling liquid-vapor interfaces that arise in boiling and condensing flows. The current liquid-vapor phase-transition techniques used with the level set method are not able to account for different thermal conductivities and specific heats in each respective phase, nor are they able to accurately account for latent heat absorption and release. This paper presents a new level set based technique for liquid-vapor phase-transition that accounts for different material properties in each respective phase, such as thermal conductivity and specific heat, while maintaining the interface at the saturation temperature. The phase-transition technique is built on the ghost fluid framework coupled with the standard level set method. A new technique is presented for constructing ghost nodes that implicitly captures the immersed boundary conditions and is second order accurate. The method is tested against analytical solutions, and it is used to model film boiling. The new phase-transition technique will greatly assist efforts to accurately capture the physics of boiling and condensing flows. In addition to presenting a new phase transition technique, a coupled level set volume of fluid advection scheme is developed for phase transition flows. The new scheme resolves the mass loss problem associated with the level set method, and the method provides an easy way to accurately calculate the curvature of an interface, which can be difficult with the volume of fluid method. A film boiling simulation is performed to illustrate the superior performance of the coupled level set volume of fluid approach over the level set method and the volume of fluid method.

Etude par mesure de conductivite electrique, par retrodiffusion rutherford et par microscopie ionique en transmission des differents aspects du melange ionique dans le systeme mt/al (mt=fe, co, ni) et fe-mg. Analyse des differents facteurs controlant la formation d'une phase et celle d'une phase amorphe. Analyse des mecanismes de transformation cristal-amorphe de l'alliage ni::(50)al::(50) en couche mince. Influence des parametres d'irradation sur cette transformation

In this work we provide several improvements in the study of phase transitions of interacting particle systems: - We determine a quantitative relation between non-extremality of the limiting Gibbs measure of a tree-based spin system, and the temporal mixing of the Glauber Dynamics over its finite projections. We define the concept of 'sensitivity' of a reconstruction scheme to establish such a relation. In particular, we focus on the independent sets model, determining a phase transition for the mixing time of the Glauber dynamics at the same location of the extremality threshold of the simple invariant Gibbs version of the model. - We develop the technical analysis of the so-called spatial mixing conditions for interacting particle systems to account for the connectivity structure of the underlying graph. This analysis leads to improvements regarding the location of the uniqueness/non-uniqueness phase transition for the independent sets model over amenable graphs; among them, the elusive hard-square model in lattice statistics, which has received attention since Baxter's solution of the analogous hard-hexagon in 1980. - We build on the work of Montanari and Gerschenfeld to determine the existence of correlations for the coloring model in sparse random graphs. In particular, we prove that correlations exist above the 'clustering' threshold of such a model; thus providing further evidence for the conjectural algorithmic 'hardness' occurring at such a point.

This project reports first-hand knowledge on the mechanical and electron interaction properties of titanate nanowires which possess a broad range of applications. Using experimental techniques, the mechanical bending and tensile behaviours of individual nanowires are analysed from which a time-dependant recovery and an atypical reversible defect motion of the nanowires are observed. Applying electron beam irradiation, joint formation between two titanate nanostructures is demonstrated with the underlying mechanisms explained. The electron-titanate interaction phenomenon is also shown to be a practical tool for tailoring structures at nanoscale.

The photoactive component of a polymeric organic solar cell can be produced by drying a mixture consisting of a volatile solvent and non-volatile polymers. As the solvent evaporates, the polymers demix and self-assemble into microscale structures, the morphology of which plays a pivotal role in determining the efficiency of the resulting device. Thus, a detailed understanding of the physical mechanisms that drive and influence structure formation in evaporating solvent-polymer mixtures is of high scientific and industrial value. This thesis explores several problems that aim to produce novel insights into the dynamics of evaporating solvent-polymer mixtures. First, the role of compositional Marangoni instabilities in slowly evaporating binary mixtures is studied using the framework of linear stability theory. The analysis is non-trivial because evaporative mass loss naturally leads to a time-dependent base state. In the limit of slow evaporation compared to diffusion, a separation of time scales emerges in the linear stability problem, allowing asymptotic methods to be applied. In particular, an asymptotic solution to linear stability problems that have slowly evolving base states is derived. Using this solution, regions of parameter space where an oscillatory instability occurs are identified and used to formulate appropriate conditions for observing this phenomenon in future experiments. The second topic of this thesis is the use of multiphase fluid models to study the dynamics of evaporating solvent-polymer mixtures. A two-phase model is used to assess the role of compositional buoyancy and to examine the formation of a polymer-rich skin at the free surface. Then, a three-phase model is used to conduct a preliminary investigation of the link between evaporation and phase separation. Finally, this thesis explores the dynamics of a binary mixture that is confined between two horizontal walls using a diffusive phase-field model and its sharp-interface and thin-film approximations. We first determine the conditions under which a homogeneous mixture undergoes phase separation to form a metastable bilayer. We then present a novel mechanism for generating a repeating lateral sequence of alternating A-rich and B-rich domains from this bilayer.

