Aluminium applications can be found in the vast majority of industries – particularly the automotive, aerospace and building sectors. Light weight, good corrosion resistance, high strength with good machining and weldability has led 6xxx series alloy to be the most widely used for extrusion products. Semi-continuous direct-chill (DC) casting is a well established process and the most widely used in the production of wrought aluminium extrusion billets. The techniques have continuously evolved since its invention in the 1930s. To ensure high productivity and a quality billet by DC casting, grain refiners are added during casting prior to solidification. It is efficient, cost effective and considered optimized in modern production techniques. However, some problems still persist, for example, macrosegregation, centerline cracking, porosity, hot tearing, etc. For surface finish critical products, particles in added grain refiners may cause surface defects during downstream processing. Additions of grain refiners are also not desirable for recycling of the end use products. As a novel DC casting technology, the melt conditioned DC casting (MC-DC) technology is developed to achieve uniform fine equiaxed grains without deliberate additions of grain refiners. The MC-DC process is implemented by submerging a rotor-stator high shear device into the mould assembly of a conventional hot-top vertical DC caster. In this work, the fundamentals of MC-DC process has been investigated by studying the flow patterns in the sump using computer modelling in combination with thermal field measurement and delineation of the sump profile. Followed is the microstructural evolution of the MC-DC castings. Then the formation of Fe-bearing intermetallics which are critical to the arrangement of homogenisation treatment are presented. The grain refining mechanism by MC-DC is due to enhanced heterogeneous nucleation on dispersed oxides and grain fragments by intensive melt shearing, in combination with dendrite fragmentation and transportation in a uniform temperature and solute field. By optimising MC-DC parameters, alleviation of macrosegregation can be achieved even compared with DC-GR castings. Another finding is the correlation between grain structure and the distribution of the Fe-intermetallic particles. It has been demonstrated that equiaxed dendritic grains with fine secondary dendritic arm spacings achieved in MC-DC are preferred rather than finer granular grains in grain refined material. MC-DC also promotes the formation of α- Fe-bearing intermetallics. All these offer the potential for the reduction of homogenisation practices currently required as part of the DC process.

Le contrôle de la fabrication des structures cristallines des médicaments est un enjeu crucial pour l'industrie pharmaceutique. Plusieurs exemples ont montré qu'une mauvaise maîtrise du polymorphisme conduisait à des situations dramatiques. Récemment, une méthode permettant la maîtrise du polymorphisme de molécule organique dissoute en solution à l'aide de la polarisation d'un faisceau laser a été découverte aux Etats-Unis. Cette thèse étudie l’effet du laser sur des solutions aqueuses de molécules de glycine, L – (+) – histidine, D – (-) – et L – (+) – acide glutamique. Afin de réaliser l’étude, un montage expérimental a été construit permettant le contrôle de nombreux paramètres et une méthode spécifique de travail a été développée afin de limiter fortement l’aléa expérimental. Une étude multi-paramètres incluant l’effet comparé des polarisations linéaire et circulaire dans du H2O et du D2O de la nucléation induite par laser non-photochimique (NPLIN) de la glycine a été menée. Une étude préliminaire de l’effet du laser sur les solutions d'histidine et de l' acide glutamique a également été réalisée. Il est montré que le solvant est un facteur déterminant du contrôle du polymorphisme. Toutefois, la conjonction de la polarisation et de la concentration a une influence sur les polymorphes de glycine obtenus dans le H2O. Les résultats obtenus permettent de contribuer à la compréhension du mécanisme en améliorant l'hypothèse initiale de l'effet Kerr. / Polymorphism control of drug molecules is one the main challenges facing drug companies. Several examples have shown than an uncontrolled polymorphism crystallization could lead to dramatic situation. One the most recent progress in the polymorphism control is the unwanted discovery of polymorphic selective crystallization of organic molecule dissolved in solution based on the laser beam polarization. This thesis deals with the implantation of this method in France for the first time based on a methodology limiting experimental hazard and a special design experimental device dedicated to this study. This work is based on an important review of known results of the field and published for the first time. An important multifactor study was done on glycine, histidine and glutamic acid, which allows to improve knowledges on the putative initial mechanism based on the Kerr effect. It has been established that the solvent is the dominant factor, letting laser polarization as the third factor for polymorphism control after concentration.

