Biodiesel has been proposed as a substitute for diesel given that biodiesel has lower net average greenhouse gas emissions than diesel. Additionally, alcohol may be added to biodiesel to improve biodiesel’s performance in a diesel engine as well to reduce engine emissions. This work will study the droplet evaporation process of alcohol-biodiesel blends. Due to alcohol’s polar nature and the fatty acid methyl esters’s (FAME) slightly polar nature, an appropriate method must be chosen to represent the evaporation process of a non-ideal mixture. The vapour-liquid equilibria was modelled in two ways: the first method uses only Raoult’s Law, while the second method uses Raoult’s law modified with activity coefficients calculated using the UNIFAC method. The comparison of the modelled results with experimental vapour-liquid equilibria data has shown that activity coefficients calculated using the UNIFAC method are able to accurately represent alcohol-biodiesel systems. Droplet evaporation experiments have been performed for biodiesel-propanol and biodiesel-pentanol blends at temperatures of 450°C and 700°C with the alcohol concentrations of 5%, 10%, 15%, and 20%. Additionally, the droplet evaporation was numerically modelled using two different models to represent the liquid state: a model with a well-mixed liquid phase and a model which includes component diffusion in the liquid phase. Comparing the experimental droplet temperatures to the numerical models has shown that the diffusion-limited model best represents the droplet evaporation process, suggesting that some of the alcohol components remain in the center of the droplet even when the droplet temperature is greater than the boiling temperature of the alcohol. This was further confirmed by observations of bubbling within the droplet during evaporation of the biodiesel-alcohol blends, in which there were both small bubbles and large bubbles forming. The formation of large bubbles has shown to correspond with the difference between experimental droplet diameter and the diffusion-limited model’s droplet diameter.

No description available.

Evaporation and wetting of droplets are a phenomena present in everyday life and in many industrial, biological or medical applications; thus controlling and understanding the underlying mechanisms governing this phenomena becomes of paramount importance. More recently, breakthroughs in the fabrication of new materials and nanomaterials have led to the synthesis of novel nanoscale particulates that dispersed into a base fluid modify the properties of this latter. Enhancement in heat transfer or the self-assembly of the particles in suspension during evaporation, are some of the areas in which nanofluids excel. Since it is a relatively new area of study, the interplay particle-particle, particle-fluid or particle-substrate at the macro-, micro-, and nanoscale is yet poorly understood. This work is an essay to elucidate the fundamental physics and mechanisms of these fluids during free evaporation, of great importance for the manipulation and precise control of the deposits. The evaporative behaviour of pure fluids on substrates varying in hydrophobicity has been studied and an unbalance Young’s force is proposed to explain the effect of substrate hydrophilicity on the pinning and the depinning forces involved during droplet evaporation. On other hand, the addition of nanoparticles to a base fluid modifies the evaporative behaviour of the latter and: a more marked “stick-slip” behaviour is observed when increasing concentration on hydrophobic substrates, besides the longer pinning of the contact line reported on hydrophilic ones when adding nanoparticles. A deposition theory to explain the final deposits observed, for the outermost ring, after the complete vanishing of a 0.1% TiO2-ethanol nanofluid droplet has also been developed. In addition, the evaporation of pinned nanofluid droplets on rough substrates at reduced pressures has been systematically studied. A revisited Young-Lippmann equation is proposed as one of the main findings to explain the enhancement on electrowetting performance of nanoparticle laden fluid droplets when compared to the pure fluid case. On the other hand, of relevant importance is the absence of “stick-slip” behaviour and the more homogeneous deposits found after the complete evaporation of a nanofluid droplet under an external electric field applied when compared to free evaporation of these fluids.

