Membrane gas absorption technology is considered as one of the promising alternatives to conventional techniques for CO2 separation from the flue gas of fossil fuels combustion. As a hybrid approach of chemical absorption and membrane separation, it may offer a number of important features, including operational flexibility, compact structure, linear scale up and predictable performance. The main challenge is the additional membrane mass transfer resistance, especially when this resistance increases due to the absorbent intruding into the membrane pores. In this thesis, the experimental was set up to investigate how the operating parameters affect the absorption performance when using absorbent in hollow fiber contactor, and to obtain the optimal range of operation parameters for the designated membrane gas absorption system . During 20 days’ continuous experiment, we observed that the CO2 mass transfer rate decreases significantly following the operating time, which is attributed to the increase of membrane mass transfer resistance resulting from partial membrane wetting. To better understand the wetting evolution mechanism, the immersion experiments were carried out to assume that the membrane fibers immersed in the absorbents would undergo similar exposure as those used in the membrane contactor. Various membrane characterization methods were used to illustrate the wetting process before and after the membrane fibers were exposed to the absorbents. The characterization results showed that the absorbent molecules diffuse into the polypropylene (PP) polymer during the contact with the membrane, resulting in the swelling of the membrane. In addition, the effects of operating parameters such as immersion time, CO2 loading, as well as absorbent type on the membrane wetting were investigated in detail. Finally, based on the analysis results, methods to smooth the membrane wetting were discussed. It was suggested that improving the hydrophobicity of PP membrane by surface modification may be an effective way to improve the membrane long-term performance. Modification of the polypropylene membrane by depositing a rough layer of PP was carried out in order to improve the non-wettability of membrane. The comparison of long-term CO2 absorption performance by PP membranes before and after modification proves that the modified polypropylene membranes retained higher hydrophobicity than the untreated polypropylene membrane. Therefore modification is likely to be more suitable for use in membrane gas absorption contactors for CO2 separation, particularly over long operation time.

<p>Membrane gas absorption technology is considered as one of the promising alternatives to conventional techniques for CO₂ separation from the flue gas of fossil fuels combustion. As a hybrid approach of chemical absorption and membrane separation, it may offer a number of important features, including operational flexibility, compact structure, linear scale up and predictable performance. The main challenge is the additional membrane mass transfer resistance, especially when this resistance increases due to the absorbent intruding into the membrane pores.</p><p>In this thesis, the experimental was set up to investigate how the operating parameters affect the absorption performance when using absorbent in hollow fiber contactor, and to obtain the optimal range of operation parameters for the designated membrane gas absorption system . During 20 days’ continuous experiment, we observed that the CO₂ mass transfer rate decreases significantly following the operating time, which is attributed to the increase of membrane mass transfer resistance resulting from partial membrane wetting.</p><p>To better understand the wetting evolution mechanism, the immersion experiments were carried out to assume that the membrane fibers immersed in the absorbents would undergo similar exposure as those used in the membrane contactor. Various membrane characterization methods were used to illustrate the wetting process before and after the membrane fibers were exposed to the absorbents. The characterization results showed that the absorbent molecules diffuse into the polypropylene (PP) polymer during the contact with the membrane, resulting in the swelling of the membrane. In addition, the effects of operating parameters such as immersion time, CO₂ loading, as well as absorbent type on the membrane wetting were investigated in detail. Finally, based on the analysis results, methods to smooth the membrane wetting were discussed. It was suggested that improving the hydrophobicity of PP membrane by surface modification may be an effective way to improve the membrane long-term performance.</p><p>Modification of the polypropylene membrane by depositing a rough layer of PP was carried out in order to improve the non-wettability of membrane. The comparison of long-term CO₂ absorption performance by PP membranes before and after modification proves that the modified polypropylene membranes retained higher hydrophobicity than the untreated polypropylene membrane. Therefore modification is likely to be more suitable for use in membrane gas absorption contactors for CO₂ separation, particularly over long operation time.</p>

