Water-mediated interactions between non-polar moieties play a crucial role in driving self-assembly processes such as surfactant micellization, protein folding, and many other diverse phenomena. Among a variety of forces contributing to the self assembly, hydrophobic interactions play a dominant role. Historically, thermodynamic models describing hydrophobic effects have invariably relied on macroscopic thermodynamic properties to infer this molecular behavior. Experimental studies help to probe the spatial correlations between model hydrophobic solutes and to measure their waters of hydration in order to examine structural perturbations in the surrounding water induced by the solute, or to measure directly the attractive forces between hydrophobic surfaces. Further, molecular simulations can be used to derive entropic and enthalpic contributions to the free energy of hydrophobic hydration in terms of water structure surrounding simple, model hydrophobic solutes, such as methane. Based on the results for simple solutes, these methods can now be extended to investigate the hydrophobic hydration of more complex molecular solutes of arbitrary size and shape such as micelles. Atomistic simulations of chemical systems provide a new perspective towards testing the theories behind the ubiquitous phenomenon of hydrophobic effect, and probe the underlying thermodynamic signatures. In this context, my research work delves into the water-mediated interactions leading to the hydrophobic hydration of short chain alkanes, volumetric properties of unfolded polypeptides and self-assembly mechanism in polymer-surfactant systems. The first part of my research involves re-optimization of existing force field interaction parameters for the CHn alkane sites (n=0 to 4) to accurately reproduce the experimental hydration free energies of linear and branched chain alkanes over a range of temperatures. This Hydrophobic Hydration-Alkane (HH-Alkane) model accounts for polarization effects in the alkane hydration and can be extended to polypeptides in water. Subsequent discussions will focus on the results from extensive molecular simulations of tri- and tetrapeptides to quantify the accuracy of the simulation model in capturing the volumetric properties of unfolded polypeptides. Group additivity correlation was used to calculate the partial molar volumes of the neutral sidechains of amino acids, glycine backbone unit and both zwitterionic and N-acetyl/amide terminal units. The simulation results will be compared to the experimental results to validate these observations. In addition, the research explores the self-assembly and aggregation mechanism in anionic sodium dodecyl sulfate (SDS) surfactant- non-ionic Polyethylene Oxide (PEO) and Poly vinyl pyrrolidone (PVP) polymer systems. Potential of mean force calculations at multiple temperatures show an increasing trend in hydrophobic attractions within the polymer-micelle system. Also, these simulations provide interesting insights into the experimentally observed phenomena between the polymers and the micelles starting from pre-formed structure as well as random configurations. / 1 / Lalitanand N. Surampudi

Nous cherchons à modéliser numériquement un jet flottant air-hélium dans une cavité avec deux ouvertures à partir de simulations aux grandes échelles (LES) et de simulations numériques directes (DNS). La configuration considérée est basée sur une étude expérimentale menée au CEA de Saclay reproduisant une fuite d'hydrogène en environnement confiné. La dimension de la cavité a été choisie pour permettre une transition laminaire-turbulent intervenant environ à la mi-hauteur de la cavité. Cette étude porte principalement sur trois points majeurs : l'influence des conditions aux limites sur le développement du jet et son interaction avec l'environnement extérieur, la validité du modèle numérique qui est analysée en comparant la distribution de vitesse obtenue numériquement aux mesures expérimentales (PIV) et, enfin, la compréhension de la distribution air-hélium et le phénomène de stratification qui s'établit à l'intérieur de la cavité. Nous observons dans un premier temps que des conditions limites de pression constante appliquées directement au ras des évents conduisent à une sous-estimation du débit volumique d'air entrant dans la cavité et donc à une surestimation de la masse de l'hélium à l'intérieur de la cavité, ce qui n'est pas acceptable dans un contexte d'évaluation du risque hydrogène. En revanche, la prise en compte, dans le domaine de calcul, d'une région extérieure à la cavité prédit correctement le flux