O desenvolvimento dos veículos atuais vem sendo impulsionado pela necessidade de redução de massa associada com o aumento da segurança para os passageiros. Na procura de novos materiais e processos para atender estas exigências, os aços bifásicos ferrítico-martensíticos ou DP vêm se destacando entre os aços avançados de alta resistência (AHSS), por apresentar elevada resistência mecânica e boa ductilidade. Da mesma forma, a soldagem a laser vem se mostrando promissora para junção desta classe de materiais. Este processo permite unir os aços DP com boa qualidade metalúrgica sem significativas distorções dimensionais. Embora os aços DP apresentem boa soldabilidade, um amolecimento localizado na zona afetada pelo calor (ZAC) também é observado, especialmente no aço DP1000, que apresenta elevada fração de martensita. Desta forma, esta Tese propõe a soldagem a laser do aço DP1000 de espessura 1,80 mm, seguida de uma sistemática caracterização microestrutural, visando a produção de juntas soldadas suficientemente resistentes. Para isto, foram produzidos cordões numa chapa de aço DP1000, variando a potência nominal de soldagem entre 0,4 e 2,0 kW e a velocidade de soldagem entre 20 e 150 mm/s. A caracterização microestrutural foi conduzida com o auxílio das técnicas de microscopia óptica (MO), microscopia eletrônica de varredura (MEV), difração de raios X (DRX) e difração de elétrons retroespalhados (EBSD). As juntas soldadas mais representativas foram submetidas a ensaios de dureza Vickers e tração uniaxial. Os resultados mostram que é possível produzir juntas soldadas resistentes no aço DP1000. Todavia, é fundamental que a combinação de parâmetros gere soldas com penetração total e mínima largura de ZAC, limitando a quantidade de amolecimento da martensita prévia e a fração volumétrica de austenita retida. Na presente Tese, os melhores resultados foram obtidos para uma potência de 2,0 kW e velocidade de 150 mm/s. / The development of modern vehicles has been driven by the need of mass reduction associated with the increase of the safety of passengers. In the search for new materials and processes to meet these requirements, ferritic-martensitic dual-phase (DP) steels are potential candidates among advanced high-strength steels (AHSS), because of their high mechanical strength and good ductility. In that sense, laser beam welding has been shown promising for joining this class of materials. This process allows joining DP steels with good metallurgical quality without large dimensional distortions. Although DP steels show good weldability, a localized softening in the heat affected zone (HAZ) is also observed, especially in DP1000 steel which contains large amounts of martensite. Thus, laser beam welding has been performed in DP1000 steel with thickness of 1.80 mm, followed by a systematic microstructural characterization, aiming at the production of resistant welded joints. For this, bead-on-plate welds were carried out in DP1000 steel, varying the welding power between 0.4 and 2.0 kW and the welding speed between 20 and 150 mm/s. The microstructural characterization was conducted with the aid of light optical microscopy (LOM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and electron backscattered diffraction (EBSD). The most representative welded joints were tested for Vickers hardness and uniaxial tensile test. Results show that it is possible to produce sound and resistant welded joints in DP1000 steel. However, it is critical that the combination of parameters allows the obtainment of welds with full penetration and minimum HAZ width, limiting the amount of softening of prior martensite and the volume fraction of retained austenite. In the present Thesis, this was achieved using a power of 2.0 kW and a welding speed of 150 mm/s.