Le procédé de galvanisation en continu consiste à recouvrir les tôles d'acier d'un revêtement de zinc en les immergeant dans un bain métallique fondu. Lors du recuit continu à 800 °C sous atmosphère N2-H2 qui précède l'immersion de la tôle dans le bain, la structure de l'acier est recristallisée et les oxydes de fer sont réduits. Il se produit en même temps la ségrégation et l'oxydation des éléments d'alliages moins nobles que le fer qui peut être à l'origine de défauts de revêtement. A fin de mieux comprendre les réactions d'oxydation sélective qui se produisent à la surface et en profondeur de l'acier, nous avons étudié la germination et la croissance d'oxydes sélectifs sur un acier ferritique. La germination des précipités a lieu à une température voisine de 700 °C. L'analyse du comportement géométrique moyen des particules externes formées en surface met en évidence la croissance des précipités au cours du recuit. Le diamètre des particules augmente tandis que leur densité surfacique diminue. Les oxydes formés sont principalement MnO, SiO2, Mn2SiO4, MnAl2O4 et B2O3. L'orientation des plans joue un rôle important sur l'oxydation externe. La germination est observée sur des surfaces {111} puis sur des surfaces {100}. L'énergie de surface, différente d'un plan cristallin à l'autre, intervient dans ce mécanisme. On observe une différence notable sur le comportement géométrique des précipités entre les principaux plans cristallins du fer. La croissance des précipités est plus avancée (la densité surfacique des précipités est faible et leur diamètre équivalent est grand) sur les plans {111} et {211} que sur les plans {110}. Le plus grand nombre de petites particules est obtenu sur les plans {100}. Un modèle simplifié adapté aux profils de concentrations en manganèse et en silicium en profondeur permet de déterminer les coefficients de diffusion de Mn et Si caractéristiques de l'oxydation sélective de notre acier. Les valeurs des coefficients de diffusion apparents obtenus prennent en compte la diffusion dans les joints de grains et dans les dislocations, présents en grand nombre dans l'acier initialement laminé à froid. / Continuous galvanizing process involving immersion in a molten zinc bath is commonly used to form zinc coatings on steel sheets. Before hot-dip galvanizing, the steel sheets are annealed at a temperature of 800 °C in a N2 atmosphere containing 5 vol.% of H2, with only traces of water. This heat treatment is used to recrystallize the steel substrate and to reduce the iron oxides in order to improve the wettability by liquid zinc. At the same time, the less-noble alloying elements of the steel preferentially oxidize and di_use towards the surface. The aim of this study is a better understanding of selective oxidation of ferritic steels. Nucleation is observed at a temperature of 700 °C. The measurements of the geometrical characteristics of the precipitates show that their diameter increases and the number of precipitates per unit surface area decreases during annealing. The oxide particles are found to be composed of MnO, SiO2, Mn2SiO4, MnAl2O4 and B2O3. External oxidation is also dependent on the crystallographic orientation of the substrate. Nucleation on {111} faces takes place earlier than nucleation on {100} faces. Surface energies can explain this observation. There is a difference in geometrical characteristics of the external particles on grains of main planes of body-centered cubic iron substrate. Growth on {111} and {211} orientation planes is ahead (surface density is lower and equivalent diameter is higher) of growth on {110} grains. The smallest number of particles is found on {100} grains. Diffusional information are calculated from obtained depth concentration profiles by means of simple models. Calculated global diffusion coefficients take into account diffusion in grain boundaries and in dislocations. Cold rolling steels contain lots of these easy paths of diffusion.