Il seguente elaborato di tesi è rivolto a dare una descrizione del tutto generale al fenomeno della decomposizione spinodale sulla base dei meccanismi microscopici della diffusione. Attraverso una opportuna correzione della equazione di diffusione di Fick è stata ricavata l'equazione di Cahn-Hilliard, che permette la descrizione corretta del fenomeno diffusivo. Il processo di deduzione dell'equazione passa per la determinazione del profilo di concentrazione all'interfaccia di due fasi come strumento di minimizzazione dell'energia interna del sistema e quindi come procedimento per raggiungere una condizione di equilibrio termodinamico. La soluzione del problema bidimensionale è stata graficata numericamente con un codice in ambiente MATLAB, da cui sono stati ricavati dati a supporto dei risultati teorici dedotti.

Des superréseaux Mn/Ir (111), Mn/Ir (100) et Fex Mn1-x/Ir (100) avec 0,3 0,8 ont été élaborés par e. J. M. La structure de Mn est cubique à faces centrées déformée trigonalement dans Mn/Ir (111), et tétragonalement dans Mn/Ir (100). Dans les deux cas, le comportement de Mn est soit paramagnétique de Pauli, soit antiferromagnétique de Tn supérieure à 400 k. Par ailleurs, l'épitaxie de l'alliage Fe-Mn est pseudomorphe avec une nucléation 2d sur 9 plans à 100°C. Cet alliage épitaxie est tétragonal centre ; il présente une transition magnéto-structurale pour X = 0,5. Son comportement est ferromagnétique lorsque le fer est majoritaire, alors que l'alliage massif correspondant est antiferromagnétique. Lorsque le manganèse est majoritaire, l'alliage épitaxie est antiferromagnétique. L’utilisation systématique du rayonnement synchrotron a permis de proposer une technique nouvelle d'étude des défauts dans les superréseaux métalliques par diffusion diffuse de rayons X. Cette méthode consiste en la mesure de l'intensité réfléchie par l'échantillon en dehors des pics de Bragg du cristal. Une analyse systématique permet alors de caractériser les interfaces par des longueurs de corrélation des défauts ou des interfaces dans le plan des interfaces et dans la direction de croissance. Ces longueurs sont reliées à la nature des défauts étudiés. Rugosité et interdiffusion d'interfaces peuvent alors être pleinement distinguées. Tous les résultats obtenus ont été confirmés par microscopie électronique à transmission en section transverse

Die vorliegende Arbeit behandelt die Wechselwirkung von Verarbeitung und Gefüge Mn-Al basierter hartmagnetischer Werkstoffe sowie die Auswirkung des Gefüges auf deren Eigenschaften. Dabei wurde das Gefüge der metastabilen tau-Phase im Anschluss an die Phasenbildung aus der Hochtemperaturphase epsilon-MnAl und die Auswirkung einer anschließenden Umformung untersucht. Der Schwerpunkt der Arbeit lag in der Analyse der Evolution verschiedener Gefügebestandteile, wie Grenzflächenverteilung, Versetzungen und Korngröße unter Verwendung von Rasterelektronenmikroskopie und Elektronenrückstreubeugung. Die epsilon-tau Umwandlung kann auf 2 verschiedene Routen erfolgen. In beiden Fällen wird die Bildung von 3 kristallographisch unterschiedlichen zwillingsähnlichen Defekten beobachtet, die als wahre Zwillinge, Ordnungszwillinge und Pseudozwillinge bezeichnet werden. Sie lassen sich als Rotationen um einen kristallographischen {111}-Pol beschreiben. Der Anteil der Zwillingsdefekte nach der Umwandlung, aber auch die Korngröße und Versetzungsdichte sind von der gewählten Umwandlungsroute abhängig. Während die Sättigungspolarisation annähernd gleich ist, reagiert die Koerzitivfeldstärke sensitiv auf den Gefügezustand. Eine niedrige Korngröße und hohe Versetzungsdichte tragen zu ihrer Erhöhung bei. Eine anschließende Kaltumformung erzeugt ein vielfach verzwillingtes Verformungsgefüge mit hoher Koerzitivfeldstärke. Wärmebehandlungen und die Analyse der Schärfe von Kikuchi-Beugungsbildern haben gezeigt, dass nicht die hohe Zwillingsdichte, sondern primär Versetzungen im Verformungsgefüge die Koerzitivfeldstärke steigern. Warmumformung von tau-MnAl führt zur dynamischen Rekristallisation. Die Kinetik der Gefügeneubildung und die resultierende Korngröße sind stark von der Umformtemperatur abhängig. Durch Umformung lässt sich eine kristallographische Texturierung von tau-MnAl erreichen. Die Orientierung der magnetisch leichten [001]-Richtung ist dabei vom gewählten Umformverfahren und gegebenenfalls von der Nachbehandlung abhängig. Statische und dynamische Rekristallisation reduzieren den Anteil der Zwillingsdefekte signifikant und besonders Pseudozwillinge und Ordnungszwillinge werden im Gefüge beseitigt. Das Rekristallisationsgefüge weist gegenüber dem Umwandlungsgefüge einen geringeren Widerstand gegen die mit der Zersetzungsreaktion verbundene Bildung von beta-Mn auf. Die Ursache liegt in einer selektiven beta-Mn-Bildung an allgemeinen Korngrenzen, während die Zwillingsdefekte einen erhöhten Widerstand gegen sie Zersetzung aufweisen.

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