abstract: Design and mitigation of infrastructure on expansive soils requires an understanding of unsaturated soil mechanics and consideration of two stress variables (net normal stress and matric suction). Although numerous breakthroughs have allowed geotechnical engineers to study expansive soil response to varying suction-based stress scenarios (i.e. partial wetting), such studies are not practical on typical projects due to the difficulties and duration needed for equilibration associated with the necessary laboratory testing. The current practice encompasses saturated “conventional” soil mechanics testing, with the implementation of numerous empirical correlations and approximations to obtain an estimate of true field response. However, it has been observed that full wetting rarely occurs in the field, leading to an over-conservatism within a given design when partial wetting conditions are ignored. Many researchers have sought to improve ways of estimation of soil heave/shrinkage through intense studies of the suction-based response of reconstituted clay soils. However, the natural behavior of an undisturbed clay soil sample tends to differ significantly from a remolded sample of the same material. In this study, laboratory techniques for the determination of soil suction were evaluated, a methodology for determination of the in-situ matric suction of a soil specimen was explored, and the mechanical response to changes in matric suction of natural clay specimens were measured. Suction-controlled laboratory oedometer devices were used to impose partial wetting conditions, similar to those experienced in a natural setting. The undisturbed natural soils tested in the study were obtained from Denver, CO and San Antonio, TX. Key differences between the soil water characteristic curves of the undisturbed specimen test compared to the conventional reconstituted specimen test are highlighted. The Perko et al. (2000) and the PTI (2008) methods for estimating the relationship between volume and changes in matric suction (i.e. suction compression index) were evaluated by comparison to the directly measured values. Lastly, the directly measured partial wetting swell strain was compared to the fully saturated, one-dimensional, oedometer test (ASTM D4546) and the Surrogate Path Method (Singhal, 2010) to evaluate the estimation of partial wetting heave. / Dissertation/Thesis / Masters Thesis Engineering 2017

La silice de précipitation, poreuse à l'échelle de 10 nm, a de nombreuses applications industrielles dans lesquelles elle est mélangée avec des fondus de polymère, composés de molécules de dimension nanométrique. La surface de la silice est de haute énergie, si bien qu'elle tend à être recouverte par la plupart des liquides. Par conséquent, lorsqu'une goutte de liquide est déposée sur la surface de la silice, un film " précurseur " s'étale au-devant de celle-ci, avec une épaisseur de l'ordre du nm. A l'aide d'observations macroscopiques et par imagerie ellipsométrique, nous avons mis en évidence que le polybutadiène et le polystyrène sont en conditions de mouillage pseudo-partiel avec la silice : une goutte macroscopique coexiste à l'équilibre avec le film précurseur en raison de la présence de forces à longue portée attractive à l'échelle du film. Le film précurseur est en fait formé de molécules quasi-isolées qui diffusent avec un coefficient de diffusion égal au coefficient d'auto diffusion mesuré en volume. Ceci nous donne des indications précieuses sur les interactions polymère/silice. Par ailleurs nous observons dans certains cas la croissance d'une instabilité, prenant la forme d'un film " secondaire " d'épaisseur supérieure à celle du film précurseur. Le polydiméthylsiloxane est quant à lui en conditions de mouillage total sur la silice, et seul un film existe à l'équilibre, les forces à longues portées étant répulsives. L'imbibition de la silice poreuse peut également se relier à ces observations. Finalement, nous déduisons que le film précurseur pour des faibles masses de polymères a peu d'impact sur la dynamique d'imbibition de pastilles de silice poreuse. / Precipitated silica, which is porous at the 10 nm scale, has various industrial uses where it is mixed with polymer melts, with characteristic molecular sizes in the nanometer range. Having a high surface energy, silica tends to be covered by most liquids. As a consequence, when a liquid droplet is deposited on silica surfaces, a thin “precursor” film spreads in front of the droplet, with a thickness of a few nanometers. By combining macroscopic observations and ellipsometry imaging, we found that polybutadiene and polystyrene melts on silica are in pseudo-partial wetting conditions, for which a droplet coexists with a precursor film at equilibrium, due to attractive long range forces at the film length scale. The precursor film is composed of quasi-isolated molecules diffusing in two dimensions with a diffusion coefficient equal to the bulk self-diffusion coefficient. This provides valuable information on the polymer/silica interactions. Furthermore, we occasionally observe the growth of an instability, as a “secondary” film which is thicker than the precursor film. In contrast, polydimethylsiloxane melts are in total wetting conditions on silica: at equilibrium, a polymer film covers the silica surface and no droplets coexist with the film, due to repulsive long range forces. Our observations of the imbibition of porous silica by polymer melts were related to these results. Eventually, for low molar mass polymers, we find that the precursor film has no significant impacts on porous silica pellets imbibition.

