A method for measurement of crystallization induction time periods using a spectrophotometer is described. The turbidity of lysozyme solutions at sodium chloride concentrations of 0%, 3%, 6%, 9% (w/v) in 0.1 M NaAc (pH 4.0) and a lysozyme concentration of 10mg/ml was monitored at 350nm and showed a dramatic increase after nucleation occurred. Heterogeneous sources of nucleation were removed via filtration with 100,000 and 500,000 MWCO filters. Larger pore size, 0.2μm, filters were not able to remove these particles. The non-filtered and 0.2μm filtered had the same turbidity profiles except that the 0.2μm filtered had an induction time of 152min compared with the 119min induction time for the non-filtered solution. The 500,000 MWCO filter had a significant reduction in the formation of prenucleation aggregates and the induction time increased from 119min for non-filtered to 178min for the 500,000 MWCO filtered. Also, when the 100,000 MWCO filter was used there was no nucleation or crystallization over the 240min time frame. The increase in turbidity was attributed to an increase in particle size and not to bacterial growth because the solutions were found to be free of bacteria or fungi by microbiological analysis. Results from hanging drop vapor diffusion crystallization on the same solutions used in the turbidity study indicate that the sources removed by filtration lead to nucleation. Finally, sodium azide was added to the solutions at a concentrations of 0.17% (w/w) and was found to interfere with or delay lysozyme nucleation.

Single levitated microdroplets of sodium chloride, potassium chloride, and natural seawater are investigated under conditions similar to that in the troposphere by using the electrodynamic balance technique. The thermodynamics and the kinetics of liquid-to-solid phase transitions have been investigated as a function of temperature and humidity. The temperature dependence of the critical partial pressure of water vapor over aqueous supersaturated aerosol droplets allows us to determine negative values for the integral heat of solution of KCl, NaCl and Mediterranean Sea droplets. In addition, the rates of homogeneous nucleation from supersaturated solution droplets are reported, where the data are fitted with three exponential functions to give three values for the nucleation rates. The phase transition processes which occur on different time scales are identified. The investigation of natural sea salt aerosol droplets collected from the Mediterranean Sea, Atlantic Ocean, Pacific Ocean, North Sea, and Suez Canal show that the phase change (liquid-to-solid) can occur at relative humidities that are greater than 33% RH, where the deliquescence humidity of MgCl2 is known to occur. It is found that there are slight variations (either a decrease or an increase) in water vapor pressure over the supersaturated aerosol droplets due to the change in water salinity, organic components that are present in the water sample, the depth, where the water sample is gathered, and its geographic location. The experimental results show that the presence of the organic substances in the aerosol particles affects the crystallization process depending on the amount and the type of the organic substance. It is observed that adding 1-heptanol to a NaCl droplet increases the crystallization diameter, which is attributed to the formation of a layer of the organic substance on the droplet surface, so that water evaporation cannot efficiently occur.

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The research addressed in this thesis focuses on monitoring and characterization of pharmaceutical compounds by laser backscattering. In particular, this study covers two topics: (1) the determination of naproxen sodium solubility in water, and its phase transition; and (2) comparisons of batch and laminar flow tubular crystallizers for the production of paracetamol (acetaminophen) and D-mannitol. Using a Lasentec™ Focused Beam Reflectance Measurement (FBRM) device, the solubility of naproxen sodium in aqueous solutions was determined over a temperature range from 15.2 to 39.7 ℃ With the determination of the solubilities of two pseudopolymorphs, anhydrous and dihydrated naproxen sodium, the phase transition point between these two forms of the pharmaceutical compound was determined to occur at 30.3 ℃ Enthalpy of solution and metastable zone widths were also determined for the experimental conditions. Crystallizations of paracetamol and D-mannitol were performed in a batch crystallizer and in a laminar flow tubular crystallizer (LFTC) system. In the latter system, supersaturation was generated rapidly in the solution being transported through a temperature-controlled tube and recovered in a batch vessel where product crystals were grown to equilibration. Because of the rapid rate at which supersaturation was generated in the LFTC, the resulting crystals were of smaller mean size than those obtained from batch crystallizations. The total time required for crystallization was significantly less with the LFTC than with the batch unit. Additionally, the rapid cooling in the LFTC led to the formation of two different polymorphs of paracetamol, Forms I and II.