Precipitation-hardened alloys are one of the most technologically significant materials that are used for structural applications, where an important mode of strengthening is due to the impediment to the movement of dislocations. The alloys, particularly possessing coherent precipitate-matrix interface, give rise to the coherency strain fields producing the coherency stresses in the matrix, which further interact with the dislocations to provide necessary strengthening. In this context, the control of the shape and distribution of the precipitates as a function of material and process parameters is important. In this thesis, we propose a diffuse-interface approach in order to compute the equilibrium shape of precipitates, which also allows us to minimize the grid-anisotropy related issues that occur in the classical sharp interface methods. The method is based on the minimization of the functional consisting of the elastic free energy and the interfacial energy, while the volume of the precipitate is conserved. Using this technique we reproduce the shape bifurcation diagram from 2D simulations for isotropic, inhomogeneous elastic energy with dilatational misfit, which is compared against the analytical solution provided by Johnson-Cahn and an existing sharp interface FEM technique. Thereafter the model has been utilized for the investigation of equilibrium shapes for different combinations of elastic misfit matrices and cubic anisotropy. Additionally, we incorporate the anisotropy in the interfacial energy, which has not been studied by previous sharp interface techniques and investigate its influence on shape bifurcation. Finally, we extend the model to calculate the equilibrium shapes of the precipitate in 3D which resembles the precipitate structures observed in real microstructures. We notice that the nature of shape bifurcation diagram in 3D is different than that observed in 2D, which is principally because there exist multiple variants of precipitate shapes for the same precipitate size e.g. prolate-like or oblate-like structures that are not equivalent. We also compute a range of equilibrium shapes in 3D, that can form as a result of symmetry breaking for different forms of anisotropy in the elastic energy. In the next part of the thesis, we extend the phase-field model for computing the equilibrium shape of single precipitates for consideration of multiple variants that allows us to investigate the equilibrium configurations of precipitates. Here, given the properties of the material such as the magnitude of misfit strain and its signs, the magnitude of the shear moduli and the size of the precipitate, one can determine the equilibrium configuration that can form during solid-state precipitation reactions. Using this method, we investigate three solid-state precipitation reactions, i.e. formation of a core-shell type of precipitates in the microstructure and two symmetry-breaking transitions namely, cubic to tetragonal (typically observed in the superalloys with γ' − γ'' microstructure) and hexagonal to orthorhombic (formation of multi-variant precipitate pattern in Ti-based alloys). We evaluate the criteria for the formation of core-shell type microstructures and show that while the formation of such structures is purely due to interfacial conditions (satisfying the wetting condition), the reaction pathway leading to their formation is assisted by elastic interactions between the precipitates. In the symmetry-breaking transitions, we investigate the formation of equilibrium configurations of the multi-variant precipitates using energetic calculations. Here, we observe that the formation of such configurations involving multiple variants is favored over the nucleation of a single precipitate of the same equivalent volume beyond a certain precipitate size. In the last part of the thesis, we relax the condition of volume preservation of the precipitates and study precipitate growth in a supersaturated matrix in the presence of anisotropy in the elastic energy. To achieve this, we utilize a phase-field model based on the grand-potential formulation for coupling the chemical driving forces with coherency stresses. Using this model we investigate the specific problem of solid-state dendrite formation occurring during certain precipitation reactions. Here, we find that the anisotropy in the elastic energy gives rise to the formation of the dendrite-like structures that are typically observed in solidification microstructures as an effect of the Mullins-Sekerka in stabilities. We determine the dendrite tip shape and tip velocity, as the precipitate grows in size as a function of different materials parameters such as the magnitude of misfit strain, supersaturation in the matrix, and the anisotropy strength in both the energies. We notice that in all the cases, the dendrite tip shape and tip velocity does not achieve steady-state which is in contrast with the dendrites observed during solidification. This modification is due to the presence of coherency stresses.