During loss-of-coolant accidents (LOCA) and reactivity-initiated accidents (RIA), nuclear fuel rods experience high heating rates that change the microstructure and properties of zirconium cladding materials, which are in forms of stress-relieved, like cold-worked (CW) or recrystallised (RX) microstructure. The present study aimed to determine how different fast heating rates and starting microstructures affect the kinetics of phase transformation, the transformation textures and eventually the mechanical response in the dual-phase region. The LOCA/RIA cycles from heating at 8 to 100C/s to alpha+beta or above beta transus temperature were achieved via resistive heating in an electro-thermal-mechanical tester. Synchrotron X-ray diffraction (SXRD) and electrical resistivity measurements showed that the approach curves of CW Zircaloy-4 shift to higher temperature at faster constant heating rates and change to a new approach curve when changing rates. 2-second holding at two-phase temperature produces identical phase fractions as equilibrium. These observations are consistent with the diffusional character of the phase trans- formation. Heated at 100oCs1, RX samples transform with 2D beta-growth while CW ones show simultaneous beta-nucleation and growth. The difference arises because the fast heating rate helps preserve low-angle grain boundaries (GB) in the CW microstructure up to phase transformation temperature, increasing beta nucleation sites and prevent beta-growth. This gives rise to different textures of RX and CW materials before transformation, producing different textures, which are weak in both cases. However, this difference is enhanced during grain growth and transformation on cooling. Thus, the RX material shows strong final alpha texture with 0002 maxima aligned in TD and tilted 20deg from ND towards TD while the CW reveals an essentially random one. In both RX and CW materials, variant selection does not occur during transformation on heating. During beta-grain growth, although there is variability in beta-textures measured by SXRD and EBSD beta reconstruction, it is clear that variant selection occurs, leading to strengthening of the beta texture. During transformation on cooling, variant selection occurs early in nucleation of the alpha phase from the shared 110 beta GB in the RX condition. The flow stresses of CW Zircaloy-4 in the two-phase regime at a given temperature depend on the heating rates, despite having the same phase fractions. Heated at a slower rate, the material shows an upper yield stress followed by softening behaviour while that heated faster has a smaller yield stress followed by a high work-hardening rate and then stable flowing stresses. The evolution of diffraction elastic strains and intensity suggest the upper yield stress and softening are due to stress-induced transformation of the harder alpha grains into large and isolated softer beta grains. In contrast, the sample heated faster develops an almost continuous film of beta grains along the GB of unrecrystallised alpha-grains which results in early beta-yielding and coherent deformation of the two phases, leading to constant flow stresses. The findings will improve the accuracy of inputs from phase fractions, microstructure and texture of zirconium claddings when modelling LOCA/RIA. A crystal plasticity model should consider the effects of heating rates and cold-work, which are often ignored. The link between deformation, fast heating rates and microstructure evolution might be relevant to other processes like additive layer manufacturing and even forging in the two-phase region.

Microbial-Induced Calcium Carbonate (CaCO3) Precipitation (MICP) is a biological process in which microbial activities alter the surrounding aqueous environment and induce CaCO3 precipitation. Because the formed CaCO3 crystals can bond soil particles and improve the mechanical properties of soils such as strength, MICP has been explored for potential engineering applications such as soil stabilisation. However, it has been difficult to control and predict the properties of CaCO3 precipitates, thus making it very challenging to achieve homogeneous MICP-treated soils with the desired mechanical properties. This PhD study investigates MICP at both micro and macro scales to improve the micro-scale understandings of MICP which can be applied at the macro-scale for improving the homogeneity and mechanical properties of MICP-treated sand. A microfluidic chip which models a sandy soil matrix was designed and fabricated to investigate the micro-scale fundamentals of MICP. The first important finding was that, during MICP processes, phase transformation of CaCO3 can occur, which results in smaller and less stable CaCO3 crystals dissolving at the expense of growth of larger and more stable CaCO3 crystals. In addition, it was found that bacteria can aggregate after being mixed with cementation solution, and both bacterial density and the concentration of cementation solution affect the size of aggregates, which may consequently affect the transport and distribution of bacteria in a soil matrix. Furthermore, bacterial density was found to have a profound effect on both the growth kinetics and characteristics of CaCO3. A higher bacterial density resulted in a quicker formation of a larger amount of smaller crystals, whereas a lower bacterial density resulted in a slower formation of fewer but larger crystals. Based on the findings from micro-scale experiments, upscaling experiments were conducted on sandy soils to investigate the effect of injection interval on the strength of MICP treated soils and the effects of bacterial density and concentration of cementation solution on the uniformity of MICP treated soils. Increasing the interval between injections of cementation solution (from 4 h to 24 h) increased the average size of CaCO3 crystals and the resulting strength of MICP-treated sand. An optimised combination of bacterial density and cementation solution concentration resulted in a relative homogeneous distribution of CaCO3 content and suitable strength and stiffness of MICP-treated sand. This thesis study revealed that a microfluidic chip is a very useful tool to investigate the micro-scale fundamentals of MICP including the behaviour of bacteria and the process of CaCO3 precipitation. The optimised MICP protocols will be useful for improving the engineering performance of MICP-treated sandy soils such as uniformity and strength.