L’étude du polymorphisme de composés pharmaceutiques est un domaine en plein essor. Cela est dû d’une part aux pressions économiques exercées par l’industrie pharmaceutique et d’autre part pour une meilleure compréhension des conséquences du polymorphisme sur les propriétés des médicaments (stabilité physique et chimique, solubilité, vitesse de dissolution,biodisponibilité, propriétés mécaniques, etc.). Cette thèse étudie la cristallisation par la technique de nucléation non-photochimique induite par laser (NPLIN) des molécules pharmaceutiques organiques. Dans ce contexte, un nouveau montage expérimental semi-automatisé adapté aux exigences des études NPLIN a été conçu et réalisé, permettant le contrôle de nombreux paramètres et le traitement simultané d’un grand nombre d'échantillons et ainsi réalisé un gain de temps considérable. Une méthode de travail a été également établie afin de limiter l’aléa expérimental. L’étude de l’impact des paramètres du laser sur la cristallisation de la carbamazepine et du sulfathiazole dans différents solvants(méthanol, éthanol, acétonitrile) a été menée. Les résultats obtenus ont permis de démontrer pour la première fois dans la littérature que la NPLIN permet d’obtenir des cristaux de CBZ et de sulfathiazole dont les formes polymorphiques dépendent de la polarisation du laser et du type de solvant. Une approche permettant la prédiction de la forme polymorphique des molécules organiques de la base CSD, dans le cas de l’utilisation de la NPLIN, a été proposée et appliquée pour les molécules CBZ et la sulfathiazole étudiées expérimentalement. A partir de nos résultats expérimentaux, des calculs d’énergie d’interactions ab initio de dimères des molécules de carbamazépine et de sulfathiazole et sur les résultats observés dans la littérature nous avons pu émettre des hypothèses quant au mécanismes impliqués dans la nucléation NPLIN. / Polymorphism study of pharmaceutical compounds is a growing field. This is due, on one hand, to the economic pressure of the pharmaceutical industry and on the other hand, to the more awareness of the polymorphism consequences on the drug properties (chemical and physical stability, solubility, dissolution rate, bioavailibality, mechanical properties,manufacturing process, etc).This thesis studies the crystallisation of organic pharmaceutical molecules by using the Non Photochemical Light Induced technique. Within this context, a new semi-automatic experimental setup suitable to the requirements of NPLIN studies was devised and realised,allowing the control of many parameters and a simultaneous processing of a great number of samples and thus saving a considerable amount of time. A strict working methodology is also established to limit experimental errors. The study of the impact of laser parameters on the crystallisation of carbamazepine and sulfathiazole within different solvents (methanol,ethanol, acetonitrile) was carried-out. The obtained results allowed demonstrating, for the first time in literature, that NPLIN allows to obtain CBZ and sulfathiazole crystals for which the polymorphic forms depend upon the laser polarisation and solvent type. An approach for predicting the polymorphic form of organic molecules in the CSD database, for the case of NPLIN, was proposed and applied for the case of CBZ and sulfathiazole that were studied experimentally. We have also provided hypotheses to explain the mechanisms involved in NPLIN nucleation.

A expansão natural de vegetação lenhosa sobre pradarias tem sido observada em escala global, mas os regimes de distúrbio influenciam a dinâmica da expansão. Basicamente dois padrões de expansão florestal podem ser considerados em áreas campestres excluídas de manejo: o avanço gradual a partir das bordas florestais e a colonização de indivíduos isolados na matriz campestre. Uma vez estabelecidas, as espécies colonizadoras de campos podem facilitar a dispersão de outras espécies sob suas copas (perch effect), servindo como poleiros naturais; e/ou ainda podem facilitar o estabelecimento dessas espécies, atuando como berçários (nurse plant effect). Neste contexto, Araucaria angustifolia é um exemplo de espécie colonizadora em campos que contribui para o processo de expansão. Além disso, A. angustifolia caracteriza-se pela formação de anéis de crescimento anuais em decorrência de variações climáticas sazonais, permitindo o estudo da dinâmica e estrutura etária das populações com o uso de métodos dendrocronológicos. Com base nisso, avaliamos nesta dissertação a estrutura etária de A. angustifolia em campos excluídos de manejo por 34 anos e a relacionamos com o processo de expansão florestal, bem como averiguamos o seu papel como facilitadora da dispersão e estabelecimento de espécies lenhosas colonizadoras de campos. Os resultados apontam para uma relação inversa entre a estrutura etária e a distância da borda florestal; e indicam que A. angustifolia atua mais como um poleiro para deposição de diásporos, do que propriamente como uma facilitadora do estabelecimento dessas espécies. / The natural expansion of woody vegetation over grassland has been observed worldwide, but the expansion dynamics is influenced by the disturbance regimes. Two patterns of forest expansion are well documented: gradual expansion from the forest borders and by the process of nucleation, which consists in the colonization of the grassland matrix by isolated trees. Once established, these colonizing species can facilitate the dispersion process by acting as perches, and/or as nurse plants by facilitating the recruitment of new colonizers. Araucaria angustifolia is an example of colonizer species in open areas contributing to forest expansion. Besides, A. angustifolia presents tree rings that reflect annual cycles of growth and dormancy, allowing us to study dynamics and population age structures using dendrochronological methods. In this dissertation, we evaluate the age structure of A. angustifolia in grasslands excluded from disturbance for 34 years and relate it to the expansion process. As well, we evaluate the role of A. angustifolia as perch (by facilitating seed dispersal) and as a nurse plant (by facilitating the establishment of other species under the crown). Our results point out to an inverse relationship between age structure and distance from the border and indicate that the role of A. angustifolia is more important as a perch than facilitating the establishment of other species.