The thesis involves computer simulation and theoretical studies of phase transition in soft-condensed matter systems and theoretical understanding of enzyme kinetics along with kinetic proofreading of tRNA-aminoacylation in biological systems. Based on the system and phenomena of interest, the work has be classified into the following four major parts: I. Surface phenomena and surface energy of vapor-liquid interface. II. Condensation of vapor in two and three dimensions. III. Liquid-solid phase transition in polydisperse systems. IV. Enzyme catalysis and kinetic proofreading in biosynthesis. Above mentioned four parts have further been divided into thirteen chapters. In the following we provide a brief chapter-wise outline of the thesis. Part I deals with surface tension and interfacial properties of vapor-liquid interface for Lennard-Jones (LJ) fluid in both two and three dimensions. In Chapter 1, we provide a brief overview of vapor-liquid interface and existing theoretical and computer simulation studies of surface/line tension. In this chapter we also discuss about the existing experimental studies. In Chapter 2, we present computer simulation studies of surface tension in two dimensional Lennard-Jones system. The sensitivity of line tension on range (potential cut-off) of interparticle interaction is discussed in this chapter. We present Density Functional Theory (DFT) of line tension of vapor-liquid interface based on Weeks-Chandler-Anderson (WCA) and Barker-Hendersen (BH) perturbation techniques. We compare the DFT prediction with the computer simulation results. In general, WCA approach has been found to be successful for 3D system in predicting the surface tension. In 2D, however, it does not give good agreement either for phase diagram or for the line tension. In fact, BH also does not give accurate values of the coexistence parameters, however, it predicts better line tension compared to WCA. In Chapter 3 we present both theoretical and computer simulation studies of gas-liquid surface tension for three dimensional Lennard-Jones fluid. We perform non-equilibrium computer simulation study following Transition Matrix Monte Carlo (TMMC) method to obtain surface tension for various ranges of potential and introduce a new scaling relation of surface tension in order to capture both the temperature and interparticle interaction range dependence. The scaling shows excellent agreement with the simulation result and it can also predict the critical temperature with sufficient accuracy. The width of the gas-liquid interface is found to be insensitive to the range of the potential, whereas the density separation of the bulk vapor and liquid phases increases with increasing range of potential. Thus, the major contribution comes from the increasing density separation of the bulk vapor and liquid phases. Part II consists of four chapters, where we focus on the age old problem of nucleation, from the perspective of thermodynamics and kinetics. We account for the rich history of the problem in the introductory Chapter 4. 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 present various experimental techniques used in the literature to obtain rate of nucleation. We conclude with a comparison between the experiments, theories and computational studies. In the next chapter (Chapter 5) we attempt to understand the mechanism of the gas-liquid nucleation in three dimension at large metastability from microscopic point of view. Here we study the nature of sequential growth of all liquid-like clusters (not just the largest cluster) at different degrees of metastability. Therefore, we have ordered the clusters according to their decreasing sizes and identified them in terms of kth largest cluster where, k = 1 denotes the largest cluster in the system, k = 2 represents the second largest and k = 3 is the third largest and so on. We have studied both the free energies and the trajectories of the liquid-like clusters in this extended set of order parameters. We further define Fkl(n) as the free energy of the kth largest cluster with size n. Classical nucleation theory provides an expression of unconditional free energy of a single cluster, F (n) (the free energy of formation of a cluster of size n), which is an intensive property of the system. The study of our conditional free energy surfaces, Fkl(n), reveals a more detailed, microscopic picture of the system’s cluster size distribution that is necessary to understand the kinetics of nucleation and growth at large metastability. The rate of nucleation shows a cross over at kinetic spinodal (the limit of metastability, ∆F1 l = 0). Below kinetic spinodal only one (largest) cluster crosses the critical size through activation whereas above this point more than one cluster grow simultaneously through barrierless diffusion. We present a theoretical analysis of the free energy of kth largest cluster based on order statistics. The theoretical predictions are in excellent agreement with computer simulation results for the range of supersaturation we studied. While the previous chapter focuses on relatively well-studied nucleation mechanism in 3dimensional (3D) LJ system at large metastability, in Chapter 6 we present our studies on the characteristics of the nucleation phenomena in two dimensional Lennard-Jones fluid for different ranges of interparticle interaction. Using various Monte Carlo (MC) methods, we calculate the free energy barrier of nucleation and bulk densities of equilibrium liquid and vapor phases, and also investigate the size and shape of the critical nuclei. We find an interesting interplay between the range of interaction potential and the extent of metastability. The free energy barrier of nucleation strongly depends on the range of interaction potential. The study is carried out at an intermediate level of supersaturation (away from the kinetic spinodal limit). A surprisingly large cutoff (rc � 7.0�, where � 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 deviation in the values of the nucleation barrier, and characteristics of the critical cluster (with respect to full range of interaction). 