Considérant une particule isolée, la différence principale entre un colloïde actif et un colloïde passif réside dans le temps de persistance du régime balistique. La transition du régime balistique vers le régime diffusif est déterminée dans les deux cas par des coefficients de friction ou de manière équivalente par des coefficients de diffusion. Le mouvement d’une particule colloïdale passive micrométrique est diffusif lorsqu’il est observé sur des intervalles de temps d’au moins une microseconde, suffisamment longs pour que la direction de la quantité de mouvement soit rendue aléatoire par des collisions avec les molécules de solvant. A l’échelle macroscopique ces collisions se traduisent par un coefficient de friction de translation. Pour une particule colloïdale active, un mouvement diffusif est observé pour des intervalles de temps de plusieurs secondes, suffisamment longs pour que la direction d’auto-propulsion soit rendue aléatoire par la diffusion rotationnelle de la particule.Dans cette thèse, nous étudions le mouvement d’une particule colloïdale active déposée à la surface de l’eau. Des particules Janus aux propriétés catalytiques ont été préparées par dépôt de platine métal à la surface de particules de silice. La profondeur d’immersion des particules ainsi que leur orientation par rapport à la surface de l’eau ont été caractérisées et discutées en tenant compte des propriétés de mouillage non-uniformes de la surface des particules Janus. Le mouvement de particules isolées en présence de quantités variables d’eau oxygénée utilisée comme source d’énergie, a été enregistré par vidéo-microscopie optique et les trajectoires analysées en termes de déplacement carré moyen et de fonction d’auto-corrélation des vitesses. L’observation de deux types de trajectoires, rectilignes et circulaires, révèle la force effective ainsi que le couple induit par la décomposition catalytique de l’eau oxygénée à la surface de la particule Janus. Le résultat principal de ce travail est que le mouvement des particules actives confinées à l’interface persiste plus longtemps dans le régime balistique que celui de particules actives totalement immergées en solution. Ceci est dû au confinement qui réduit le nombre de degrés de liberté de rotation mais aussi aux conditions de mouillage partiel qui font apparaître des contributions supplémentaires à la friction de rotation. / At the single-particle level, the main difference between active colloids and passive ones is the time scale over which the motion crosses over from ballistic to diffusive regime. In both cases, friction coefficients or equivalently diffusion coefficients determine this time scale. For instance, the motion of a passive colloid of 1m radius is diffusive when observed over lag times longer than a microsecond, once the direction of its momentum has been randomized by collisions with solvent molecules. At the macroscopic scale these collisions are accounted for by the translational friction coefficient. For an active colloid the effective diffusive behavior observed over lag times larger than few seconds results from the randomization of the direction of self-propulsion by rotational diffusion. In this thesis we investigated the motion of an active Janus colloid trapped at air-water interface. Spherical catalytic Janus colloids have been prepared through the deposition of platinum metal at the surface of silica particles. Immersion depth of the Janus colloid as well as their orientation with respect to the water surface, has been characterized and interpreted in terms of the non-uniform wetting properties of the Janus particles. The motion of the active Janus colloids in the presence of various concentration of hydrogen peroxide H2O2 as fuel was characterized by video microscopy and the trajectories analyzed through the mean square displacement and the velocity autocorrelation function. The types of trajectories, directional and circular ones that we observed in our experiments, revealed the effective force and torque induced by the catalytic decomposition of H2O2. At the water surface, active colloids perform more persistent directional motions as compared to the motions performed in the bulk. This has been interpreted as due to the loss of degrees of freedom resulting from the confinement at interface and also to the partial wetting conditions that possibly bring new contributions to the rotational friction at interface.

The thesis deals on the theory of partial wetting of a wall, whereby a relation between the velocity of a droplet moving along an inclined plane and time is derived. There are explained basic definitions coherent to the theory of partial wetting. According to divergence of a normal vector of the droplet surface, there is developed a technique for mathematical evaluation of the component of dynamic adhesive force. Within the scope of diploma paper, there was an experimental measurement performed, whereat a velocities of droplets of various volumes and at different inclination angles on four analyzed surfaces were determined. By using non-linear regression, unknown parameters such as the adhesion coefficient, the component of a dynamic adhesive force, initial and terminal velocity of a droplet were evaluated from the experiment results. Within the thesis there was performed a simulation of droplet motion on an inclined plane in ANSYS Fluent. Conclusion includes an assessment and a comparison of results obtained, and new procedures that may be helpful at further research of descending droplet.