Les aciers Dual-Phase (DP) sont des aciers à très haute résistance mécanique (AHSS) fortement utilisés pour des applications automobiles en raison de leur très bon compromis résistance mécanique/ductilité ainsi que par leur habilité à répondre aux multiples exigences industrielles (bas prix, assemblage, revêtement etc.). A l'heure actuelle, le développement d'aciers DP apparait durable pour la caisse-en-blanc des structures automobiles. La microstructure ferrite-martensite, caractéristique des aciers DP, est obtenue par un traitement thermique complexe composé de différentes étapes au cours desquelles différents mécanismes métallurgiques entrent en jeux. Les principales difficultés de production sont liées au fait (i)que les évolutions microstructurales sont influencées par les différents paramètres de traitement thermique (vitesse de chauffe, température ...), (ii) que les différentes étapes de traitement sont interconnectées et que (iii) les évolutions microstructurales peuvent se chevaucher et, part conséquent, interagir entre elles. Ces travaux de thèse ont pour objectif d'améliorer la compréhension des évolutions métallurgiques entrant en jeux lors des traitements thermiques des aciers DP, et notamment d'améliorer la compréhension de l'influence des paramètres de traitement. Les différentes évolutions métallurgiques ont été, dans un premier temps, caractérisées en couplant un ensemble de techniques expérimentales (dilatométrie, dureté, TPE ...) et grâce à un protocole assurant de décorréler les mécanismes se superposant et interconnectés. A titre d'exemple, les deux principaux mécanismes entrant en jeux lors de l'étape de recuit intercritique ont été, dans un premier temps, étudiés séparément ((1) la recristallisation a été étudié en dessous de la température de formation d'austénite et (2) la formation d'austénite a été étudié sur un acier pré-recristallisé) avant de se concentrer sur le cas des aciers laminés à froid où la recristallisation et formation d'austénite se superposent. Le projet avait également pour objectif de développer des outils de prédictions permettant de décrire les évolutions microstructurales basés sur des approches empiriques (loi de JMAK) ainsi que vers des modèles à base plus physique (mixed-mode modèle et modèle diffusif). Une attention particulière a été dédié à discuter de la fiabilité, l'adaptabilité, des forces et limitations des différentes approches développées. / Dual-Phase steels (DP) are one of the most used Advanced High Strength Steels (AHSS) for automotive applications because they present good strength/ductility compromise and they adapt to number of industrial constraints (low price, shaping, welding, coating etc.). Nowadays, the development of DP steels seems to be promising and sustainable for the body-in-white structure. The typical ferrite-martensite microstructure, characteristic of DP steels, are obtained by a thermal treatment composed of different stages during which metallurgical evolutions occur. Major difficulties of their processing are due to the fact that (i) microstructural evolution kinetics are influenced by cycle parameters (heating rate, annealing temperature etc.), (ii) different stages are interconnected and (iii) some microstructural evolutions may overlap and, therefore, interact. This PhD-work aimed at getting a better understanding of microstructural evolutions during the thermal cycle of DP steel and, namely, the influence of cycle parameters. Different microstructural evolutions occurring during the thermal cycle were first characterized coupling different experimental techniques (dilatometry, hardness, TPE etc.) and with a particular protocol in order to decorrelate overlapping and interconnected phenomena. As example, two major evolutions occurring during the intercritical annealing were first studied individually ((1) recrystallization was investigated below austenite formation temperature and (2) austenite formation was investigated on prior recrystallized steels) before investigated cold-rolled steel case where recrystallization and austenite formation overlap. The study was then attached to develop some predictive tools to describe microstructural evolutions based on phenomenological approaches (JMAK law) towards more physical based models (mixed-mode, diffusive models). A particular care was attached to discuss on model reliability, versatility, strengths and limitations.

Les films de ZrO2 pur sont déposés par MOCVD (Metal-Organic Chemical Vapor Deposition) en variant de nombreux paramètres du processus. L'influence des conditions de dépôt sur l'évolution de la microstructure (morphologies, structure cristalline/phase, texture et contrainte résiduelle) a été étudiée et clarifiée. Par des analyses approfondies des résultats expérimentaux, trois mécanismes typiques de croissance de dépôt de ZrO2 ont été proposées. Les contraintes de croissance de compression sont en relation directe avec la diffusion atomique et la quantité d'espèces piégées dans les films. La formation de la texture cristallographique est complexe et deux types de textures ont été analysées dans la phase tétragonale : la texture de fibre {1 1 0}t est contribuée par l'effet superplastique des nano-cristallites de ZrO2 et par la contrainte de croissance de compression ; tandis que la morphologie en facette est due à la croissance concurrentielle de différents plans cristallographiques. La stabilisation de la phase tétragonale de ZrO2 a été analysée et discutée. En plus de la taille critique des cristallites, la stabilisation de la phase tétragonale est favorisée par deux autres mécanismes : la grande quantité des défauts cristallins et la morphologie des cristallites.

