<p>The removal of vegetation and overburden changes the naturalwater purifying processes and thus decreases the groundwaterprotection in gravel pit areas. The sand and gravel depositsusedfor aggregate extraction in Sweden are also often valuablefor extraction of groundwater as a drinking water resource. TheSwedish legislation requires that gravel pits be restored afterthe cessation of extraction, the aim being to reestablishvegetation and to reinstate groundwater purifyingprocesses.</p><p>The objective of this study was to improve our understandingof the processes governing groundwater protection andvegetation establishment so that these could be applied toimproving restoration methods for reestablishing naturalgroundwater protection. The focus was on the importance of soilphysical properties of the topsoil for vegetation establishmentand groundwater recharge.</p><p>Actual field methods for restoration were reviewed.Conflicts between aggregate extraction and groundwaterinterests were common. In many cases the actual restorationcarried out differed from pre-planned specifications in permitdocumentation.</p><p>Commonly available substrates that might be used forrestoration of gravel pits were investigated. The soils weredescribed as regards texture, organic content, porosity, waterretention and hydraulic conductivity. The way in which acombination of the water retention characteristic and theunsaturated conductivity influenced the behaviour of thesoil-plant-atmosphere system was demonstrated using aprocess-orientated simulation model. Plants with well-developedaboveground characteristics and shallow roots in particularexerted the highest requirements on the soil physicalproperties.</p><p><b>Key words:</b>groundwater protection, soil physicalproperties, CoupModel, unsaturated conductivity, waterretention, transpiration, soil evaporation</p>

The objective of this thesis is to develop an easy-to-use and computationally economical numerical tool to investigate the flow field in the Pulsed Pressure Chemical Vapour Deposition (PP-CVD) reactor. The PP-CVD process is a novel thin film deposition technique with some advantages over traditional CVD methods. The numerical modelling of the PP-CVD flow field is carried out using the Quiet Direct Simulation (QDS) method, which is a flux-based kinetic-theory approach. Two approaches are considered for the flux reconstruction, which are the true directional manner and the directional splitting method. Both the true directional and the directional decoupled QDS codes are validated against various numerical methods which include EFM, direct simulation, Riemann solver and the Godunov method. Both two dimensional and axisymmetric test problems are considered. Simulations are conducted to investigate the PP-CVD reactor flow field at 1 Pa and 1 kPa reactor base pressures. A droplet flash evaporation model is presented to model the evaporation and transport of the liquid droplets injected. The solution of the droplet flash evaporation model is used as the inlet conditions for the QDS gas phase solver. The droplet model is found to be able to provide pressure rise in the reactor at the predicted rate. A series of parametric studies are conducted for the PP-CVD process. The numerical study confirms the hypothesis that the flow field uniformity is insensitive to the reactor geometry. However, a sufficient distance from the injection inlet is required to allow the injected precursor solution to diffuse uniformly before reaching the substrate. It is also recommended that placement of the substrate at the reactor’s centre axis should be avoided.

Present work is focused on the numerical study of evaporation of sessile liquid droplets on top of smooth solid substrates. The process of evaporation of a sessile liquid droplet has lots of different applications both in industry and research area. This process has been under study for many years, and still it is an actual problem, solution of which can give answers on some fundamental and practical questions. Instantaneous distribution of mass and heat fluxes inside and outside of an evaporating sessile droplet is studied in this research using computer simulations. The deduced dependences of instantaneous fluxes are applied for self-consistent calculations of time evolution of evaporating sessile droplets. The proposed theory of evaporating sessile droplets of liquid has been validated against available experimental data, and has shown a good agreement. Evaporation of surfactant solution droplets is studied experimentally. The theory, proposed for two stages of evaporation, fits experimental data well. An additional evaporation stage, specific for surfactant solutions, is observed and described. Mathematical modelling of this stage requires further research on surfactant adsorption and its influence on the value of receding contact angle. Numerical study of the evaporation of microdroplets is conducted in order to evaluate the significance of different evaporation mechanisms (diffusive and kinetic models of evaporation) and different physical phenomena (Kelvin s equation, latent heat of vaporization, thermal Marangoni convection, Stefan flow).