This thesis details the ACTIVE campaign in the tropics of northern Australia during 2005-2006 (based in Darwin). The focus of the campaign was to find the influence of tropical convection on the aerosol and chemical content of the Tropical Tropopause Layer [TTL] and the cirrus cloud cover in the area, which is important for the global energy budget. This study details the background climatology of the Darwin region with statistical categorisation of the trace gases and particles. The TTL had regions of extremely high aerosol number concentration, much higher than that of the PBL. The 10 to 1000 nm particle concentrations were as high as 25,000 cm-3 and 100 to 1000 nm were as high as 1000 cm-3. High aerosol concentrations were usually found in cloud-free conditions; cloudy regions were typically low in aerosol number. Wind data and trajectories (BADC) were used to find the origin of the high particle concentrations. Aerosols were found to be nucleating in outflow regions of convective anvils. SO2 oxidation to H2SO4 is a widely accepted mechanism for nucleation. A binary mechanism (H2O-H2SO4), with SO2 as the precursor, was found to be inadequate in explaining the nucleation and growth rates -- tested using an aerosol sectional model. However, it was found, via back trajectory analysis, that the climatology of Darwin was influenced by local and long-range sources, including advection from Indonesia and the Tropical Warm Pool. These distant sources could have introduced condensable matter, with aerosol precursor properties (certain organic compounds). The aerosol model found a condensable precursor concentration of at least 300 pptv was necessary to replicate the observations.

Second phase particles play an important role in the recrystallization of aluminium alloys. They give rise to high level of local lattice misorientation around the particle, in particle deformation zone (PDZ) during processing. These can act as potent nucleation sites for new recrystallized grains in a process known as particle stimulated nucleation (PSN). This mechanism is essential to produce material with a more random texture and small grain size, which helps e.g. ductility and formability. A new HRDIC technique is used here in combination with EBSD to investigate the evolution of deformation structures by linking the local deformation (by Digital Image Correlation, DIC) to the lattice orientation before and after deformation by EBSD measurements and compared with the CPFEM predictions. The results show that strain is very heterogeneous during deformation and concentrates mainly in slip bands. The spacing between these bands is affected by several factors: applied strain, crystallographic orientation and the existence of small dispersoids. Thus, the relationship between the strain, particle size and rotation in the deformation zone is much more complex than predicted by existing models.

Nucleation is the first step in the formation of a new phase in a thermodynamic system. The Classical Nucleation Theory (CNT) is the traditional theory used to describe this phenomenon. The object of this thesis is to investigate nucleation beyond one of the most significant limitations of the CNT: the assumption that the surface tension of a nucleating cluster of the new phase is independent of the cluster’s size and has the same value that it would have in the bulk of the new phase. In order to accomplish this, we consider a microscopic, two-dimensional Lattice Gas Automata (LGA) model of precipitate nucleation in a supersaturated system, with model input parameters Ess (solid particle-to-solid particle bonding energy), Esw (solid particle-to-water particle bonding energy), η (next-to-nearest neighbour bonding coeffiicent in solid phase), and Cin (initial solute concentration). The LGA method was chosen for its advantages of easy implementation, low memory requirements, and fast computation speed. Analytical results for the system’s concentration and the crystal radius as functions of time are derived and the former is fit to the simulation data in order to determine the system’s equilibrium concentration. A mean first-passage time (MFPT) technique is used to obtain the nucleation rate and critical nucleus size from the simulation data. The nucleation rate and supersaturation are evaluated using a modification to the CNT that incorporates a two-dimensional, radius-dependent surface tension term. The Tolman parameter, δ, which controls the radius-dependence of the surface tension, decreases (increases) as a function of the magnitude of Ess (Esw), at fixed values of η and Esw (Ess). On the other hand, δ increases as η increases while Ess and Esw are held constant. The constant surface tension term of the CNT, Σ0, increases (decreases) with increasing magnitudes of Ess (Esw) fixed values of Esw (Ess), and increases as η is increased. Together, these results indicate an increase in the radius-dependent surface tension, Σ, with respect to increasing magnitude of Ess relative to the magnitude of Esw. Σ0 increases linearly as a function of the change in energy during an attachment or detachment reaction, |ΔE|, however with a slope less than that predicted for a crystal that is uniformly packed at maximum density.