<p>Mixing excipients is a common way to produce pharmaceutical materials with suitable properties for drug formulation. An understanding of the basic mechanisms involved in the formation and transformation of the structures of solid state mixtures is crucial if one is to be able to produce materials with the desired properties in a reliable way. </p><p>In the first part of the thesis, the atomic force microscopy (AFM) technique was used to visualise the re-crystallisation of spray-dried amorphous particles comprised of lactose and PVP. The transformation was quantified on a single particle level and analysed with a common kinetic model, the JMAK-equation. The way in which the PVP was incorporated into the particles and the impact this had on their physical stability on exposure to increasing levels of humidity was investigated. The amount and, to a certain extent, the molecular weight of the PVP affected the moisture induced crystallisation of the particles. The inhibition was further discussed in terms of nucleation and growth. </p><p>In the second part of the thesis, the formation of phases in solid dispersions of monoolein (MO) in PEGs was studied by the use of SAXS and DSC. Upon solidification of a melt, the components phase separated, resulting in a PEG-rich phase and an MO phase. MO was intercalated into the amorphous domains of the lamellar structure of PEG. A second MO phase appeared in the mixtures where the average molecular weight of PEG was 1500 and 4000 g/mol. It was hypothesised that this second phase was formed in conjunction with the expulsion of MO as the PEG unfolded. </p><p>This thesis describes the application of two relatively unexplored solid state techniques on two different solid mixtures of pharmaceutical interest and, in so doing, contributes to the knowledge of phase formation and transformations in the solid state.</p>

Le second chapitre introduit les différents couplages présents dans une analyse mécanique thermique métallurgique. Il rappelle ensuite les notions de métallurgie nécessaires à la compréhension de ce travail. Le troisième chapitre décrit la modélisation adoptée pour l'analyse thermique métallurgique non couplée au problème mécanique. Le modèle choisi est celui de FERNANDES (CP30). Le code développé par ce dernier était limité à l'étude de cylindres infiniment longs, c'est-à-dire à un problème unidimensionnel. L'intégration de ce modèle, dans le code LAGAMINE apporte une grande liberté quant aux formes géométriques traitées. Actuellement, les cas bidimensionnels (état plan ou axisymétrique) peuvent être traités, une extension aux cas tridimensionnels ne pose pas de problème si ce n'est celui des temps de calcul. Du point de vue théorique, nous avons proposé une formulation différentielle de la modélisation des transformations par diffusion. Cette approche, indépendante de celle de SJOSTROM (CP38) a permis de vérifier cette dernière par une voie différente. En outre, la comparaison de cette approche avec celle plus classique de FERNANDES constitue un élément nouveau intéressant. Pour terminer, des tests de validation des développements correspondants dans le code LAGAMINE sont présentés. Le chapitre quatre est consacré aux problèmes numériques à résoudre pour réaliser une simulation de refroidissement d'une pièce métallique. Une bibliographie des schémas d'intégration temporelle des problèmes thermiques linéaires et non linéaires est présentée. A ce niveau, nous ne pouvons parler de contribution originale puisqu'il s'agit de schémas devenus classiques. Cependant, il est assez rare de trouver un résumé de ces notions souvent dispersées dans de nombreux articles. A ce titre, nous considérons ce point comme un apport intéressant de cette thèse. La prise en compte des changements de phase a occasionné un grand nombre de recherches. Après avoir fait le point sur les méthodes proposées par la littérature, nous décrivons les développements introduits dans le code LAGAMINE. Le calcul des flux et de la matrice tangente est détaillé. Ce dernier point constitue un apport personnel original, surtout au niveau de la contribution des transformations de phase à la matrice tangente. Le chapitre cinq est consacré aux interactions existant entre les phénomènes mécaniques, thermiques et métallurgiques. Une présentation approfondie de chaque couplage est réalisée et la notion de plasticité de transformation est introduite. Notre contribution personnelle et originale réside dans :  une loi élasto-plastique thermique couplée pour un matériau monophasique,  une loi élasto-plastique thermique métallurgique pour un matériau multiphasique. L'intégration des lois élasto-plastiques thermiques, métallurgiques ou non, dans le code LA GAMINE constitue le chapitre six. Les points suivants constituent un apport original de cette thèse:  schéma d'intégration temporelle de base pour ces lois couplées,  apport des sous-intervalles d'intégration,  étude de la matrice tangente couplée d'un élément isoparamétrique à 8 nuds,  amélioration du schéma d'intégration temporelle de base pour assurer la stabilité en cas de transformation martensitique,  développement de la notion d'état plan généralisé pour l'étude du refroidissement d'une poutrelle métallique. Le chapitre sept présente le problème du remaillage. Après une description succincte des solutions proposées par la