<p>Thin film deposition techniques are indispensable to the development of modern technologies as thin film based optical coatings, optoelectronic devices, sensors, and biological implants are the building blocks of many complicated technologies, and their performance heavily depends on the applied deposition technique. Particularly, the emergence of novel solution-processed materials, such as soft organic molecules, inorganic compounds and colloidal nanoparticles, facilitates the development of flexible and printed electronics that are inexpensive, light weight, green and smart, and these thin film devices represent future trends for new technologies. One appealing feature of solution-processed materials is that they can be deposited into thin films using solution-processed deposition techniques that are straightforward, inexpensive, high throughput and advantageous to industrialize thin film based devices. However, solution-processed techniques rely on wet deposition, which has limitations in certain applications, such as multi-layered film deposition of similar materials and blended film deposition of dissimilar materials. These limitations cannot be addressed by traditional, vacuum-based deposition techniques because these dry approaches are often too energetic and can degrade soft materials, such as polymers, such that the performance of resulting thin film based devices is compromised.</p><p>The work presented in this dissertation explores a novel thin film deposition technique, namely emulsion-based, resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE), which combines characteristics of wet and dry deposition techniques for solution-processed materials. Previous studies have demonstrated the feasibility of emulsion-based RIR-MAPLE to deposit uniform and continuous organic, nanoparticle and blended films, as well as hetero-structures that otherwise are difficult to achieve. However, fundamental understanding of the growth mechanisms that govern emulsion-based RIR-MAPLE is still missing, which increases the difficulty of using rational design to improve the performance of initial RIR-MAPLE devices that have been demonstrated. As a result, it is important to study the fundamentals of emulsion-based RIR-MAPLE in order to provide insight into the long-term prospects for this thin film deposition technique.</p><p>This dissertation explores the fundamental deposition mechanisms of emulsion-based RIR-MAPLE by considering the effects of the emulsion target composition (namely, the primary solvent, secondary solvent, and surfactant) on the properties of deposited polymer films. The study of primary solvent effects on hydrophobic polymer deposition helps identify the unique method of film formation for emulsion-based RIR-MAPLE, which can be described as cluster-by-cluster deposition of emulsified particles that yields two levels of ordering (i.e., within the clusters and among the clusters). The generality of this film formation mechanism is tested by applying the lessons learned to hydrophilic polymer deposition. Based on these studies, the deposition design rules to achieve smooth polymer films, which are important for different device applications, are identified according to the properties of the polymer.</p><p>After discussion of the fundamental deposition mechanisms, three applications of emulsion-based RIR-MAPLE, namely thin film deposition of organic solar cells, polymer/nanoparticle hybrid solar cells, and antimicrobial/fouling-release multifunctional films, are studied. The work on organic solar cells identifies the ideal deposition mode for blended films with nanoscale domain sizes, as well as demonstrates the relationships among emulsion target composition, film properties, and corresponding device performance. The studies of polymer/nanoparticle hybrid solar cells demonstrate precise control of colloidal nanoparticle deposition, in which the integrity of nanoparticles is maintained and a distinct film morphology is achieved when co-deposited with polymers. Finally, the application of antimicrobial and fouling-release multifunctional films demonstrates the importance of blended film deposition with nanoscale phase separation, a key feature to achieving reusable bio-films that can kill bacteria when illuminated with ultraviolet light.</p><p>Thus, this dissertation provides great insight to the fundamentals of emulsion-based RIR-MAPLE, serves as a valuable reference for future development, and paves the pathway for wider adoption of this unique thin film deposition technique, especially for organic solar cells.</p> / Dissertation

Fundamental studies on thermodynamic properties of vanadium-containing oxides systems are essential to understand practical vanadium metallurgical process. The CALPHAD technique is here applied to the thermodynamic modelling of the V-O, Ca-V-O and Ti-V-O systems. The compound energy formalism is used for all the solution phases. All optimization processes and calculations are performed using the Thermo-Calc software package. The present work attempts to develop a self-consistent thermodynamic database of all phases in the studied systems. The obtained datasets can be used to calculate thermodynamic properties, stable as well as metastable phase equilibria and driving forces for oxidation etc. Steelmaking slag is an important secondary source for vanadium extraction. The phase relationships and vanadium distribution in the CaO-SiO2-MgO-V2O3-Al2O3 synthetic slags, whose compositions were chosen based on the relevance to the steel producers, are also studied. Phase equilibria in the temperature range of 1773 to 1823 K at oxygen partial pressure of 10-10 bar and 0.21 bar were characterized. An investigation of the volatilization of vanadium oxide was also carried out in the present work. Isothermal evaporation of vanadium pentoxide in the temperature range between 1723 and 1873 K was investigated by Thermogravimetric Analysis under different oxygen partial pressures, viz. oxygen, air or CO2. The Arrhenius activation energy for the evaporation reaction in various atmospheres was calculated from the experimental results. A mathematical model was developed to describe the kinetics of the evaporation process. Evaporation coefficients and enthalpies in various atmospheres were also estimated. The present results may have some implications in recovering vanadium from different vanadium-bearing sources. / <p>QC 20161202</p>