Nucleation is a key step in the crystallisation process, where a new crystalline solid phase is created from a supersaturated solution. The applications of crystallisation as a purification and separation technique span many industries, yet still no definitive molecular mechanism for nucleation exists. This PhD is part of a critical mass research project involving researchers from both the Universities of Manchester and Leeds. The aim is to reveal the relationship between structural components of the nucleation transition state, solution phase molecular self-assembly and nano cluster formation, through to critically sized crystalline nuclei which then grow to crystals. All work has been carried out on a small organic molecule, p-aminobenzoic acid (PABA). This PhD has delivered successful characterisation of PABA in the solid and solution state, along with a detailed understanding of its nucleation kinetics and growth rates from a range of solvents. PABA has two enantiotropically related polymorphs, α and β, with the former constructed of carboxylic acid dimers and the latter of a hydrogen bonded tetramer network linking alternate acid and amine functionalities. New determinations of the crystal structures of both forms were submitted to the CCDC with Ref codes of AMBNAC07 and 08 for α and β PABA respectively. A detailed morphological study on both forms of PABA employing modelling and experimental methods has revealed the effect of solvent on the growth habit. In all polar solvents, α PABA displays a more important or slower growing (002) face than the calculated morphology implies. In water, β PABA has a much smaller (101 ̅) face in comparison to β PABA grown from alcohols. Crystallisation experiments demonstrate a clear solvent effect on the appearance of the two polymorphs. From organic solvents only α PABA is obtained, from water both α and β PABA are crystallised. A database search (CCDC) suggests that water may play an important role in the stabilisation of the nucleation transition state for both α and β PABA. This is not possible in organic solvents. Detailed nucleation and crystal growth kinetics have been measured for α PABA at 20°C in water, acetonitrile, ethyl acetate and 2-propanol. A clear solvent trend was observed in both the derived rates of molecular attachment and crystal growth. These were fastest in water, followed by acetonitrile, then ethyl acetate and finally slowest, in 2-propanol. This can be explained by the solvation of the carboxylic acid functional group, where 2-propanol is deemed the most effective solvator of building units in solution and on a crystal surface. This conclusion is supported by the solution FTIR spectroscopy, which clearly confirms strong solvation.

Le contrôle des caractéristiques des cristaux de glace, gouvernées par l'étape de nucléation, demeure un enjeu majeur dans les procédés de congélation et de lyophilisation industriels. Cependant la nucléation est par nature un phénomène aléatoire. L'application d'ultrasons de puissance, capable de générer de la cavitation acoustique, compte très certainement parmi les plus prometteuses méthodes permettant de contrôler le déclenchement de la nucléation, mais le matériel et les conditions opératoires à mettre en oeuvre afin d'industrialiser le procédé restent encore à définir.Le premier objectif de ce travail a été de corréler empiriquement les caractéristiques géométriques des cristaux de glace et les conditions opératoires dans le cas de la congélation d'une solution aqueuse de mannitol en vials. Il a été montré, grâce à une analyse de surface de réponses basée sur un plan d'expérience de deuxième ordre, que l'augmentation du sous refroidissement et de la puissance acoustique provoquent une diminution de la taille moyenne des cristaux et une augmentation de leur circularité.Le deuxième objectif était la modélisation de la cinétique de nucléation de glace dans de l'eau pure déclenchée par cavitation acoustique. D'après les simulations réalisées, la nucléation peut être initiée à de faibles sous-refroidissements (quelques degrés) au moyen de pressions acoustiques modérées (de l'ordre de un bar). Le nombre de nuclei créés est d'autant plus important que le sous-refroidissement et la pression acoustique sont élevés.Ces résultats sont cohérents si l'on considère que la taille des cristaux est inversement proportionnelle au nombre de nuclei générés. / Ice crystal characteristics control, which are governed by the nucleation step, remains a key issue in industrial freezing and freeze-drying processes. However nucleation is by nature arandom phenomenon. Power ultrasounds, able to generate acoustic cavitation, are one of the most promising methods of triggering nucleation, but operating conditions pertaining to an industrial freezing process have not yet been defined.This work aims first at empirically correlating the ice crystals' geometry to the operating conditions, in the case of mannitol aqueous solution in vials freezing. A response surface analysis based on a second order experimental design proved that increasing both supercooling and acoustic power resulted in decreasing ice crystals' mean size and increasing their circularity.The second goal was the modelling of ice nucleation triggered by acoustic cavitation in pure water. According to simulations, the nucleation could be initiated with moderate acoustic pressure amplitude (around one bar) even at low supercooling levels (around few degrees). The number of generated nuclei appeared to increase with the super cooling and with the acoustic power which should lead to a decrease of ice crystals' size as observed experimentally.These results are consistent if the ice crystals' size is considered to be inversely proportional to the number of generated nuclei.