A mathematical model is developed to describe the micro/nano-scale fluid flow and heat/mass transfer phenomena in an evaporating extended meniscus, focusing on the transition film region under nonisothermal interfacial conditions. The model incorporates thermocapillary stresses at the liquid-vapor interface, a slip boundary condition on the solid wall, polarity contributions to the working fluid field, and binary mixture evaporation. The analytical results show that the adsorbed film thickness and the thin film length decrease with increasing superheat by the thermocapillary stresses, which influences detrimentally the evaporation process by degrading the wettability of the evaporating liquid film. In contrast, the slip effect and the binary mixture enhance the stability of thin film evaporation. The slip effect at the wall makes the liquid in the transition region flow with smaller flow resistance and thus the length of the transition region increases. In addition, the total evaporative heat flow rate increases due to the slip boundary condition. The mixture of pentane and decane increases the length of the thin film by counteracting the thermocapillary stress, which enhances the stability of the thin film evaporation. The polarity effect of water significantly elongates the thin film length due to the strong adhesion force of intermolecular interaction. The strong interaction force restrains the liquid from evaporation for a polar liquid compared to a non-polar liquid. In the experimental part, laser induced fluorescence (LIF) thermometry has been used to measure the microscale temperature field of a heated capillary tube with a 1 mm by 1 mm square cross section. For the temperature measurement, the calibration curve between the temperature and the fluorescent intensity ratio of Rhodamine-B and Rhodamine-110 has been successfully obtained. The fluorescent intensity ratio provides microscale spatial resolution and good temperature dependency without any possible bias error caused by illuminating light and background noise usually encountered in conventional LIF techniques. For the validation of the calibration curve obtained, thermally stratified fields established inside a glass cuvette of 10 mm width were measured. The measurement result showed a good agreement with the linear prediction. The temperature measurement in a 1 mm capillary tube could provide the feasible method of temperature measurement for the thin film region in the future.

A mathematical model is developed to describe the micro/nano-scale fluid flow and heat/mass transfer phenomena in an evaporating extended meniscus, focusing on the transition film region under nonisothermal interfacial conditions. The model incorporates thermocapillary stresses at the liquid-vapor interface, a slip boundary condition on the solid wall, polarity contributions to the working fluid field, and binary mixture evaporation. The analytical results show that the adsorbed film thickness and the thin film length decrease with increasing superheat by the thermocapillary stresses, which influences detrimentally the evaporation process by degrading the wettability of the evaporating liquid film. In contrast, the slip effect and the binary mixture enhance the stability of thin film evaporation. The slip effect at the wall makes the liquid in the transition region flow with smaller flow resistance and thus the length of the transition region increases. In addition, the total evaporative heat flow rate increases due to the slip boundary condition. The mixture of pentane and decane increases the length of the thin film by counteracting the thermocapillary stress, which enhances the stability of the thin film evaporation. The polarity effect of water significantly elongates the thin film length due to the strong adhesion force of intermolecular interaction. The strong interaction force restrains the liquid from evaporation for a polar liquid compared to a non-polar liquid. In the experimental part, laser induced fluorescence (LIF) thermometry has been used to measure the microscale temperature field of a heated capillary tube with a 1 mm by 1 mm square cross section. For the temperature measurement, the calibration curve between the temperature and the fluorescent intensity ratio of Rhodamine-B and Rhodamine-110 has been successfully obtained. The fluorescent intensity ratio provides microscale spatial resolution and good temperature dependency without any possible bias error caused by illuminating light and background noise usually encountered in conventional LIF techniques. For the validation of the calibration curve obtained, thermally stratified fields established inside a glass cuvette of 10 mm width were measured. The measurement result showed a good agreement with the linear prediction. The temperature measurement in a 1 mm capillary tube could provide the feasible method of temperature measurement for the thin film region in the future.