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 � 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/�, where � 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 for full potential (without truncation) to make the predictions of CNT inaccurate. In Chapter 7 we report the computer simulation study of nucleation in three dimensional LJ system. At a fixed supersaturation the free energy barrier of nucleation increases with increasing range of interparticle interaction. On increasing range of intermolecular interaction, the kinetic spinodal where the mechanism of nucleation changes from activated barrier crossing to barrierless diffusion, shifts towards the deep metastable region. Both the critical cluster size and pre-critical minimum in the free energy surface of kth largest cluster shift towards the smaller size at their respective kinetic spinodal as we increase the range of potential. We find only a weak non-trivial (other than supersaturation and surface tension) contribution to the free energy barrier of nucleation. Part III consists of two chapters and focuses on the liquid-solid phase transition of polydisperse fluid. In Chapter 8 we introduce polydisperse systems and their classification based on different identities. We describe the importance and abundance of polydisperse system in nature. The theoretical modeling of different polydisperse systems and their extent of applicability have also been presented. We have discussed about the various factors which control the phase diagram and various phenomena related to the structure and phase transition. In Chapter 9 we present computer simulation study on freezing/melting of Lennard-Jones (LJ) fluid at different polydispersities. The freezing/melting of polydisperse LJ fluids presents an interesting case study, because, as the polydispersity increases the energy-entropy balance becomes increasingly unfavorable for the solid to exist as a stable phase. The energy of the solid increases due to build up of strain energy because of increasing mismatch in size of the neighbors, while the entropy of the liquid increases. These two factors lead to the existence of a terminal polydispersity. We find beyond the terminal ploydispersity, δ. 0.11system remains in the disorder state even at very high pressure and low temperature. The terminal polydispersity obtained in the present study is close to the experimental value (δt. ≈ 12%). Interestingly, contrary to hard sphere polydisperse fluid, LJ fluid does not exhibit reentrant melting. The last part (Part IV) of the thesis consists of three chapters that deal with the enzyme catalysis and kinetic proofreading of tRNA-aminoacyl synthetases. In Chapter 10 we describe protein synthesis process in biological system and corresponding two processes: aminoacylation of tRNA and translation of amino acid in ribosome. Our interest is to understand the enzyme catalysis involved in aminoacylation of tRNA in the process of protein synthesis. We present the classification of 20 aminoacyl-tRNA synthetases into two classes based on their structure and mode of binding to ATP and tRNA. We discuss all the steps involved in whole tRNA-aminoacylation process. Then we introduce kinetic proofreading during aminoacylation reaction. In Chapter 11 we theoretically analyze the single turn over and steady state reaction mechanism of two classes of aminoacyl-tRNA synthetases. Class I enzymes not only differ in their structure but they also differ with respect to the pre-steady kinetics compared to class II enzymes. We find that the strong binding of product to class I enzymes causes the product release step to be rate limiting step leading to the burst of product formation in pre-steady reaction. On the other hand class II enzymes do not show any burst kinetics. The present study based on time dependent probability statistics is successful in explaining all the experimental results quantitatively. In Chapter 12 we present an augmented kinetic scheme and then employ methods of time dependent probability statistics to understand the mechanism of kinetic proofreading of isoleucyl-tRNA synthetase (IRS) which belongs to class I. We investigate that the enhanced hydrolysis of wrong substrate (Val) enables IRS to discriminate the correct substrate (Ile) and wrong substrate (Val) efficiently. It has been observed that an extra CP1 editing domain serves as an activating domain towards enhanced hydrolysis of Val. The present study is able to explain most of the existing experimental observations. In the concluding note, Chapter 13 lists a few relevant problems that may prove worthwhile to be addressed in future. In the Appendices, we present two of the techniques used in our present computer simulation and theoretical studies. Appendix A describes Grand Canonical Transition Matrix Monte Carlo (GC-TMMC) method which is employed in computer simulation studies of nucleation and surface tension. In Appendix B we present the probabilistic method of waiting time distribution computation used in enzyme catalysis and kinetic proofreading.