The hydrophobicity of a surface is defined as the degree to which it repels water molecules, and the internal contact angle that the droplet makes with the surface is a measure of the hydrophobicity. Contact angles less than 90° occur on hydrophilic surfaces, while contact angles greater than 90° occur on hydrophobic surfaces. If a surface's contact angle is greater than 120° the surface is commonly defined as superhydrophobic (SH). Superhydrophobicity is accomplished through a combination of microscale surface roughness and water repellant surface chemistry. The roughness creates cavities, or pockets, of vapor underneath the droplet which act to increase the effects of surface tension and lead to increased contact angles. The cavity fraction, F_c, of a surface is a measure of the surface roughness and is defined as the ratio of the projected cavity area to the projected total area of the surface. This thesis investigates the effects of varying cavity fraction, F_c, and substrate temperature, T_s, on heat transfer to evaporating water droplets. Distilled water droplets of nominally 3 mm in diameter were placed on heated SH substrates of varying F_c (0.5, 0.8, and 0.95). A smooth hydrophobic surface was included in the experiments for comparative purposes. The temperature of the surface was held constant at temperatures ranging from 60 to 230°C while the droplet evaporated. Measurements of droplet temperature and size were taken throughout the evaporation process using CCD and infrared camera images. These images were analyzed to yield heat transfer rates for the various surface types and surface temperatures studied. At temperatures below the saturation point of water, average droplet temperatures and heat transfer rates decrease with increasing cavity fraction. Differences in heat transfer rate between substrates increase with substrate temperature. Nusselt number decreases as cavity fraction is increased. Cavity fractions less than about 0.5 show only modest differences in Nusselt number between surfaces. As cavity fraction approaches unity, differences in Nusselt number become amplified between surfaces. At temperatures above the saturation point of water, boiling behavior on SH surfaces deviates dramatically from that of smooth untextured surfaces. Average heat transfer rates decrease with increasing cavity fraction. Nucleate boiling is delayed to highter superheats than normal or is not observed. The Liedenfrost point is advanced to lower superheats as cavity fraction is increased. Similar heat transfer rates are observed beyond the Leidenfrost point.

Droplet evaporation and condensation are two important topics of interest, since these two phase-change phenomena not only occur in the cycle of global water, e.g., the formation of rain, fog, dew, and snow in nature, but also play a critical role in a variety of applications including phase-change heat transfer enhancement, surface chemistry and energy system optimization. Especially, in the past two decades, the rapid development of the nature-inspired non-wetting surfaces has promoted the applications of droplet-based phase change phenomena in various scenarios. However, most previous studies focused on the sessile droplets on one flat surface in the open space, and the effects of surface topography, i.e., surface curvature or configurations, on droplet evaporation and dropwise condensation are still elusive. This dissertation aims to explore droplet-based evaporation and condensation in more complex spaces and to elucidate how the surface topography affects the evaporating or coalescing droplet dynamics during these phase-change processes. The coalescence-induced jumping of nanodroplet on curved superhydrophobic surface is modeled via molecular dynamic simulations. As the surface curvature increases from 0 to 2, the corresponding energy conversion efficiency of jumping droplet during the coalescence process could be significantly improved about 20 times. To explain this curvature-enhanced jumping effect, the contact line dissipation, i.e., an important source of energy dissipation in nanoscale, is considered in our scaling energy analysis. And this energy-effective jumping of coalesced droplet could be mainly attributed to the reduction of contact line dissipation due to the decrease of contact line length and contact time on curved surface. As the droplets are confined between two parallel or non-parallel low-energy surfaces, i.e., hydrophobic or superhydrophobic surfaces, with a narrow gap, the total evaporation time of the squeezed droplets would be dramatically prolonged about two times. An ellipsoidal segment diffusion-driven model is established to successfully predict the evolution of contact radius and volume of the squeezed droplets during the evaporation process and to clarify it is the vapor enrichment inside the confined space giving rise to the mitigated evaporation. If two hydrophobic surfaces are configured as non-parallel, the confined droplet inside the V-shaped grooves would be self-transported towards the cusp/corner during the evaporation. Based on our energy and force analyses, the asymmetrically confined droplet would move towards an equilibrium location le, where the Laplace pressure induced force is balanced with normal adhesion force, to minimize its Gibbs surface energy. As le decreases during the evaporation, this equilibrium location would directionally shift towards the cusp, which could be regarded as the origin of this evaporation-triggered unidirectional motion. For the first time, the solvent transport and colloidal extraction could be accurately controlled in a combined manner. / Doctor of Philosophy / Droplet evaporation and condensation are two important topics of interest, since these two phase-change phenomena not only occur in the global cycle of water including the formation of rain, fog, dew, and snow in nature, but also play a critical role in a variety of applications including heat transfer enhancement, surface chemistry, and the energy system optimization. Generally, the droplets in these scenarios are deposited on one flat surface opened to the atmosphere. and the effects of surface topography on droplet evaporation and dropwise condensation are still elusive. This dissertation aims to explore droplet-based evaporation and condensation in more complex spaces and to clarify how the surface curvature or configurations affects evaporating or condensing droplet dynamics accompanying these phase change processes. As the coalesced droplet jumps off the curved superhydrophobic surfaces during dropwise condensation, the corresponding energy conversion efficiency would be significantly improved about 20 times due to the increases of curvature. It is demonstrated that the decrease of contact line length and contact time would give rise to the reduction of contact line dissipation, which should be the main factor driving this energy-effective jumping of the coalesced droplets. As the droplets are confined between two parallel or non-parallel low-energy surfaces, i.e., hydrophobic or superhydrophobic surfaces, with a narrow gap, the total evaporation time of the squeezed droplets would be dramatically prolonged about two times in the small space. An ellipsoidal segment diffusion-driven model is established to successfully predict the evolution of contact radius and volume of the squeezed droplets during the evaporation and to clarify it is the vapor enrichment in the confined space giving rise to the mitigated evaporation. If two hydrophobic surfaces are configured as non-parallel, the confined droplet inside the V-shaped grooves would be self-transported towards the cusp/corner of the structure during evaporation. Based on our energy and force analyses, the asymmetrically confined droplet would move towards an equilibrium location le, where the Laplace pressure induced force is balanced with normal adhesion force, to minimize its Gibbs surface energy. As le decreases in the scale of during the evaporation, this equilibrium location would directionally shift towards the cusp, which could be regarded as the origin of this evaporation-triggered unidirectional motion.