d'air entrant. Les résultats numériques sont alors en bon accord avec les données PIV. Il a été montré que les prédictions de la DNS, par rapport à la LES, concordent mieux avec les mesures de vitesse par PIV. Le champ de concentration prédit numériquement présente une couche homogène en haut de la cavité, dont la concentration est en accord avec le modèle théorique de Linden et al. 1990. Cependant, sa position et son épaisseur ne correspondent pas au modèle. Ceci est principalement dû aux interactions directes entre le jet flottant et, d'une part, avec les limites solides de la cavité et d'autre part, avec l'environnement extérieur. L'analyse statistique concernant la production de la flottabilité de l'énergie cinétique turbulente (TKE) a permis d'identifier les limites du jet flottant. / We present numerical results from large eddy simulations (LES) and coarse direct numerical simulations (DNS) of an air-helium buoyant jet rising in a two vented cavity. The geometrical configuration mimics the helium release experimental set-up studied at CEA Saclay in the framework of security assessment of hydrogen-based systems with an indoor usage. The dimension of the enclosure was chosen to ensure a laminar-turbulent transition occurring at about the middle height of the cavity. This study focuses mainly on three key points : the influence of the boundary conditions on the jet development and its interaction with the exterior environment, the validity of the numerical model which is analyzed by comparing the numerical velocity distribution versus the measured particle image velocimetry (PIV) ones, and finally understanding the distribution of air-helium and the stratification phenomenon that takes place inside the cavity. We observe at first that applying constant pressure outlet boundary conditions directly at the vent surfaces underestimates the volumetric flow rate of air entering the enclosure and thus overestimate the helium mass inside the cavity. On the contrary, modelling an exterior region in the computational domain better predicts the air flow-rate entrance and numerical results matches better with the experimental PIV data. It has been figured out that the coarse DNS predictions match better with the velocities PIV measurements, compared to the LES. Numerical prediction of the helium field depicts a homogeneous layer formed at the top of the cavity, with a concentration in good agreement with the theoretical model of Linden et al. 1990. However, the position and the thickness of the layer do not correspond to the theory. This is mainly due to the direct interactions between the buoyant jet and both the solid boundaries of the cavity and the exterior environment. Statistical analysis regarding the buoyancy production of the turbulent kinetic energy (TKE) served to identify the limits of the buoyant jet.

Que sait-on du niveau des pollutions dans les différents milieux, comme l'air des agglomérations, les sols de friches industrielles, les cours d'eau ou les nappes ? Le mémoire présente l'application de la géostatistique à la quantification de ces pollutions et à l'évaluation de l'incertitude associée. L'analyse exploratoire des données vise à caractériser la variabilité spatiale ou temporelle des concentrations, ainsi que leurs relations avec le milieu. Obtenus pour des sites particuliers, mais généralisables à des contextes analogues, les résultats empiriques aident à mieux comprendre la pollution et guident la modélisation. Les modèles classiques sont alors adaptés, ou de nouveaux sont développés, par exemple pour décrire les concentrations le long d'un réseau hydrographique. Pour des problèmes complexes, le recours aux simulations devient nécessaire. Les applications sont nombreuses : prise en compte d'informations semi-quantitatives pour améliorer la précision de l'estimation, cartographie d'un risque de dépassement de seuil, adaptation de l'échantillonnage, améliorations conceptuelles pour la réglementation environnementale. Divisé en quatre parties, le mémoire débute par une synthèse bibliographique, avec une revue des principales méthodes utilisées en « géostatistique environnementale ». La deuxième partie présente des exemples de modélisation de pollutions à l'échelle locale ou régionale, dans les sols, les cours d'eau, et l'air. La troisième partie traite des simulations : le modèle gaussien seuillé pour représenter les hétérogénéités des formations, ainsi que les variables liées par des équations aux dérivées partielles, avec l'application à un écoulement simplifié. Des perspectives de recherche sont proposées dans la dernière partie.

