Predicting events in metastable systems is an important but challenging problem. It can help society forecast, prevent, or prepare for upcoming catastrophes. However, many metastable systems in nature operate near a critical point and are empirically unpredictable. We developed machine learning predictors, applied them to the prediction of nucleation events in the metastable Ising model, near and far from the spinodal critical point. We observed decreasing predictability as the critical point is approached, and found that this unpredictability is due to the vanishing density difference between the nucleating droplet and the background. We also developed a tensor representation of Lennard-Jones con gurations using the symmetry order parameters of the particles and use this representation to predict nucleation in a dense Lennard Jones liquid. Finally, we investigated the noise-induced critical point in two variations of the OFC model - a coupled OFC model and a OFC model with multiplicative noise. In both variations, we found a critical phase boundary that separates the ergodic and non-ergodic phase and the termination point of the phase boundary, which is consistent with a higher-order phase transition.

Cette thèse a pour but de démontrer la faisabilité de la technique de Nucléation non-Photochimique Induite par Laser (NPLIN) appliquée aux composés pharmaceutiques organiques. Avec nos résultats expérimentaux, ceux obtenus dans la littérature et calculs théoriques ab initio, nous avons discuté du mécanisme de la méthode NPLIN.Cette thèse a décrit en premier lieu, le nouveau montage expérimental semi-automatisé adapté aux exigences des études NPLIN développé à CentraleSupelec. Des expériences NPLIN sur le sulfathiazole (STZ), l-acid glutamique (LGA) et la glycine (GLY) sont menées pour étudier l’impact des paramètres du laser et de la sursaturation des solutions sur leur cristallisation. Les résultats expérimentaux montrent que la technique NPLIN permet d’obtenir des cristaux de STZ, LGA and GLY. L’efficacité de la nucléation croit avec l’augmentation de la densité d’énergie du laser et de la sursaturation. Un indice nouveau Ind50 a été défini correspondant au couple densité d’énergie/sursaturation où 50% nucléation est atteinte. Son comportement est discuté. Il est trouvé que le nombre cristaux STZ induits par laser dépend linéairement avec le temps d’irradiation. Une dépendance du polymorphe des cristaux induit par le laser avec la polarisation du faisceau laser est également découvert pour STZ et GLY. Un autre indice Det(A) est utilisé pour caractériser l’impact de la polarisation sur le polymorphisme. Des calculs théoriques ab initio par le logiciel Gaussian09 permettent de donner une estimation des énergies d’interaction des différents dimères pour des polymorphes de STZ, LGA, GLY, l-histidine (LH) et urée. L’empilement des molécules dans les clusters pré-existant est prédit en accord avec la détermination des énergies d’interaction. L’analyse de corrélation entre la symétrie d’empilement et des résultats expérimentaux souligne l’hypothèse de l’effet Kerr pour expliquer cet impact de la polarisation du faisceau laser sur le polymorphisme. / This thesis concerns the demonstration of the feasibility of Non-Photochemical Laser Induced Nucleation (NPLIN) of some organic pharmaceutical compounds. Using our experimental results and those obtained in literature together with ab initio theoretical calculations we have been able to discuss the mechanism of the NPLIN method.This thesis presents a new experimental set-up developed at CentraleSupelec and dedicated to perform NPLIN experiments. NPLIN experiments on sulfathiazole (STZ), l-glutamic acid (LGA) and glycine (GLY) have been carried out to examine the impact of laser parameters and solution supersaturation on their crystallization. Experimental results show that crystals of STZ, LGA and GLY have been obtained by means of NPLIN. For these compounds, nucleation efficiency increases with laser power density and solution supersaturation. A new index Ind50 corresponding to the couple (energy density/supersaturation) where 50% of nucleation is teached, has been defined. Its behavior has been discussed. It was found that laser induced STZ crystal number depends almost linearly on exposure duration. Moreover, for STZ and GLY, a dependance of laser induced crystal polymorph on laser polarization has been found. Another new index Det(A), has been used for characterization of the impact of the polymorphism. Ab initio quantum computations using Gaussian09, provided an interaction energy estimate for different dimers in different polymorphs of STZ, LGA, GLY, l-histidine (LH) and urea. Packing mode in pre-existing clusters is predicted in agreement with interaction energy determinations. Correlation analysis between packing symmetry and experimental results, shed new light on the Kerr effect hypothesis relative to the impact of laser polarization on polymorphism.

With the advent of the new" high Tc superconductors as well as the increasing use of cryo-cooled conventional electronics, liquid nitrogen will be one of the preferred cryogens used to cool these materials. Consequently, a more thorough understanding of the heat transfer characteristics of liquid nitrogen is required. In these investigations the transient heating characteristics of liquid nitrogen to states of nucleate and film boiling under different liquid flow conditions are examined. Using a metal hot wire/plate technique, it is verified that there is a premature transition to film boiling in the transient case at power levels as much as 30 percent lower than under steady state nucleate boiling conditions. It is also shown that the premature transition can be reduced or eliminated depending on the flow velocity The second part of this research analyses the nucleation (boiling) process from a dynamical systems point of view. By observing how the boiling system variables evolve and fluctuate over time, it is hoped that physical insight and predictive information can be gained. One goal is to discover some indicator or signature in the data that anticipates the transition from nucleate boiling to film/boiling. Some of the important variables that make up the boiling system are the temperature of the heater and the heat flux through the heater surface into the liquid nitrogen. Results, gained by plotting the system’s trajectory in the heat flux-temperature plane, are that on average the system follows a counterclockwise trajectory. A physical model is constructed that explains this behavior. Also, as the applied heater power approaches levels at which the transition to film is known to occur, the area per unit time swept out in the heat flux-temperature plane is seen to reach a maximum. This could be of practical interest as the threshold to film boiling can be anticipated and possibly prevented.