Le processus de retrait-gonflement des sols argileux est à l'origine des dommages au bâti durant les périodes de sécheresse. Dans cette thèse, les processus de retrait-gonflement de deux formations de sol argileux en France qui sont les Argiles Plastiques du Sparnacien et l'argile d'Héricourt du Lias sont étudiés à différentes échelles et différents états (intact, remanié, compacté et traité à la chaux) en considérant spécialement le rôle de la microstructure. Pour ce faire, une partie de la recherche est réalisée sur la caractérisation des sols étudiés pour analyser leurs propriétés minéralogiques, microstructurales, géotechniques et hydriques par rapport à leur propriété de retrait-gonflement. La deuxième partie de la recherche est consacrée à l'analyse des processus de gonflement, de retrait, de fissuration des sols au cours d'un cycle simple ou de cycles répétés d'humidification-séchage à l'échelle de l'éprouvette. Les processus de retrait-gonflement de sol à une échelle plus grande sont étudiés dans la troisième partie en réalisant les essais d'infiltration et d'évaporation dans une chambre environnementale. Les résultats obtenus mettent en évidence les différences de comportement au retrait-gonflement pour différents états des sols étudiés. Les minéraux argileux ainsi que le quartz, les carbonates et des hydrates, mais aussi la microstructure des sols contrôlent ces phénomènes de retrait-gonflement lors des échanges hydriques. Tous les changements de volume de sol argileux au cours de gonflement-retrait sont gouvernés principalement par la famille de pores inter-agrégats naturels. Ces résultats sont apportés par les analyses microstructurales porosimétriques et au MEB. / The shrink-swell process of clayey soils is causing damage to the structures during periods of drought. In this thesis, the shrink-swell process of two clayey soils in France that are the Plastic Clays of Sparnacian age and Héricourt clay of Lias is studied at different scales and different conditions (intact, remoulded, compacted and lime treated) by insisting on the role of microstructure. To do this, a part of the study is carried out on the characterisation of soils studied to analyse their mineralogical, microstructural, geotechnical and hydraulic properties in relation with their shrink-swell property. The second part of the study focuses on the analysis of swelling, shrinkage, cracking processes of soil during a single cycle or repeated wetting-drying cycles at specimen scale. The shrink-swell process of soil at a larger scale is studied in the third part by performing infiltration and evaporation tests in the environmental chamber. The results highlight the difference in the shrink-swell behavior at different conditions of soils studied and emphasize the importance of the presence and nature of clay minerals also quartz, hydrates and microstructure of soil to the shrinkage and swelling during water exchange. All changes in the volume of clayey soil during shrinkage and swelling are mainly governed by natural inter-aggregate pores, which are showed by microstructural analyses of MIP and SEM tests.

Approved for public release, distribution is unlimited / A study of the performance of the Coupled Ocean Atmosphere Mesoscale Prediction System (COAMPS) was performed based on collected METOC properties affecting radar propagation during the Roughness and Evaporation Duct (RED) experiment conducted off the windward coast of Oahu, HI. The measured refractivity influencing parameters (SST, air temperature, humidity, and wind speed) were compared to COAMPS predicted values. Using the NPS bulk evaporation duct model, profiles of the modified refractivity were computed from the buoy data and compared to profiles computed from the COAMPS data. The profiles were obtained concurrently with S-Band propagation measurements along a 26-km path. The radar propagation predictions created by APM from the modified refractivity profiles, derived from the measured METOC values and COAMPS modeled values, were compared to the in situ measured propagation losses. The mean RMS error of the prop loss predictions derived from the COAMPS forecasted METOC values was <4 dB compared to a mean RMS error of <3 dB from the in situ measurement derived prop loss predictions. Significantly larger errors occurred at the COAMPS analysis times. Overall, the results are very promising for this trade wind region, where the air is cooler than the relatively warm sea surface. / Lieutenant, United States Navy