Addition of nanopacticles in a base solvent leads to suspensions with enhanced physiochemical properties, compared to base solvent. This new type of suspensions is called nanofluids, with applications ranging from biomedicine to automotives. As a consequence extensive research is being conducted in the field, in particular, on the evaporation of these fluids as it leads to well-defined and highly ordered coffee-rings. However, the exact physics governing this phenomenon remain elusive. The goal of this experimental investigation is to elucidate how various parameters affect the progression of nanofluid coffee-stain formation. Examination of the coffee-ring structuring, produced by the free evaporation of sessile droplets containing nanoparticles, revealed an unexpected, disordered region at the exterior edge of the ring. A self-assembly mechanism with two components, particle velocity and wedge constraints, was proposed to describe the deposition of particles at contact lines of evaporating drops. Environmental pressure was used as a method to control particle crystallinity in the coffee-rings. Essentially, evaporation rate and pressure were found to be inversely proportional. Macroscopically, lowering pressure led to a transition from “stick-slip” to constant pinning. Nanoscopically, lowering pressure promoted crystallinity. Findings supported the proposed, in this thesis, particle self-assembly mechanism. Particle aspect ratio and flexibility were subsequently examined. Pinning strength was found to be a function of particle aspect ratio and rigidity, leading to constant pinning. The proposed, in this thesis, particle self-assembly mechanism was found to be applicable to a variety of aspect ratios and flexibilities. Lastly, particulate crystals grew following different pathways depending on particle flexibility.