In recent years, membrane gas absorption technology has been considered as one of the promising alternatives to conventional techniques for CO2 capture due to its favorable mass transfer performance. As a hybrid approach of chemical absorption and membrane separation, it exhibits a number of advantages, such as operational flexibility, compact structure, high surface-area-to-volume ratio, linear scale up, modularity and predictable performance. One of the main challenges of membrane gas absorption technology is the membrane wetting by absorbent over prolonged operating time, which may significantly decrease the mass transfer coefficients of the membrane module. In this thesis, the experimental was set up to investigate the dependency of CO2 removal efficiency and mass transfer rate on various operating parameters, such as the gas and liquid flow rates, absorbent type and concentration and volume fraction CO2 at the feed gas inlet. In addition, the simultaneous removal of SO2 and CO2 was investigated to evaluate the feasibility of simultaneous desulphurization and decarbonization in the same membrane contactor. During 14 days of continuous operation, it was observed that the CO2 mass transfer rate decreased significantly following the operating time, which was attributed to partial membrane wetting. To better understand the wetting mechanism of membrane pores during their prolonged contact with absorbents, immersion experiments for up to 90 days were carried out. Various membrane characterization methods were used to illustrate the wetting process before and after the membrane fibers were exposed to the absorbents. The characterization results showed that the absorbent molecules diffused into the polypropylene polymer during the contact with the membrane, resulting in the swelling of the membrane. In addition, the effects of operating parameters such as immersion time and absorbent type on the membrane wetting were investigated in detail. Finally, based on the analysis results, methods to smooth the membrane wetting were discussed. It was suggested that improving the hydrophobicity of polypropylene membrane by surface modification may be an effective way to improve the long-term operating performance of membrane contactors. Therefore, the polypropylene hollow fibers were modified by depositing a thin superhydrophobic coating on the membrane surface to improve their hydrophobicity. The mixture of cyclohexanone and methylethyl ketone was considered as the best non-solvent to achieve the fiber surface with good homogeneity and acceptably high hydrophobicity. In the long-period operation, the modified membrane contactor exhibited more stable and efficient performance than the untreated one. Hence, surface treatment provides a feasibility of improving the system stability for CO2 capture from the view of long-term operation. / En av de tekniker som under senare framhållits som ett lovande alternativ till konventionell CO2-avskiljning är membran-gas-absorptionstekniken på grund av god prestanda vad gäller masstransport. Det blandade angreppssättet med både kemisk absorption och membranseparation har en rad fördelar, såsom driftflexibilitet, kompakt konstruktion, högt yt-volymsförhållande, linjär uppskalning, modularitet och förutsägbar prestanda. En av de viktigaste utmaningarna för membran-gas-absorptionstekniken är vätningen av membranet med absorbenten under långa drifttider, vilket väsentligt kan minska membranmodulens masstransportkoefficienter.  I avhandlingen har en rad olika driftparametrars påverkan på CO2-reningsgraden och massöverföringshastigheten undersökts. Driftparametrar inkluderar gas- och vätskeflöden, typ av absorbent och koncentration och volymfraktion av CO2 vid gasinloppet. Avskiljning av SO2 och CO2 har dessutom undersökts för att utvärdera möjligheten att samtidigt, i samma membranenhet, avlägsna svavel och kol. Under 14 dagars kontinuerlig drift konstaterades det att massöverföringshastigheten för CO2 minskade avsevärt med drifttiden, vilket hänfördes till partiell vätning av membranet.   För att bättre förstå mekanismerna för vätning av membranporer under långvarig kontakt med absorbenter genomfördes doppningsexperiment i upp till 90 dagar. Olika metoder för karakterisering av membran användes för att illustrera vätningsprocessen före och efter det att membranfibrerna exponerades för absorbenterna. Resultaten av karakteriseringen visade att absorbentmolekylerna spreds in i polypropenpolymeren under kontakten med membranet, vilket ledde till att membranet svällde. Dessutom undersöktes effekterna av driftsparametrar såsom nedsänkningstid och typ av absorbent i detalj. Slutligen, på grundval av analysresultaten, diskuterades metoder för att underlätta vätningen av membran. Att förbättra polypropylenmembranets hydrofobicitet genom modifiering av ytan föreslogs kunna vara ett effektivt sätt att förbättra den långsiktiga driftprestandan för membranenheter. Därför modifierades de ihåliga fibrerna av polyproylen med ett tunt lager av en superhydrofob beläggning på membranets yta för att förbättra hydrofobiciteten. En blandning av cyklohexanon och metyletylketon ansågs vara det bästa icke-lösningsmedlet för att få en fiber yta med god homogenitet och acceptabelt hög hydrofobicitet. Under lång driftperiod, uppvisade den modifierade membranenheten stabilare och effektivare prestanda än den obehandlade. Därför erbjuder ytbehandling en möjlighet till att förbättra systemets stabilitet för CO2-avskiljning när det gäller långsiktig drift. / VR-SIDA Swedish Research Links Programme