littérature, nous justifions notre choix d'un remaillage avec maillage indépendant. Ce dernier semble en effet le mieux adapté aux problèmes de forgeage et d'estampage que nous désirons résoudre. Le chapitre huit est consacré à la détermination de l'instant opportun pour réaliser un remaillage. Nous distinguerons deux types de critères: a. les critères avec estimation de l'erreur, développés dans le cadre de l'optimisation des maillages d'éléments finis lors d'une analyse linéaire, ou adaptés aux problèmes non linéaires de formage des métaux, b. les critères sans estimation de l'erreur, basés sur des mesures de distorsion des éléments, les valeurs propres, les mesures des interpénétrations de la pièce forgée et de la matrice. Concernant les critères du type a, notre contribution personnelle est la suivante:  étude bibliographique traduisant dans un vocabulaire d'ingénieur, les développements mathématiques souvent présents lors des études d'estimateurs d'erreur,  adaptation du critère proposé par ZIENKIEWICZ aux lois élastoviscoplastiques présentes dans LAGAMINE et essai d'une variante basée sur une idée personnelle. Concernant les critères de type b, nous proposons des mesures de distorsions originales pour un élément isoparamétrique plan à 8 nuds et nous présentons une analyse des valeurs propres de la matrice tangente. Pour terminer, nous présentons une comparaison des critères de type a et b programmés dans LAGAMINE. A notre connaissance, une telle comparaison n'avait encore jamais été réalisée. Elle nous permet de vérifier la concordance des deux approches. Les avantages et inconvénients de chacune de ces méthodes sont établis. Ils permettent de réaliser un choix des critères à conserver dans l'optique d'un remaillage automatique. Le chapitre neuf présente succinctement la création du nouveau maillage. Les exigences relatives à un mailleur automatique adapté au problème de remaillage sont précisées. Une première approche fut réalisée par nos soins grâce à un programme interactif REMDATA. Les développements originaux de ce programme sont détaillés en annexe 3. Le chapitre dix traite le transfert des informations de l'ancien maillage au nouveau maillage. A ce niveau, deux types d'informations sont considérés: a. les informations relatives aux éléments de solide, b. les informations relatives aux éléments modélisant le contact Le transfert des informations de type a est une opération souvent traitée par la littérature. Après une revue bibliographique des méthodes proposées, nous présentons une méthode originale et personnelle de transfert. Ses qualités principales sont sa précision, sa facilité de mise en uvre et sa souplesse d'utilisation. Une comparaison de cette méthode avec deux autres méthodes basées respectivement sur les moindres carrés et sur l'extrapolation nodale des valeurs aux points d'intégration est présentée. Concernant les informations de type b, nous n'avons trouvé aucune référence qui traitait leur transfert d'un maillage à l'autre. Ce point est cependant important, comme le montrent des essais de remaillage réalisés sans interpolation de ces variables. Les deux méthodes de transfert présentées dans cette thèse montrent l'évolution de notre approche de ce problème. Toutes deux constituent des apports personnels et originaux. Le chapitre onze présente cinq exemples d'application des développements réalisés: 1. l'analyse thermique métallurgique d'une poutrelle métallique refroidie par arrosage et refroidissement naturel, 2. l'analyse thermique métallurgique mécanique d'une poutrelle métallique refroidie par arrosage et refroidissement naturel, 3. l'analyse thermique métallurgique mécanique de la trempe d'un cylindre en acier 60NCD11, 4. la simulation de l'estampage d'une aube de turbine (analyse mécanique avec remaillage), 5. la simulation de l'estampage d'un pignon de machine (analyse mécanique avec remaillage). Hormis l'application 3 qui constitue l'application du code à un cas test déjà traité par DENIS et SJOSTROM (CP31), ces exemples constituent des contributions originales. Quelques conclusions sont proposées au chapitre douze. Parmi nos contributions originales, certaines nous semblent d'une ampleur et d'un intérêt plus grands :  la loi élastoplastique thermique métallurgique et son schéma d'intégration prennent en compte les couplages existant entre les différents phénomènes. Le nombre de codes réalisant une telle analyse est assez réduit alors que des calculs réalistes de contraintes résiduelles de trempe, de soudure ne peuvent être obtenus par des analyses découplées. De plus, l'adaptation des modèles développés à d'autres traitements thermiques (revenu n.) constitue de nouvelles perspectives de recherches pour l'équipe de M.S.M.,  une présentation des estimateurs d'erreur disponibles dans le cadre de la méthode des éléments finis est une information précieuse pour les ingénieurs numériciens comme pour les industriels qui ont recours à ces calculs,  les différents avantages et inconvénients des critères de remaillage basés respectivement sur les estimateurs d'eITeur et les mesures des distorsions des éléments constituent un élément important pour ceux qui doivent faire un choix entre ces deux types de critères,  l'importance du transfert des informations relatives au contact a été mis en évidence, alors que ce sujet n'est pas abordé dans la littérature.

