Superhydrophobic (SHS) and lubricant-infused surfaces (LIS) exhibit exceptional non-wetting characteristics that make them attractive for energy production applications including steam condensation and fouling mitigation. The dissertation work focuses on application of non-wetting surfaces to energy production using a systematic approach examining each component of surface fabrication in three functional areas. First, SHS and LIS are fabricated using robust, scalable methods and tested for durability in heated, wet conditions and under high-energy water jet impingement. Clear performance differences are shown based on surface texturing, functionalizing agent, and infused lubricant. Second, SHS and LIS are applied to tube exteriors and evaluated for their ability to produce sustained dropwise condensation in a typical power plant condenser environment. The surfaces are shown to produce heat transfer coefficients up to 7-10 times that of film-wise condensation, with condenser effectiveness of 0.92 or better compared to effectiveness of about 0.6 in conventional condensers. Third, LIS on the interior of tubes are assessed in accelerated mineral fouling conditions. LIS are shown to mitigate calcium sulfate and calcium carbonate fouling under laminar conditions. The results of the study bear profound benefits to reducing the levelized cost of condensers and water uptake in thermoelectric power plants, that currently consume about 50% of the total water use in the U.S. / Doctor of Philosophy / Creating durable, hybrid surfaces for improved steam condensation and fouling mitigation would provide substantial impact to power generation worldwide. Bioinspired, non-wetting surfaces, such as superhydrophobic (SHS) and lubricant-infused surfaces (LIS) exhibit exceptional non-wetting characteristics that make them attractive for energy applications. Each of these non-wetting technologies, however, faces durability and scalability challenges that make them unfeasible for widespread, practical adoption. As a result, decades of materials science research have stagnated in the research laboratories with limited demonstrations of dropwise condensation and fouling mitigation in static situations. The dissertation work focuses on application of SHS and LIS to energy production using a systematic approach examining each component of surface fabrication in three functional areas. First, SHS and LIS are fabricated using robust, scalable methods and tested for durability using ASTM standard static and dynamic evaluation methods. Clear performance differences are shown based on surface texturing, functionalizing agent, and infused lubricant. Second, dropwise steam condensation on the surfaces are shown to exhibit heat transfer performance an order of magnitude greater than film-wise condensation in a typical power plant condenser environment. The surfaces are shown to produce heat transfer coefficients up to 7-10 times that of film-wise condensation, with condenser effectiveness of 0.92 or better compared to effectiveness of about 0.6 in conventional condensers. This work presents for the first time, a non-dimensional correlation for a priori prediction of LIS heat transfer performance given known qualities of the LIS. Third, challenges of fouling mitigation in power plants have been studied for over a decade. This work demonstrates for the first time that LIS applied to the interior of tubes mitigate calcium sulfate and calcium carbonate fouling in both static and laminar flow conditions.

The current study is focused on the characterization of four natural leaf species (quaking, bigtooth and columnar european aspen as well as black locust) possessing a unique dual-scale cuticle structure composed of micro- and nano-scale asperities, which are able to effectively resist wetting (superhydrophobic), characteristic of The Lotus Effect. Scanning Electron Microscopy (SEM) was used to track the growth and evolution of their distinctive nano-scale epicuticular wax (ECW) morphologies over one full growing season. In addition, the stability of their superhydrophobic property was tested in various environments. It was determined that the long-term stability of these surfaces is tentatively linked to various environmental stress factors. Specifically, a combination of high temperature and humidity caused the degradation of nano-scale asperities and loss of the superhydrophobic property. The dual-scale surface structure was found to provide a suitable template for the design of future superhydrophobic engineering materials.

The current study is focused on the characterization of four natural leaf species (quaking, bigtooth and columnar european aspen as well as black locust) possessing a unique dual-scale cuticle structure composed of micro- and nano-scale asperities, which are able to effectively resist wetting (superhydrophobic), characteristic of The Lotus Effect. Scanning Electron Microscopy (SEM) was used to track the growth and evolution of their distinctive nano-scale epicuticular wax (ECW) morphologies over one full growing season. In addition, the stability of their superhydrophobic property was tested in various environments. It was determined that the long-term stability of these surfaces is tentatively linked to various environmental stress factors. Specifically, a combination of high temperature and humidity caused the degradation of nano-scale asperities and loss of the superhydrophobic property. The dual-scale surface structure was found to provide a suitable template for the design of future superhydrophobic engineering materials.