The thesis involves computer simulation and theoretical studies of phase transition in soft-condensed matter systems and theoretical understanding of enzyme kinetics along with kinetic proofreading of tRNA-aminoacylation in biological systems. Based on the system and phenomena of interest, the work has be classified into the following four major parts: I. Surface phenomena and surface energy of vapor-liquid interface. II. Condensation of vapor in two and three dimensions. III. Liquid-solid phase transition in polydisperse systems. IV. Enzyme catalysis and kinetic proofreading in biosynthesis. Above mentioned four parts have further been divided into thirteen chapters. In the following we provide a brief chapter-wise outline of the thesis. Part I deals with surface tension and interfacial properties of vapor-liquid interface for Lennard-Jones (LJ) fluid in both two and three dimensions. In Chapter 1, we provide a brief overview of vapor-liquid interface and existing theoretical and computer simulation studies of surface/line tension. In this chapter we also discuss about the existing experimental studies. In Chapter 2, we present computer simulation studies of surface tension in two dimensional Lennard-Jones system. The sensitivity of line tension on range (potential cut-off) of interparticle interaction is discussed in this chapter. We present Density Functional Theory (DFT) of line tension of vapor-liquid interface based on Weeks-Chandler-Anderson (WCA) and Barker-Hendersen (BH) perturbation techniques. We compare the DFT prediction with the computer simulation results. In general, WCA approach has been found to be successful for 3D system in predicting the surface tension. In 2D, however, it does not give good agreement either for phase diagram or for the line tension. In fact, BH also does not give accurate values of the coexistence parameters, however, it predicts better line tension compared to WCA. In Chapter 3 we present both theoretical and computer simulation studies of gas-liquid surface tension for three dimensional Lennard-Jones fluid. We perform non-equilibrium computer simulation study following Transition Matrix Monte Carlo (TMMC) method to obtain surface tension for various ranges of potential and introduce a new scaling relation of surface tension in order to capture both the temperature and interparticle interaction range dependence. The scaling shows excellent agreement with the simulation result and it can also predict the critical temperature with sufficient accuracy. The width of the gas-liquid interface is found to be insensitive to the range of the potential, whereas the density separation of the bulk vapor and liquid phases increases with increasing range of potential. Thus, the major contribution comes from the increasing density separation of the bulk vapor and liquid phases. Part II consists of four chapters, where we focus on the age old problem of nucleation, from the perspective of thermodynamics and kinetics. We account for the rich history of the problem in the introductory Chapter 4. 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 present various experimental techniques used in the literature to obtain rate of nucleation. We conclude with a comparison between the experiments, theories and computational studies. In the next chapter (Chapter 5) we attempt to understand the mechanism of the gas-liquid nucleation in three dimension at large metastability from microscopic point of view. Here we study the nature of sequential growth of all liquid-like clusters (not just the largest cluster) at different degrees of metastability. Therefore, we have ordered the clusters according to their decreasing sizes and identified them in terms of kth largest cluster where, k = 1 denotes the largest cluster in the system, k = 2 represents the second largest and k = 3 is the third largest and so on. We have studied both the free energies and the trajectories of the liquid-like clusters in this extended set of order parameters. We further define Fkl(n) as the free energy of the kth largest cluster with size n. Classical nucleation theory provides an expression of unconditional free energy of a single cluster, F (n) (the free energy of formation of a cluster of size n), which is an intensive property of the system. The study of our conditional free energy surfaces, Fkl(n), reveals a more detailed, microscopic picture of the system’s cluster size distribution that is necessary to understand the kinetics of nucleation and growth at large metastability. The rate of nucleation shows a cross over at kinetic