We present results of molecular simulations, quantum mechanical calculations, and experimental data aimed towards the rational design of solvent formulations. In particular, we have found that the rate limitation of oxidation of methionine groups is determined by the breaking of O-O bonds in hydrogen peroxide, not by the rate of acidic catalysis as previously thought. We have used this understanding to design molecular level parameters which are correlated to experimental data. Rate data has been determined both for G-CSF and for hPTH(1-34). / Singapore-MIT Alliance (SMA)

1. Scope of the Study<BR> ---------------------<BR> In the modern engineering world, technological advancements drive the product design process. Increasingly powerful CAD programs make more complex product designs possible, which in turn boost the demand for more complex prototypes. At the same time, fast-moving competitive markets require frequent design changes, shorter lead times, and tighter budgets. In short, prototyping must be faster, better, and less expensive.<BR> <BR> Within this context, rapid prototyping in sheet metal is highly desirable because the manufacturing of functional prototypes speeds up the time to market. While the market is well developed when it comes to rapid prototyping for plastic parts, the options for prototyping geometrically complicated sheet metal components are more limited and extremely expensive, because all the methods available require expensive tooling, machinery or manual labor.<BR> <BR> Unlike many other sheet metal forming processes, incremental forming does not require any dedicated dies or punches to form a complex shape. Instead, the process uses a standard smooth-end tool, the diameter of which is far smaller than the part being made, mounted on a three-axis CNC milling machine.<BR> <BR> The sheet metal blank is clamped around its edges using a blank-holder. During the forming process, the tool moves along a succession of contours, which follow the final geometry of the part, and deforms the sheet into its desired shape incrementally.<BR> <BR> 2. Context of the Research<BR> --------------------------<BR> The work presented in this thesis was started in October 2003 in the framework of the SeMPeR project (Sheet Metal oriented Prototyping and Rapid manufacturing). This was a four-year-long project, whose purpose was to develop a research platform that would support an in-depth analysis of the incremental forming and laser forming processes. This platform supported experimental, numerical, and analytical research activities, the interaction between which was expected to lead to the design of new and improved process variants and the identification of effective process planning and control strategies.<BR> <BR> Four research partners from three different universities were involved in the project, covering the various academic disciplines required. As project leader, the PMA Department of the Catholic University of Leuven (KUL) provided extensive background knowledge in numerically controlled sheet metal forming processes, as well as long-term experience of experimental hardware development and process planning. This department was in charge of the experimental study of the processes. The MTM Department from the same university studied the processes in detail using accurate finite element models. The MEMC Department of the Free University of Brussels (VUB) provided expertise in in-process strain and displacement measurement, and material characterization by means of inverse method techniques. Finally, the ArGEnCo Department of the University of Liège (ULg), to which the present author is affiliated, undertook the task of developing a finite element code adapted to the incremental forming process.<BR> <BR> Because of its promising outcome, the project held wide industrial interest: several companies assisted in ensuring the ultimate industrial relevance of the research and provided logistical support in terms of hardware, materials, and specific data.<BR> <BR> 3. Objective of the Thesis<BR> --------------------------<BR> Although the SeMPeR project aimed at studying two rapid prototyping processes, the present work focused only on one of those: incremental forming. The goal of the team at the University of Liège was to adapt a department-made finite element code, Lagamine, to the incremental forming process. In particular, the computation time had to be reduced as much as possible while maintaining a sufficient level of accuracy.<BR> <BR> 4. Outline of the Thesis<BR> ------------------------<BR> The body of the text is divided into three parts.<BR> <BR> The first part contains two chapters. The first of these provides a literature review in the field of incremental forming. More specifically, it introduces the process, presents an overview of its practical implementation and experimental setup requirements, and shows its benefits and limitations. Then, the chapter focuses on the latest developments in terms of finite element modeling and analytical computations.