Yes / This study focuses on numerical modeling of condensation of water vapor in a Laval nozzle, using the liquid drop nucleation theory. Influence of nozzle geometry, pressure, and temperature on the average drop size is reported. A computer program written in MATLAB was used used to calculate the nucleation and condensation of water vapor in the nozzle. The simulation results are validated with the available experimental data in the literature for steam condensation. The model reveals that the average drop size is reduced by increasing the divergent angle of the nozzle. The results also confirm that increasing the inlet pressure has a direct effect on the average drop size while temperature rise has an inverse effect on the drop size.

<p>The effect of molybdenum on the isothermal proeutectoid ferrite reaction has been studied in low to medium (.05 - .43) carbon steels containing 1% molybdenum by weight. At 600 - 700°C molybdenum additions to steel result in the production of a dark etching ferrite constituent which has been shown to be heavily dislocated. The origin and stability of this transformation induced substrctures is considered.</p> <p>In these alloys the austenite twin boundaries are sites for nucleation of ferrite. A simple model to describe nucleation on twins has been constructed and consequences for the equilibrium shape of a ferrite crystal in austenite developed. The equilibrium shape was determined experimentally and the shape is commensurate with the model developed.</p> / Thesis / Master of Engineering (ME)

<p> Nonaqueous poly(methyl methacrylate) latices were prepared by nonaqueous dispersion polymerization of poly(methyl methacrylate) in heptane in the presence of either trimethylsilyl terminated or vinyl terminated polydimethylsiloxane stabilizer. Poly(methyl methacrylate) particles stabilized by vinyl terminated polydimethylsiloxane showed smaller particle sizes than did those stabilized by trimethylsilyl terminated polydimethylsiloxane. Diameters of the various latex preparations ranged from 1.4 to 0.8 μm and silicone content was around 2 mole percent in each case. Differences between the two types of latex were explained in terms of the nucleation mechanism operating during the preparation of the latices and in terms of the type of attachment of the stabilizer chain to the poly(methyl methacrylate) core.</p> <p> The effect of the silicone concentration present during particle formation was investigated. Vinyl terminated polydimethylsiloxane stabilized latex gave better stabilized particles than did methyl terminated polydimethylsiloxane stabilized latex. The results of varying the concentration and type of initiator were consistent with the conclusions about differences in nucleation and grafting mechanisms.</p> <p> The stability of polydimethylsiloxane stabilized poly(methyl methacrylate) particles was investigated in n-heptane. Acidified montmorillonite clay was determined as the optimum catalyst for this latex system. Flocculation set in at 70% of the original silicone content when the siloxane on the particle surface was degraded with montmorillonite clay in a good solvent. Flocculation was irreversible and occurred abruptly. The point of flocculation was reproducible and the rate of flocculation was identical for two different types of silicone stabilized poly(methyl methacrylate) latex.</p> / Thesis / Master of Science (MSc)

<p> Etch pits can be produced in iron whose shape reflects the crystallography of the crystal. It is shown that pit morphology can be adequately predicted from an orientation dependent dissolution theory. The influence of an air-formed surface oxide film on pit nucleation and morphology is demonstrated. </p> / Thesis / Master of Science (MSc)

<p> This investigation is an original study in nucleate pool boiling heat transfer, consisting of two parts: an experimental study and a theoretical study. The experimental study was performed with water boiling at atmospheric pressure on a single copper surface. Two different levels of heat flux were investigated. For the lower level of heat flux (92.21 kW/m2), three different levels of subcooling (0, 6.5, 12°C) were studied and for the higher level of heat flux (192.11 kW/m2), two different levels of subcooling (0, 7.5°C) were studied as well. </p> <p> The cross-spectral density function ·and the crosscorrelation function were used to determine the time elapsed (-r) between the start of bubble growth at two neighbouring active sites with separation (S). The experimental results indicate that for the lower level of heat flux at three different levels of subcooling, the separation (S) and the time elapsed (-r) are related. For the higher level of heat flux at 0°C subcooling it was not possible to detect any correlation, but for the 7.5°C subcooled condition a weak correlation was found to exist. For the lower level of heat flux, all the experimental data for the saturated and subcooled boiling conditions plotted as (S-Rd) versus (T-Tg) drew together into a single curve, indicating that a single relationship could fit all the data. </p> <p> Three different theoretical models were devised in an attempt to·explain the experimental observations. The first model involved heat diffusion in the water; the second model was based upon the disturbance caused by the propagation of a pressure pulse in a mixture of water and vapour and finally the third model involved heat diffusion in the solid. The first two models failed to give satisfactory agreement with the experimental results, but the theoretical predictions corresponding to heat diffusion through the solid gave good agreement with the experimental findings. </p> / Thesis / Doctor of Philosophy (PhD)

<p> The major part of the present work dealt with adapting the droplet technique to the study of nucleation from solution of some analytically important metal chelates. Precipitation from homogenous solution was introduced as the means of gradually increasing the supersaturation in the droplets. This new method of producing supersaturation enabled the extention of the droplet technique to nucleation studies of sparingly soluble substances. </p> <p> In addition, a second novel way of achieving supersaturation in the droplets was devised. In contrast to the first method, which increased the amount of solute at constant droplet volume, the second method maintained the amount of solute constant, while gradually reducing the volume of the droplet. This permitted studies on nucleation from solution of soluble substances to be carried out isothermally. </p> <p> The two techniques mentioned above were applied successfully to the study of nucleation from solution of four analytically important metal chelates and to several inorganic salts, respectively. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.