Supersaturated substitutional alloys formed by ion implantation and rapid liquid-phase epitaxial regrowth induced by pulsed-laser annealing have been studied using Rutherford-backscattering and ion-channeling analysis. A series of impurities (As, Sb, Bi, Ga, In, Fe, Sn, Cu) have been implanted into single-crystal (001) orientation silicon at doses ranging from 1 x 10^15/cm2 to 1 x 10^17/cm2. The samples were subsequently annealed with a Ω-switched ruby laser (energy density ~1.5 J/cm2, pulse duration 15 x 10-9 sec). Ion-channeling analysis shows that laser annealing incorporates the Group III (Ga, In) and Group V (As, Sb, Bi) impurities into substitutional lattice sites at concentrations far in excess of the equilibrium solid solubility. Channeling measurements indicate the silicon crystal is essentially defect free after laser annealing. The maximum Group III and Group V dopant concentrations that can be incorporated into substitutional lattice sites are determined for the present laser-annealing conditions. Dopant profiles have been measured before and after annealing using Rutherford backscattering. These experimental profiles are compared to theoretical model calculations which incorporate both dopant diffusion in liquid silicon and a distribution coefficient (k') from the liquid. It is seen that a distribution coefficient (k') far greater than the equilibrium value (k0) is required for the calculation to fit the experimental data. In the cases of Fe, Zn, and Cu, laser annealing causes the impurities to segregate toward the surface. After annealing, none of these impurities are observed to be substitutional in detectable concentrations. The systematics of these alloys systems are discussed.

Les modèles d'éléments finis des automobiles donnent des grandes tailles de problèmes matriciels, ce qui demeure coûteux en ressources numériques pour une procédure d'optimisation. La multiplicité des phénomènes couplés du problème d'interaction de l'air de l'habitacle et de la superstructure rend plus sensible, à des variations mineures des paramètres, une optimisation directe du véhicule. Pour réduire les temps de calculs et l'espace mémoire liés à la simulation numérique en éléments finis, une méthode de double synthèse modale est appliquée sur la structure et le fluide. Ceci permet de diminuer le nombre de degrés de liberté de frontière. Egalement, un algorithme a été développé pour minimiser le nombre d'évaluations de fonction au cours des itérations d'optimisation. L'approche modale permet également de décomposer le problème d'optimisation de la réponse vibro-acoustique par des sous-problèmes couplés d'optimisation de critères modaux. Ces critères modaux explicitent les couplages fréquentiels par des termes d'amplification et les couplages spatiaux par des paramètres effectifs modaux. Ils favorisent ainsi le développement d'une stratégie d'optimisation robuste par le contrôle modal des effets prépondérants sur la qualité vibro-acoustique des véhicules. / Finite element models and the complexity of vehicle passenger compartments make it harder the optimization, mainly because of expensive computing resources and multiple coupled phenomena of fluid-structure problems. Strategies to improve time and memory performance consist in the use of reduction methods, and combined with efficient optimization techniques, vibro-acoustic solutions of better quality can be performed. The complexity of the system is taken into account thanks to a hierarchical optimization process. Both reduction method and gradient-based optimization algorithm are investigated. Based on modal synthesis, special criteria help to determine critical vibration propagation paths. A modified SQP (Sequential Quadratic Programming) algorithm is also developed in order to provide a faster convergence speed. Such process is to be applied on an academic example and hollow parts and panels of a whole passenger compartments. It allows to find relevant and non obvious solutions by minimizing noise and vibration transfer functions in a relatively wide range of frequencies.