spinodal (the limit of metastability, ∆F1 l = 0). Below kinetic spinodal only one (largest) cluster crosses the critical size through activation whereas above this point more than one cluster grow simultaneously through barrierless diffusion. We present a theoretical analysis of the free energy of kth largest cluster based on order statistics. The theoretical predictions are in excellent agreement with computer simulation results for the range of supersaturation we studied. While the previous chapter focuses on relatively well-studied nucleation mechanism in 3dimensional (3D) LJ system at large metastability, in Chapter 6 we present our studies on the characteristics of the nucleation phenomena in two dimensional Lennard-Jones fluid for different ranges of interparticle interaction. Using various Monte Carlo (MC) methods, we calculate the free energy barrier of nucleation and bulk densities of equilibrium liquid and vapor phases, and also investigate the size and shape of the critical nuclei. We find an interesting interplay between the range of interaction potential and the extent of metastability. The free energy barrier of nucleation strongly depends on the range of interaction potential. The study is carried out at an intermediate level of supersaturation (away from the kinetic spinodal limit). A surprisingly large cutoff (rc � 7.0�, where � 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 deviation in the values of the nucleation barrier, and characteristics of the critical cluster (with respect to full range of interaction). 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 � 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/�, where � 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 for full potential (without truncation) to make the predictions of CNT inaccurate. In Chapter 7 we report the computer simulation study of nucleation in three dimensional LJ system. At a fixed supersaturation the free energy barrier of nucleation increases with increasing range of interparticle interaction. On increasing range of intermolecular interaction, the kinetic spinodal where the mechanism of nucleation changes from activated barrier crossing to barrierless diffusion, shifts towards the deep metastable region. Both the critical cluster size and pre-critical minimum in the free energy surface of kth largest cluster shift towards the smaller size at their respective kinetic spinodal as we increase the range of potential. We find only a weak non-trivial (other than supersaturation and surface tension) contribution to the free energy barrier of nucleation. Part III consists of two chapters and focuses on the liquid-solid phase transition of polydisperse fluid. In Chapter 8 we introduce polydisperse systems and their classification based on different identities. We describe the importance and abundance of polydisperse system in nature. The theoretical modeling of different polydisperse systems and their extent of applicability have also been presented. We have discussed about the various factors which control the phase diagram and various phenomena related to the structure and phase transition. In Chapter 9 we present computer simulation study on freezing/melting of Lennard-Jones (LJ) fluid at different polydispersities. The freezing/melting of polydisperse LJ fluids presents an interesting case study, because, as the polydispersity increases the energy-entropy balance becomes increasingly unfavorable for the solid to exist as a stable phase. The energy of the solid increases due to build up of strain energy because of increasing mismatch in size of the neighbors, while the entropy of the liquid increases. These two factors lead to the existence of a terminal polydispersity. We find beyond the terminal ploydispersity, δ. 0.11system remains in the disorder state even at very high pressure and low temperature. The terminal polydispersity obtained in the present study is close to the experimental value (δt. ≈ 12%). Interestingly, contrary to hard sphere polydisperse fluid, LJ fluid does not exhibit reentrant melting. The last part (Part IV) of the thesis consists of three chapters that deal with the enzyme catalysis and kinetic proofreading of tRNA-aminoacyl synthetases. In Chapter 10 we describe protein synthesis process in biological system and corresponding two processes: aminoacylation of tRNA and translation of amino acid in ribosome. Our interest is to understand the enzyme catalysis involved in aminoacylation of tRNA in the process of protein synthesis. We present the classification of 20 aminoacyl-tRNA synthetases