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The polymer electrolyte membrane fuel cell (PEMFC) converts the chemical energy of hydrogen and oxygen (air) into usable electrical energy. At the cathode (the positive electrode), a considerable amount of platinum is generally required to catalyse the sluggish oxygen reduction reaction (ORR). This has implications regarding the cost in high-power applications, and for making a broad commercialisation of the PEMFC technology possible, it would be desirable to lower the amount of Pt used to catalyse the ORR. In this thesis a number of techniques are described that have been developed in order to investigate catalytic activity at the cathode of the PEMFC. These methodologies resemble traditional three-electrode research in liquid electrolytes, including cyclic voltammetry in inert gas, but with the advantage of performing the experiments in the true PEMFC environment. From the porous electrode studies it was seen that it is possible to reach mass activities close to 0.2 gPt/kW at potentials above 0.65 V at 60 ◦C, but that the mass activities may become considerably lower when raising the temperature to 80 ◦C and changing the measurement methodology regarding potential cycling limits and electrode manufacturing. The model electrode studies rendered some interesting results regarding the ORR at the Pt/Nafion interface. Using a novel measurement setup for measuring on catalysed planar glassy carbon disks, it was seen that humidity has a considerable effect on the ORR kinetics of Pt. The Tafel slopes become steeper and the activity decreases when the humidity level of the inlet gases decreases. Since no change in the the electrochemical area of the Pt/Nafion interface could be seen, these kinetic phenomena were ascribed to a lowered Pt oxide coverage at the lower humidity level, in combination with a lower proton activity. Using bi-layered nm-thick model electrodes deposited directly on Nafion membranes, the behaviour of TiO2 and other metal oxides in combination with Pt in the PEMFC environment was investigated. Kinetically, no intrinsic effect could be seen for the model electrodes when adding a metal oxide, but compared to porous electrodes, the surface (specific) activity of a 3 nm film of Pt deposited on Nafion seems to be higher than for a porous electrode using ∼4 nm Pt grains deposited on a carbon support. Comparing the cyclic voltammograms in N2, this higher activity could be ascribed to less Pt oxide formation, possibly due to a particle size effect. For these bi-layered films it was also seen that TiO2 may operate as a proton-conducting electrolyte in the PEMFC. / I polymerelektrolytbränslecellen (PEMFC) omvandlas den kemiska energin hos vätgas och syrgas (luft) direkt till användbar elektrisk energi. På katoden (den positiva elektroden) krävs betydande mängder platina för att katalysera den tröga syrereduktionsreaktionen (ORR). Detta inverkar på kostnaden för högeffektsapplikationer, och för att göra en bred kommersialisering av PEMFC-teknologin möjlig skulle det vara önskvärt att minska den Pt-mängd som används för att katalysera ORR. I denna avhandling beskrivs ett antal tekniker som utvecklats för att undersöka katalytisk aktivitet på katoden i PEMFC. Metodiken liknar traditionella treelektrodexperiment i vätskeformig elektrolyt, med cyklisk voltammetri i inert gas, men med fördelen att försöken utförs i den riktiga PEMFC-miljön. I försök med porösa elektroder visades att det är möjligt att nå massaktiviteter nära 0.2 gPt/kW för potentialer över 0.65 V vid 60 ◦C, men massaktiviteterna kan bli betydligt lägre om temperaturen höjs till 80 ◦C, och om potentialsvepgränser och elektrodentillverkningsmetod ändras. Försök med modellelektroder resulterade i intressanta resultat rörande ORR i gränsskiktet Pt/Nafion. Genom att använda en ny metodik för att mäta på katalyserade plana elektroder av vitröst kol (glassy carbon), var det möjligt att se att gasernas fuktighet har en betydande inverkan på ORR-kinetiken hos Pt. Tafellutningarna blir brantare och aktiviteten minskar när inloppsgasernas fuktighetsgrad minskar. Eftersom den elektrokemiska arean hos Pt/Nafion-gränsskiktet inte ändrades, ansågs dessa kinetiska effekter bero på en lägre täckningsgrad av Ptoxider vid lägre fuktigheter, i kombination med lägre protonaktivitet. Genom att använda Nafionmembran belagda med nm-tjocka tvåskiktsmodellelektroder undersöktes hur Pt i kombination med TiO2 och andra metalloxider verkar i PEMFC-miljön. Kinetiskt sett hade tillsatsen av metalloxider ingen inre påverkan på aktiviteten, men vid jämförelse med porösa elektroder tycks den specifika ytaktiviteten vara högre hos en 3 nm film av Pt på Nafion än för en porös elektrod baserad på ∼4 nm Pt-korn belagda på ett kolbärarmaterial. Jämför man de cykliska voltammogrammen i N2, kan den högre aktiviteten tillskrivas en lägre grad av Pt-oxidbildning, vilket i sin tur kan bero på en storlekseffekt hos Pt-partiklarna. Försöken med dessa tvåskiktselektroder visade också att TiO2 kan verka som protonledande elektrolyt i PEMFC. / QC 20100706

<p dir="ltr">Boiling processes have long had an important role in power generation and air conditioning applications. The efficient and reliable heat dissipation afforded through the phase change process in the boiling has led to their generation of a substantial body of work in this field over several decades. Despite decades of efforts, the heat transfer performance prediction in boiling has been highly empirical with models working only for a narrow range of surface/fluids or other operating conditions. The limitation in these models is a result of a lack of mechanistic understanding of the underlying heat and mass transfer process. Surface dryout or boiling crisis is a process wherein there is a spontaneous formation of vapor film on top of the surface causing a catastrophic increase in surface temperature. The heat flux at which this formation of vapor film occurs is called critical heat flux (CHF). The CHF demarcates the upper limit to the regime of stable nucleating bubbles called nucleate boiling. The mechanism causing dryout is under debate for over half a century and several conflicting theories that cause dryout have been suggested since the 1950s including hydrodynamic, irreversible dryspot expansion, macrolayer dryout/liftoff, critical bubble distributions, vapor-recoil based theories and more. The lack of consensus is due to limitation in the information collected on the dynamic multiscale and chaotic bubble interactions. Recent advances in high-fidelity spatiotemporal phase, temperature, and heat flux measurements now enable diagnostic tools that can be leveraged to understand the complex heat transfer processes emerging from bubble-surface interaction on the boiling surface. In this work, we develop such techniques to understand various transport mechanisms underlying boiling and its crisis.