Mixing excipients is a common way to produce pharmaceutical materials with suitable properties for drug formulation. An understanding of the basic mechanisms involved in the formation and transformation of the structures of solid state mixtures is crucial if one is to be able to produce materials with the desired properties in a reliable way. In the first part of the thesis, the atomic force microscopy (AFM) technique was used to visualise the re-crystallisation of spray-dried amorphous particles comprised of lactose and PVP. The transformation was quantified on a single particle level and analysed with a common kinetic model, the JMAK-equation. The way in which the PVP was incorporated into the particles and the impact this had on their physical stability on exposure to increasing levels of humidity was investigated. The amount and, to a certain extent, the molecular weight of the PVP affected the moisture induced crystallisation of the particles. The inhibition was further discussed in terms of nucleation and growth. In the second part of the thesis, the formation of phases in solid dispersions of monoolein (MO) in PEGs was studied by the use of SAXS and DSC. Upon solidification of a melt, the components phase separated, resulting in a PEG-rich phase and an MO phase. MO was intercalated into the amorphous domains of the lamellar structure of PEG. A second MO phase appeared in the mixtures where the average molecular weight of PEG was 1500 and 4000 g/mol. It was hypothesised that this second phase was formed in conjunction with the expulsion of MO as the PEG unfolded. This thesis describes the application of two relatively unexplored solid state techniques on two different solid mixtures of pharmaceutical interest and, in so doing, contributes to the knowledge of phase formation and transformations in the solid state.

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.

The utilization of ferromagnetic shape memory alloys (FSMAs) in small scale devices has attracted considerable attention within the last decade. However, the lack of sufficient studies on their reversible shape change mechanisms, i.e, superelasticity, magnetic field-induced martensite variant reorientation and martensitic phase transformation, at the micron and submicron length scales prevent the further development and the use of FSMAs in small scale devices. Therefore, investigating the size effects in these mechanisms has both scientific and technological relevance. Superelastic behavior of Ni54Fe19Ga27 shape memory alloy single crystalline pillars was studied under compression as a function of pillar diameter. Multiple pillars with diameters ranging between 200 nm and 10 µm were cut on a single crystalline bulk sample oriented along the [110] direction in the compression axis and with fully reversible two-stage martensitic transformation. The results revealed size dependent two-stage martensitic transformation which was suppressed for pillar sizes of 1 µm and below. We also demonstrated that the reduction in pillar diameter decreases the transformation temperature due to the difficulty of martensite nucleation in small scales. Size effects in the magnetic field-induced martensite variant reorientation were investigated in the Ni50Mn28.3Ga21.7 single crystals oriented along the [100] direction of the austenite phase. Single crystalline compression pillars were fabricated on the martensite twins between the sizes of 630 nm and 20 µm. It was found that the stress-induced and magnetic field-induced martensite variant reorientation are size dependent and became more difficult with the reduction in sample size. Surprisingly, it was still possible to magnetically activate the shape change in the micropillars which indicates the fact that magnetocrystalline anisotropy energy increases with the reduction in sample dimensions. Ni45Mn36.6Co5In13.4 pillars between the 600 nm and 10 µm diameters were investigated along the [100] direction of the austenite to study the size effects in the magnetic field-induced phase transformation (MFIPT). MFIPT was obtained down to 5 µm size in these pillars with reasonable magnetic field levels similar to their bulk counterparts.