La physique de mouillage et de séchage de sang n’est pas encore bien connue. Dans le cadre d’un travail collaboratif, une étude est réalisée afin d’apporter de nouveaux outils aux équipes d’investigations criminelles. L’objectif est de comprendre les dynamiques qui entrent en jeu dans la formation de traces de sang, un fluide complexe. Nous nous intéressons aux traces dites passives telles que l’égouttement ou l’accumulation, qui résultent de l’action de la pesanteur. Nous considérons d’abord les gouttes passives. Le comportement d’impact de gouttes de fluides complexes est un sujet qui a été largement étudié mais suscite encore de vifs débats. Bien que le séchage d’une goutte déposée ait déjà été étudié, ceci n’est pas le cas pour des gouttes qui viennent impacter perpendiculairement une surface, tombant depuis une certaine hauteur. Parallèlement nous étudions le séchage de flaques de sang car leur dynamique de séchage n’a pas été étudiée jusqu’à présent. Différents paramètres tels que la nature des substrats, l’humidité et la température sont pris en compte afin de comprendre le lien entre la typologie des motifs séchés et les phénomènes observés en vue de répondre à des applications criminelles. Enfin des relations empiriques sont établies. Grace à des méthodes inverses, ces relations permettent, par la suite, d’obtenir une estimation de la vitesse d’impact de gouttes séchées. / The physics behind wetting and drying of blood is not yet completely understood. In the context of a collaborative project, new techniques have been developed to provide evidence for investigators in crime solving. Given that blood is a complex fluid, the major aim has been to investigate the dynamics involved in the patterns of stain formation. Interest is focused on passive stains, which result from the action of gravity in dripping or blood flow accumulation. In the case of drip stains, the impact behaviour of complex fluid droplets, despite many studies, raises much debate. Although the drying dynamics of a deposited drop of blood were already studied, this is not the case for drops of blood impacting perpendicularly a surface, falling from a certain height. Beside this, until the present work, little attention has been paid to the dynamics controlling the drying of blood pools. In both situations, the influence of different parameters such as substrates, humidity and temperature are examined. Empirical relations are established between final dried blood patterns and the generating mechanism, yielding possible application in blood pattern analysis for forensic investigations. Finally, using inverse methods, the empirical relations allow estimating an impact velocity, for dried drip stains.

<div>The evaporation of a liquid drop containing particles resting on a substrate have diverse industrial applications including inkjet printing, spray coating, fabrication of functional nanomaterials, disease diagnosis, among others. In addition to these wide ranging practical applications, the sessile drop evaporation can be observed in everyday life with dew drops, coffee spills, and the dry patterns of other beverages.</div><div><br></div><div>The self-assembly of particles during drop evaporation is a process that is affected by various factors, such as contact line (CL) behaviors, microfluidic flows, short-range interactions of particle-interface and particle-particle. Each of these factors are complicated enough to study, let alone the total effects on the process. The primary goal of this work is to investigate the influence of microfluidic flows and the particle-interface interaction, viz. the evaporation process was subject to a pinned CL and the particle-particle interaction was neglected under dilute particle concentration. </div><div>To accomplish this goal, the Galerkin/Finite Element Method (G/FEM) is used to solve for the flow, the temperature and the particle concentration profiles. </div><div><br></div><div><br></div><div>The complexity of the problems comes from various surface phenomena, one of which is the surface tension. The surface tension brings capillary force in the normal direction and capillary flow toward the CL, which results in the well-known coffee-ring effect. Moreover, the surface tension changes with temperature, surfactant concentration, etc. resulting in Marangoni stresses in the tangential direction. The Marangoni stress on the surface leads to circulations of flow inside the drop and the circulation can be either clockwise or counterclockwise depending on the direction of the stress. </div><div><br></div><div>When the Marangoni stress is merely caused by temperature change, the circulation direction changes not only in time but also in space. At late stage of evaporation, i.e. with a small contact angle (CA), multi-circulation flow profiles emerge. This flow profiles are featured with stagnation points and transition points. The stagnation points can be further categorized into capillary-induced stagnation points and Marangoni-induced stagnation points. By introducing the concept of capillary-induced stagnation points, the simulations reached agreement with experiments in terms of the radial location of the observed stagnation points.</div><div><br></div><div><br></div><div>The multi-circulation flow profiles implied regional segregation inside the drop. When a large circulation is observed in most part of the drop and a small circulation exists near the CL, particle concentrations are relatively uniform in each individual region but differs significantly across the two regions. Transition points are used to characterize the location of the regional segregation, which can be adjusted by Marangoni stress.</div><div><br></div><div><br></div><div>Marangoni circulations in different directions revealed distinct influences on particle distribution and deposition. First, while both directions facilitate even distribution of particles, a clockwise circulation strengthens CL accumulation for a small Marangoni stress. Second, a counterclockwise circulation with a small Marangoni stress impedes the deposition rate of particles, while a clockwise circulation facilities the deposition no matter how small the Marangoni stress is. This results is under a condition of a strong adsorption between particles and substrates. </div><div><br></div><div>The analysis and understanding of the above results are crucial to elucidating and controlling the final deposition patterns of particles. Thus, the focus of this research is to understand the combined effect of Marangoni stress and capillary flow on particle deposition during sessile drop evaporation.</div><div><br></div>