</p><p dir="ltr">In this work, an experimental technique for collecting synchronized through-substrate visual and infrared (IR) measurements of a boiling surface is developed. An IR and visually transparent sapphire substrate with an IR-opaque indium-tin-oxide (ITO) heater layer is used to measure the phase (liquid and vapor areas) and temperature of the ITO layer. The visual camera collects the light reflected off the substrate from a red LED and the images collected show a contrast between liquid and vapor areas that is used to generate binarized phase maps. The temperature from the IR camera is used as boundary condition to solve a conduction problem for heat fluxes going into the fluid. Four distinct heat flux signatures corresponding to liquid, contact line, vapor and rewetting regions are observed. A post-processing methodology utilizing synchronous phase measurements to identify and partition these regions is introduced. The high-fidelity phase measurements allow for detection of fine features that are not discernable using heat flux maps alone. Analysis of the heat flux and temperature maps of partitioned regions for HFE-7100 fluid on the ITO surface show qualitative agreement with the trends in mechanisms underlying those areas. The experiment and post-processing methodology introduced in this work is the first to provide partitioning of underlying heat transfer mechanisms for multi-bubbles throughout the entire range of the boiling curve during both steady and transient scenarios.</p><p dir="ltr">The technique developed is used to probe the mechanisms underlying the boiling crisis. Theories suggested in the literature for boiling crisis are carefully evaluated and evidence against hydrodynamic instability, macrolayer dryout, vapor recoil, irreversible expansion of dryspots, macrolayer liftoff model, and bifurcations from critical distributions is observed. The signature in the peak of the spatially averaged fluid heat flux is observed to precede any other signs of dryout. Beyond the peak heat flux an increase in superheat leads to reduced heat dissipated by boiling and further increases the temperature causing a thermal runaway in the substrate that eventually leads to dryout. Hence, the boiling crisis is found to be a consequence of a peak in the nucleate boiling curve. The cause for the peak in the boiling heat flux for the surface-fluid combination tested was due to degradation of heat transfer caused by the replacement of high-heat-transfer contact line region with lower-heat-transfer vapor covered regions, among the multiple competing mechanisms. Hence, we propose that mechanistically modeling the boiling crisis rests on prediction of the peak in the upper portion of the nucleate boiling curve by considering all underlying heat transfer mechanisms. A modeling framework based on heat flux partitioning, where the overall heat transferred during boiling is calculated as the sum of the heat transferred by individual mechanisms is demonstrated as potential pathway to predict the upper portion of the nucleate boiling curve and thereby critical heat flux. Based on the terms involved in summation for individual mechanisms, we propose that the boiling curve for any given surface be interpreted as a path on a multidimensional surface (boiling manifold). Estimation of such a boiling manifold allows for prediction of the boiling curve for any surface, given development of the relations between these parameters and surface-fluid properties, and can further be used to backtrack relevant thermophysical or nucleation properties for enhanced boiling performance.</p><p dir="ltr">Enhancement of pool boiling heat transfer performance using surface modifications is of major interest to applications and this work further delves into characterizing the boiling performance using traditional surface averaged measurements of microstructured surfaces using HFE-7100. We find that microlayer evaporation from the imbibed liquid layer underneath the growing vapor bubbles is the key mechanism of boiling heat transfer enhancement in microstructures. Further, this implies that characterization of microstructured surfaces for evaporative performance can serve as an important proxy to enable heat transfer coefficient enhancement prediction during pool boiling. Hence, we also developed an easily calculated Figure of Merit (FOM) that characterizes the efficacy of evaporation from microstructured surfaces.</p><p dir="ltr">To summarize, in this work we developed an experimental technique using synchronous through-substrate high-speed visual and IR imaging methods. New post-processing techniques for partitioning of different heat transfer mechanisms are proposed and used to analyze boiling on an ITO-coated sapphire substrate with HFE-7100 as the working fluid. We reveal thermal runaway in the substrate caused due to a negative-sloping boiling curve as the mechanism of dryout. Mechanistic modeling of the critical heat flux thus involves calculating the peak in the nucleate boiling curve. A framework to predict the nucleate boiling curve and subsequently critical heat flux is proposed based on the partitioning analysis. The experimental method developed lays the groundwork for measuring heat flux and superheats associated with various mechanisms, and hence, enables validation of future partitioning-based boiling heat transfer models that intrinsically enable prediction of the peak.</p>