<BR> <BR> The second chapter presents the numerical tools used throughout this research. This consists mainly of the finite element code, the elements, and the constitutive laws. Then, this chapter gives an overview of the experimental setup and measuring devices used during the experimental tests performed in Leuven. The second part focuses on dynamic explicit simulations of incremental forming and contains four chapters. The first justifies the use of a dynamic explicit strategy. The second presents the new features added to the finite element code in order to be able to model incremental forming with such a strategy. The third explains the computation of the mass matrix of the shell element used throughout this part of the thesis and justifies this computation. Finally, the fourth chapter analyzes the overall performance of the dynamic explicit simulations both in terms of accuracy and computation time.<BR> <BR> The third part of this thesis contains an in-depth analysis of the incremental forming process using more classic implicit finite element simulations. This analysis is performed in two steps. In a first chapter, the influence of using a partial mesh for the simulations is evaluated in terms of accuracy and computation time. Then, in a second and final chapter, a detailed analysis of the deformation mechanism occurring during this forming process is carried out.<BR> <BR> Finally, this thesis ends with the major conclusions drawn from the research and perspectives on possible means of further improving the simulation tool.<BR> <BR> 5. Original Contributions<BR> -------------------------<BR> Through this research, several major contributions were achieved.<BR> <BR> First, a comprehensive literature review of the incremental forming process was carried out. In particular, the review focused on original articles concerning the limitations of the process and possible ways of bypassing them; on the most recent explanations for the increased formability observed during the process; and on the state of the art in finite element simulations of incremental forming. Understanding the concepts and difficulties inherent in these publications was made possible particularly by the SeMPeR project thanks to the discussions held and the monthly follow-ups on research performed by its members.<BR> <BR> Secondly, Lagamine's shell element was corrected and its mass matrix modified to enable its use with an explicit strategy. Following this, a new approach for modeling the contact between an element and the forming tool during simulations in a dynamic explicit strategy was developed and thoroughly tested. A detailed comparison of the influence of various finite element parameters on the simulations' results was performed, in particular regarding the choice between using the implicit and explicit strategies and the use of mass scaling to reduce the computation time.<BR> <BR> In addition, many simulations were validated thanks to experimental results.<BR> <BR> Moreover, the computation time required for simulations of the forming of parts with rotational symmetry was radically reduced by using a partial model with a new type of boundary conditions.<BR> <BR> Finally, the material behavior occurring during incremental forming was analyzed.

Because the bulk optical properties of dust are largely dependent on their chemical composition, published reports from numerous dust field studies enabled us to compile observation data sets to derive the effective complex refractive indices of Saharan and Asian dust. We considered the individual mineral components as aggregates and used the Bruggeman approximation to derive the effective refractive indices. Using the results, we calculated the single-scattering properties, including phase matrix, single-scattering albedo and asymmetry factor, with a combination of the T-matrix method and an improved geometric optics method (IGOM). The single-scattering properties were averaged by the measured particle size distribution to provide bulk optical properties for radiative transfer simulations. Using a Rapid Radiative Transfer Model (RRTM), the radiative forcing of mineral dust was computed at both the top of the atmosphere and the surface. By analyzing samples from various in-situ measurements, we assumed the Saharan and Asian dust to have average volume compositions and average aspect ratios. The effective refractive indices for Saharan and Asian dust were derived based on the assumed composition models. Bulk optical properties were integrated using the modified log-normal particle size distributions. The aspect ratio assumed in this study is 1.6 for both Saharan and Asian dust. The longwave radiative (IR) forcings at the top of the atmosphere (TOA) and at the surface were found to be positive and sensitive to wavelength. The shortwave (solar) radiative forcing at TOA, was also positive, but may possibly have been due to the strong absorption components considered in the composition models.