In recent years, the need for high performance power sources has increased dramatically with the proliferation of ultra-compact electronic systems for mobile communication, man-portable and versatile military equipment, and electric vehicles. Volume- and mass- based power density are two of the most important performance metrics for portable power sources, including hydrogen generating fuel reforming systems (onboard) for hydrogen fuel cells. Two innovative multifunctional reactor concepts, CO2/H2 Active Membrane Piston (CHAMP) and Direct Droplet Impingement Reactor (DDIR), are combined for the purpose of hydrogen generating fuel reforming system (onboard) for fuel cells. In CHAMP-DDIR, a liquid fuel mixture is pulse-injected onto the heated catalyst surface for rapid flash volatilization and on-the-spot reaction, and a hydrogen selective membrane is collocated with the catalyst to reduce the diffusion distance for hydrogen transport from the reaction zone to the separation site. CHAMP-DDIR allows dynamic variation of the reactor volume to optimally control the residence time and reactor conditions, such as pressure and temperature, thus improving both the reaction and separation processes. A comprehensive CHAMP-DDIR model, which couples key physical processes including 1) catalytic chemical reactions, 2) hydrogen separation/permeation at membrane, 3) liquid fuel evaporation, and 4) heat and mass transport, has been developed to investigate the behavior of this novel reactor system, aiming at maximizing the volumetric power density of hydrogen generation from methanol/water liquid fuel. The relationships between system design parameters and the rate-limiting process(es), i.e., reaction, permeation, and transport, which govern reactor output, have identified. Experimental characterization of the prototype reactor has been performed for laboratory demonstration of the concept and model validation. Both model predictions and experiments successfully demonstrate the unique practical performance improvements of CHAMP-DDIR through combining time-modulated fuel introduction and the active change of reactor volume/pressure. This work has led to a number of fundamental insights and development of engineering guidelines for design and operation of CHAMP-DDIR class of reactors, which can be extended to a broad range of fuels and diverse practical applications.

Evaporation of pure and binary liquid droplets is of interest in thermal sprays and spray drying of food, ceramics and pharmaceutical products. Understanding the rate of heat and mass transfer in any drying process is important not only to enhance evaporation rate or vapor-gas mixing, but also to predict and control the final morphology and microstructure of the precipitates. Acoustic levitation is an alternative method to study micron-sized droplets without wall effects, which eliminates chemical and thermal contamination with surfaces. This work uses an ultrasonic levitation technique to investigate the vaporization dynamics under radiative heating, with focus on evaporation characteristics, precipitation kinetics, particle agglomeration, structure formation and droplet stability. Timescale and temperature scales are developed to compare convective heating in actual sprays and radiative heating in the current experiments. These relationships show that simple experiments can be conducted in a levitator to extrapolate information in realistic convective environments in spray drying. The effect of acoustic streaming, droplet size and liquid properties on internal flow is important to understand as the heat and mass transfer and particle motion within the droplet is significantly controlled by internal motion. Therefore, the droplet internal flow is characterized by Particle Image Velocimetry for different dropsize and viscosity. Nanosuspension droplets suspended under levitation show preferential accumulation and agglomeration kinetics. Under certain conditions, they form bowl shaped structures upon complete evaporation. At higher concentrations, this initial bowl shaped structure morphs into a ring structure. Nanoparticle iv migration due to internal recirculation forms a density stratification, the location of which depends on initial particle concentration. The time scale of density stratification is similar to that of perikinetic-driven agglomeration of particle flocculation. The density stratification ultimately leads to force imbalance leading to a unique bowl-shaped structure. Chemically active precursor droplet under acoustic levitation shows events such as vaporization, precipitation and chemical reaction leading to nanoceria formation with a porous morphology. The cerium nitrate droplet undergoes phase and shape changes throughout the vaporization process followed by formation of precipitate. Ex-situ analyses using TEM and SEM reveal highly porous morphology with trapped gas pockets and nanoceria crystalline structures at 70oC. Inhomogeneity in acoustic pressure around the heated droplet can induce thermal instability. Short wavelength (Kelvin-Helmholtz) instability for diesel and bio-diesel droplets triggers this secondary atomization, which occurs due to relative velocity between liquid and gas phase at the droplet equator. On the other hand, liquids such as Kerosene and FC43 show uncontrollable stretching followed by a catastrophic break-up due to reduction in surface tension and viscosity coupled with inhomogeneity of pressure around the droplet. Finally, a scaling analysis has been established between vaporizing droplets in a convective and radiative environment. The transient temperature normalized by the respective scales exhibits a unified profile for both modes of heating. The analysis allows for the prediction of required laser flux in the levitator experiments to show its equivalence in a corresponding heated gas stream. The theoretical equivalence shows good agreement with experiments for a range of droplet sizes.

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).