<p>Microscale environments provide significant resolution and distortion challenges with respect to measurement techniques; however, with improvements to existing techniques, it is possible to gather relevant data to better understand the thermal and fluidic mechanisms at such small scales in evaporating droplets.</p> <p> </p> <p>Infrared thermography provides several unique challenges at small scales. A primary issue is that the low native resolution of traditional infrared cameras significantly hamper the collection of details of microscale features. Furthermore, surfaces exhibiting vastly different emissivities, results in inaccurate temperature measurements that can only be corrected with irradiance-based emissivity maps of the surface; however, due to the resolution limitations of infrared thermography, these emissivity maps can also display significant errors. These issues are overcome through the use of multi-frame super-resolution. The enhanced resolution allows for better capture of microscale features, therefore, enhancing the emissivity map. A quantitative error analysis of the system is conducted to quantify the feature size resolution improvement as well as the smoothing effect of super-resolution reconstruction. Furthermore, a sensitivity analysis is conducted to quantify the impact of registration uncertainty on the accuracy of the reconstruction. Finally, the improved emissivity map from super-resolution is demonstrated to show the increased accuracy over low-resolution mapping.</p> <p> </p> <p>When applied to water droplets, particularly on nonwetting surfaces, infrared thermography is confounded by the presence of nonuniform reflectivities due to the spherical curvature of the liquid-air interface. Thus, when measuring the temperature along the vertical axis of a water droplet, it is necessary to correct the reflection. Using a controlled background environment, in conjunction with the Fresnel equations, it is possible to correct the reflective effects on the interface and calculate the actual temperature profile. This allows for a better understanding of the governing mechanisms that determine the thermal transport within the droplet. While thermal conduction is the primary transport mechanism along the vertical axis of the droplet, it is determined that the temperature drop is partially dampened by the convective transport from the ambient air to the liquid interface. From this understanding revealed by the measurements, the vapor-diffusion-based model for evaporation was enhanced to better predict evaporation rates.</p> <p> </p> <p>Further exploration into the mechanisms behind droplet evaporation on nonwetting surfaces requires accurate knowledge of the internal flow behavior. In addition, the influence of the working fluid can have a significant impact on the governing mechanisms driving the flow and the magnitude of the flowrate. While water droplet evaporation has been shown to be governed by buoyancy-driven convection on nonwetting substrates, similar studies on organic liquid droplets are lacking. Particle image velocimetry is effective at generating a velocity flow field, but droplets introduce distortion due to the refraction from the spherical interface of the droplet. As such, velocity correction using a ray-tracing approach was conducted to correct the velocity magnitudes and direction. With the velocity measurements, the flow was determined to be surface-tension-driven and showed speeds that are an order of magnitude higher than those seen in buoyancy-driven flow in water droplets. This resulted in the discovery that advection plays a significant role in the transport within the droplet. As such, the vapor-diffusion-governed evaporation model was adjusted to show a dramatic improvement at predicting the temperature gradient along the vertical axis of the droplet.</p> <p> </p> <p>Armed with the knowledge of flow behavior inside droplets, it is expected that droplets with aqueous solutions should exhibit buoyancy-driven convection. The final part of this work, therefore, leverages this phenomenon to enhance mixing during reactions. Colorimetry is a technique that is widely utilized to measure the concentration of a desired sample within some liquid; the sample reacts with a reagent dye the color change is measured, usually through absorbance measurements. In particular, the Bradford assay is used to measure protein concentration by reacting the protein to a Coomassie^TM Brilliant Blue G-250. The absorbance of the dye increases, most significantly at the 590 nm wavelength, allowing for precise quantitation of the amount of protein in the solution. A droplet-based reaction chamber with buoyancy-enhanced mixing has the potential to speed up the measurement process by removing the need for a separate pre-mixing step. Furthermore, the reduced volume makes the process more efficient in terms of reactant usage. Experimental results of premixed solutions of protein sample and reagent dye show that the absorbance measurement through a droplet tracks strongly with the protein concentration. When the protein sample and dye reagent are mixed <i>in situ</i>, the complex interaction between the reactants, the mixing, and the adsorption of protein onto the substrate creates a unique temporal evolution in the measured absorbance of the droplet. The characteristic peaks and valleys of this evolution track strongly with concentration and provide the framework for measurement of concentration in a droplet-based system.</p> <p> </p> <p>This thesis extends knowledge about droplet thermal and fluidic behavior through enhanced measurement techniques. This knowledge is then leveraged in a novel application to create a simple, buoyancy-driven colorimetric reaction setup. Overall, this study contributes to the field of miniaturized, efficient reaction and measurement devices.</p>