Nonadiabatic dynamical processes are ubiquitous in chemistry and biology. Such events are directly connected to the treatment of energetically close lying states which gives rise to strong vibronic interactions in which case the Born-Oppenheimer approximation tends to break down. In case of biradicals, nonadiabatic events are facilitated by conical intersections, as a result of symmetry lowering of degenerate electronic states due to Jahn-Teller distortion. A central problem in the treatment of the nonadiabatic molecular dynamics is posed by the representation of potential energy surfaces. A point by point calculation of a potential energy surface on a multi-dimensional grid is very cumbersome and in general does not provide with an analytical functional form of the potential. This becomes even more complicated when the adiabatic surfaces have cusps, where the function becomes non-differentiable. Vibronic model Hamiltonians, which represent the potential in the form of a potential matrix which contains the electronic energies as well as the couplings in a diabatic basis. A Taylor series expansion of the potential matrix can be done to get a smooth analytical functional form of the potential matrix elements. These models can then be used to perform nuclear dynamics using either exact diagonalization time-independent method or the wavepacket propagation based time-dependent methods. Thus, vibronic models provide a compact representation of complicated coupled potential energy surfaces, which can be used in conjunction with non-adiabatic nuclear dynamics Vibronic models have been constructed for selected biradicals, for which photodetachment spectra have been simulated using the time-independent (VIBRON) as well as time-dependent (MCTDH) methods. Consistent results have been obtained with both the approaches for small systems. This also assures the use of MCTDH program for larger systems, where the time-independent methods are not applicable. Moreover, for biradicals, the parent anionic state also undergoes a Jahn-Teller distortion, or often the ground state potential energy surface is highly anharmonic in nature. This requires the description of anionic ground state by a vibronic model. Therefore, in order to simulate the photodetachment spectra of biradicals, three vibronic models are constructed for each simulation. The first model describes the ground and excited states of the parent anionic (neutral) species. Two other vibronic models describe singlet and triplet states of the target neutral (cation) species, and the spectrum is simulated using the vibronic ground state(s) of the anion (neutral) as the absorbing state in VIBRON/MCTDH. The electronic states and vibronic model parameters are obtained using the IP-EOM-CCSD and DIP-STEOM-CCSD methodology as coded in the ACESII quantum chemistry program package. The photodetachment spectra of nitrate radical, cyclobutadiene negative ion and trimethylene negative ion have been studied using this methodology.

Sense of place is important because it enhances the user experience in a setting, promotes well maintained public places and encourages public participation in planning. In addition, sense of place has recently been recognized for its significance in ecosystem and resource management. Unfortunately, due to lack of a clear definition and disorganization in the literature, the significance of sense of place has not translated well from theory to practice. This research narrows the gap between theory and practice in place-making by distilling common place-making principles from the literature to develop a set of clear, practical guidelines for place-making. Using Pier 21 in Halifax, Nova Scotia, these principles (and the techniques that fulfill them) were incorporated into twenty ‘what-if’ visual simulations. Using a multi-sort technique, combined with open-ended interviews, these simulations were used to evoke participant responses to the principles and techniques distilled from the literature. Generally, it was found that sense of place is enhanced with the addition of these principles/techniques, but five unexpected ‘key findings’ were also discovered – there is a hierarchy amongst the principles; there is a hierarchy amongst the techniques; significant techniques are lacking in the literature; the principles/techniques need not be exhausted; and, with familiarity, mystery becomes meaning. Practically, it is demonstrated that the guidelines developed through this research are capable of providing solutions to issues recognized in current Canadian design guidelines. Academically, this research presents an initial exploratory study in bridging the gap between theory and practice in place-making. A number of opportunities are recognized to further test the principles/techniques distilled in this research.