Precise manipulation of heterogeneous droplets on an open droplet microfluidic platform could have numerous practical advantages in a broad range of applications, from proton exchange membrane (PEM) fuel cells and microreactors, to medical diagnostic platforms capable of assaying complex biological analytes. Toward the aim of developing electrically controllable micropost arrays for use in open droplet manipulation, custom-designed titanium dioxide (TiO2)- loaded poly(dimethylsiloxane) (PDMS) micropost arrays were developed in this work and indirectly mechanically actuated by applying an electric field. Initial experiments explored the bulk properties of TiO2-loaded PDMS films, with scanning electron microscopy (SEM) confirming a uniform TiO2 particle distribution in the PDMS, and tensile testing of bulk films showing an inverse relationship between TiO2 % (w/w) and Young’s Modulus with the Young’s Moduli quantified as 4.22 ± 0.51 MPa for unloaded PDMS, 2.27 ± 0.18 MPa for 10 % (w/w) TiO2, and 1.39 ± 0.20 MPa for 20 % (w/w) TiO2. Following bulk material evaluation, soft lithography methods were developed to fabricate TiO2- loaded PDMS micropost arrays. Mathematical predictions were applied to design microposts of varying shape, length, and gap spacing to yield super-hydrophobic surfaces actuatable by an electric field. Visual inspection and optical microscopy of the resulting arrays confirmed a non- collapsed micropost geometry. Overall, round microposts that were 100, 200, and 300 μm in length, 15 μm in diameter, and spaced 50 μm apart were produced largely free of defects, and used in contact angle measurements and micropost deflection experiments. Droplet contact angles measured on the arrays remained above 120° indicating the arrays successfully provided super- hydrophobic surfaces. Individual microposts deflected most notably above an electric field strength of 520 kV/m (12.5 kV nominal voltage). The ability to mechanically deflect customized microposts using an electric field demonstrated by this work is promising for translating this technology to precise droplet manipulation applications. Indirect actuation of droplets could enable the manipulation of liquids with varying electrical properties, which is a limitation of current micropumping technologies. Once optimized, electrically actuated micropost arrays could significantly contribute to the micro- handling of heterogeneous, highly ionic, and/or deionized fluids. / Thesis (Master, Chemical Engineering) -- Queen's University, 2013-03-03 17:25:49.785