into two classes based on their structure and mode of binding to ATP and tRNA. We discuss all the steps involved in whole tRNA-aminoacylation process. Then we introduce kinetic proofreading during aminoacylation reaction. In Chapter 11 we theoretically analyze the single turn over and steady state reaction mechanism of two classes of aminoacyl-tRNA synthetases. Class I enzymes not only differ in their structure but they also differ with respect to the pre-steady kinetics compared to class II enzymes. We find that the strong binding of product to class I enzymes causes the product release step to be rate limiting step leading to the burst of product formation in pre-steady reaction. On the other hand class II enzymes do not show any burst kinetics. The present study based on time dependent probability statistics is successful in explaining all the experimental results quantitatively. In Chapter 12 we present an augmented kinetic scheme and then employ methods of time dependent probability statistics to understand the mechanism of kinetic proofreading of isoleucyl-tRNA synthetase (IRS) which belongs to class I. We investigate that the enhanced hydrolysis of wrong substrate (Val) enables IRS to discriminate the correct substrate (Ile) and wrong substrate (Val) efficiently. It has been observed that an extra CP1 editing domain serves as an activating domain towards enhanced hydrolysis of Val. The present study is able to explain most of the existing experimental observations. In the concluding note, Chapter 13 lists a few relevant problems that may prove worthwhile to be addressed in future. In the Appendices, we present two of the techniques used in our present computer simulation and theoretical studies. Appendix A describes Grand Canonical Transition Matrix Monte Carlo (GC-TMMC) method which is employed in computer simulation studies of nucleation and surface tension. In Appendix B we present the probabilistic method of waiting time distribution computation used in enzyme catalysis and kinetic proofreading.

Die vorliegende Arbeit behandelt die Wechselwirkung von Verarbeitung und Gefüge Mn-Al basierter hartmagnetischer Werkstoffe sowie die Auswirkung des Gefüges auf deren Eigenschaften. Dabei wurde das Gefüge der metastabilen tau-Phase im Anschluss an die Phasenbildung aus der Hochtemperaturphase epsilon-MnAl und die Auswirkung einer anschließenden Umformung untersucht. Der Schwerpunkt der Arbeit lag in der Analyse der Evolution verschiedener Gefügebestandteile, wie Grenzflächenverteilung, Versetzungen und Korngröße unter Verwendung von Rasterelektronenmikroskopie und Elektronenrückstreubeugung. Die epsilon-tau Umwandlung kann auf 2 verschiedene Routen erfolgen. In beiden Fällen wird die Bildung von 3 kristallographisch unterschiedlichen zwillingsähnlichen Defekten beobachtet, die als wahre Zwillinge, Ordnungszwillinge und Pseudozwillinge bezeichnet werden. Sie lassen sich als Rotationen um einen kristallographischen {111}-Pol beschreiben. Der Anteil der Zwillingsdefekte nach der Umwandlung, aber auch die Korngröße und Versetzungsdichte sind von der gewählten Umwandlungsroute abhängig. Während die Sättigungspolarisation annähernd gleich ist, reagiert die Koerzitivfeldstärke sensitiv auf den Gefügezustand. Eine niedrige Korngröße und hohe Versetzungsdichte tragen zu ihrer Erhöhung bei. Eine anschließende Kaltumformung erzeugt ein vielfach verzwillingtes Verformungsgefüge mit hoher Koerzitivfeldstärke. Wärmebehandlungen und die Analyse der Schärfe von Kikuchi-Beugungsbildern haben gezeigt, dass nicht die hohe Zwillingsdichte, sondern primär Versetzungen im Verformungsgefüge die Koerzitivfeldstärke steigern. Warmumformung von tau-MnAl führt zur dynamischen Rekristallisation. Die Kinetik der Gefügeneubildung und die resultierende Korngröße sind stark von der Umformtemperatur abhängig. Durch Umformung lässt sich eine kristallographische Texturierung von tau-MnAl erreichen. Die Orientierung der magnetisch leichten [001]-Richtung ist dabei vom gewählten Umformverfahren und gegebenenfalls von der Nachbehandlung abhängig. Statische und dynamische Rekristallisation reduzieren den Anteil der Zwillingsdefekte signifikant und besonders Pseudozwillinge und Ordnungszwillinge werden im Gefüge beseitigt. Das Rekristallisationsgefüge weist gegenüber dem Umwandlungsgefüge einen geringeren Widerstand gegen die mit der Zersetzungsreaktion verbundene Bildung von beta-Mn auf. Die Ursache liegt in einer selektiven beta-Mn-Bildung an allgemeinen Korngrenzen, während die Zwillingsdefekte einen erhöhten Widerstand gegen sie Zersetzung aufweisen.