In this work, the peroxide-initiated degradation of polypropylene (PP) in co-rotating intermeshing twin-screw extruders (COITSEs) is analyzed by means of numerical simulations. This reactive extrusion (REX) operation is simulated by implementing (i) a one-dimensional and (ii) a three-dimensional (3D) modeling approach. In the case of the 1D modeling, a REX mathematical model previously developed and implemented as a computer code is used for the evaluation of two scale-up rules for COITSEs of various sizes. The first scale-up rule which is proposed in this work is based on the concept of thermal time introduced by Nauman (1977), and the second one is based on specific energy consumption (SEC) requirements. The processing parameters used in testing the previously referred to scale-up approaches are the mass throughput, the screw rotating speed, and the peroxide concentration, whereas the extruder screw configuration and the barrel temperature profiles are kept constant. The results for the simulated operating conditions show that when the REX operation is scaled-up under constant thermal time, very good agreement is obtained between the weight-average molecular weight (Mw) and poly-dispersity index (PDI) from the larger extruders and the values of these parameters corresponding to the reference extruder. For the constant SEC approach, on the other hand, more significant variations are observed for both of the aforementioned parameters. In the case of the implemented constant thermal time procedure, a further analysis of the effect of the mass throughput and screw speed of the reference device on the scaled-up operation is performed. It is observed that when the lower mass throughput is implemented for the smaller extruder keeping a constant screw speed, the predicted residence times of extrusion for the larger extruders are lower, in general terms, than those corresponding to the reference device, and a converse situation occurs for the higher implemented value of the mass throughput. Also, in general terms, the higher increase of the reaction temperature on the scaled-up operation corresponds to the lower mass throughputs and higher screw speeds specified for the reference extruder. For the 3D modeling approach, two different case studies are analyzed by means of a commercial FEM software package. The REX simulations are performed under the assumption of steady-state conditions using the concept of a moving relative system (MRS). To complement the information obtained from the MRS calculations, simulations for selected conditions (for non-reactive cases) are performed considering the more realistic transient-state (TS) flow conditions. The TS flow conditions are associated to the time periodicity of the flow field inside the conveying elements of COITSEs. In the first case study, the peroxide-initiated degradation of PP is simulated in fully-filled screw elements of two different size COITSEs in order to evaluate scale-up implications of the REX operation. In the second case, the reacting flow is simulated for a conventional conveying screw element and a conveying screw element having a special design and corresponding to the same extruder size. For both of the analyzed cases, the effects of the initial peroxide concentration and mass throughput on the final Mw and PDI of the degraded resin are studied. The effect of the processing conditions is discussed in terms of the residence time distribution (RTD), the temperature of reaction, and the distributive mixing capabilities of the REX system. When analyzing the scale-up case, it is found that for the implemented processing conditions, the final Mws and PDIs are very close to each other in both of the analyzed flow geometries when the specified flow is close to that corresponding to the maximum conveying capabilities of the screw elements. For more restrictive flow conditions, the final Mws and PDIs are lower in the case of the screw element of the larger extruder. It is found that the distributive mixing ability of the reactive flow is mainly related to the specified mass throughput and almost independent of the specified peroxide concentration for a particular extruder size. For the analyzed screw elements, the conveying element corresponding to the small size extruder shows a slightly better distributive mixing performance. For this same case study, a further evaluation of the proposed scale-up criterion under constant thermal time confirms the trend of the results observed for the 1D simulations. In the second case study, the special type of screw element consists of screws rotating at different speeds which have different cross sections. In this case, the outer and inner diameters of both the special and the conventional type of screw elements are specified to be the same. As in the previous case study, the distributive mixing capabilities appear to be independent of the specified peroxide concentrations but dependent on the mass flow rate. It is speculated from the simulation results, from both the transient- as well as the steady-state flow conditions, that the screw element with the special design would yield lower final values of the PDI and Mw. Also, this screw element appears to have improved distributive mixing capabilities as well as a wider RTD.

Sense of place is important because it enhances the user experience in a setting, promotes well maintained public places and encourages public participation in planning. In addition, sense of place has recently been recognized for its significance in ecosystem and resource management. Unfortunately, due to lack of a clear definition and disorganization in the literature, the significance of sense of place has not translated well from theory to practice. This research narrows the gap between theory and practice in place-making by distilling common place-making principles from the literature to develop a set of clear, practical guidelines for place-making. Using Pier 21 in Halifax, Nova Scotia, these principles (and the techniques that fulfill them) were incorporated into twenty ‘what-if’ visual simulations. Using a multi-sort technique, combined with open-ended interviews, these simulations were used to evoke participant responses to the principles and techniques distilled from the literature. Generally, it was found that sense of place is enhanced with the addition of these principles/techniques, but five unexpected ‘key findings’ were also discovered – there is a hierarchy amongst the principles; there is a hierarchy amongst the techniques; significant techniques are lacking in the literature; the principles/techniques need not be exhausted; and, with familiarity, mystery becomes meaning. Practically, it is demonstrated that the guidelines developed through this research are capable of providing solutions to issues recognized in current Canadian design guidelines. Academically, this research presents an initial exploratory study in bridging the gap between theory and practice in place-making. A number of opportunities are recognized to further test the principles/techniques distilled in this research.