La synthèse d'une membrane composite formée d'une couche fine de surface de structure très réticulée et permsélective aux gaz déposée sur un substrat poreux a été étudiée comme solution pour accroître la perméabilité aux gaz tout en conservant une sélectivité importante. Une couche mince de polymère-plasma SiOCH a été retenue comme membrane de séparation gazeuse car elle possède une structure dont l'ultramicroporisté peut être contrôlée en ajustant les paramètres du procédé plasma comme la puissance, le flux de monomère et la pression de travail. Néanmoins, dans la membrane SiOCH, la taille moyenne des pores et leur distribution sont difficiles à appréhender par des techniques de caractérisation classiques, notamment proche de la surface car elle est très fine. Ce mémoire de thèse concerne le contrôle de la structure poreuse dans une couche mince de polymère-plasma SiOCH déposée sur un substrat polymère en utilisant un précurseur organosilicié. La spectroscopie d'annihilation de positron couplée à un faisceau de positron lent a été utilisée pour identifier la microstructure de couches minces SiOCH avec la profondeur. Ceci a nécessité tout d'abord l'acquisition d'une bonne connaissance de la caractérisation de l'annihilation de positron de matériaux polymères et céramiques. Des couches minces de SiOCH conformes ou superhydrophobes (SHP) ont été obtenues à deux fréquences différentes, respectivement à 13,56 MHz ou 40 kHz. Pour une couche conforme, le type de substrat, la structure chimique du précurseur et la puissance RF sont les paramètres majeurs qui influencent la structure des pores. Quand les films de SiOCH sont composées de deux couches (couche uniforme de surface et couche de transition) déposées sur un substrat poreux, l'analyse PAS met en évidence une couche de transition large et l'ensemble possède une perméabilité aux gaz élevée grâce à la porosité de surface du support. Lors de la préparation des couches minces SHP, quand la pression totale dépasse 0,6 mbar, la nucléation en phase gaz apparaît ce qui augmente la rugosité de la surface. Ceci induit des angles de contact à l'eau supérieurs à 160° et une hystérésis d'angles de contact avancée-reculée de seulement 2°. La préservation des chaînes carbonées et la microstructure sont les facteurs déterminant pour accroître l'hydrophobicité des couches minces de SiOCH. / In gas separation, the fabrication of composite membranes consisting of a permselective thin top layer with high cross-linking structures and a porous substrate has been regarded as a solution for improving gas permeability and simultaneously retaining high selectivity. A plasma-polymerized SiOCH film has been known as an appropriate gas separation membrane because it possesses a dense structure, the crosslinking degree of which could be controlled by adjusting plasma parameters such as plasma power, monomer flow rate, and system pressure. However, the pore size and distribution in SiOCH films, especially in the region of depth profile, are difficult to measure by conventional techniques because of they are very thin.This thesis is concerned with the control of pore structure in a plasma-polymerized SiOCH film on a polymeric substrate by using an organosilicon source. The positron annihilation spectroscopy (PAS) coupled to the slow positron beam technique was used to identify the microstructure of SiOCH films as a function of depth. This step required to have a good understanding of the positron annihilation characteristics of different materials such as organic, inorganic, and hybrid materials. Depending on plasma frequency adjustments, SiOCH films with a flat and a superhydrophobic (SHP) surface were fabricated at 13.56 MHz and 40 kHz, respectively. For a flat SiOCH film, substrate type, chemical structure of precursor, and RF power were the major variables that influenced the pore structure. When SiOCH films composed of two layers (bulk and transitions layers) were deposited on porous substrates, they displayed a long transition layer based on the PAS analysis and possessed a high gas permeability due to the surface porosity of the substrate. When the precursor used possessed a cyclic ring structure, an opportunity of a break-up of the cyclic ring would increase with increasing RF power and then induce formation of new big pores. For the preparation of SHP films, when the total pressure was higher than 0.6 mbar, the gas nucleation reaction was enhanced to induce roughness on SiOCH films, and it would show a high WCA of over 160o and a low WCAH of only 2 degrees. Both the hydrocarbon preservation and microstructure were the main factors in improving the surface superhydrophobicity of SiOCH films.

Examples of superhydrophobic surfaces found in nature such as self-cleaning property of lotus leaf and walking on water ability of water strider have led to an extensive investigation in this area over the past few decades. When a water droplet rests on a textured surface, it may either form a liquid-solid-vapor composite interface by which the liquid droplet partially sits on air pockets or it may wet the surface in which the water replaces the trapped air depending on the surface roughness and the surface chemistry. Super water repellent surfaces have numerous applications in our daily life such as drag reduction, anti-icing, anti-fogging, energy conservation, noise reduction, and self-cleaning. In fact, the same concept could be applied in designing and producing surfaces that repel organic contaminations (e.g. low surface tension liquids). However, superoleophobic surfaces are more challenging to fabricate than superhydrophobic surfaces since the combination of multiscale roughness with re-entrant or overhang structure and surface chemistry must be provided. In this study, simple, cost-effective and potentially scalable techniques, i.e., airbrush and electrospray, were employed for the sake of making superhydrophobic and superoleophobic coatings with random and patterned multiscale surface roughness. Different types of silicon dioxide were utilized in this work to in order to study and to characterize the effect of surface morphology and surface roughness on surface wettability. The experimental findings indicated that super liquid repellent surfaces with high apparent contact angles and extremely low sliding angles were successfully fabricated by combining re-entrant structure, multiscale surface roughness, and low surface energy obtained from chemically treating the fabricated surfaces. In addition to that, the experimental observations regarding producing textured surfaces in mask-assisted electrospray were further validated by simulating the actual working conditions and geometries using COMSOL Multiphysics.

De nombreuses techniques de lithographie sont proposées aujourd'hui pour structurer des surfaces à l'échelle micrométrique et nanométrique. Parmi elles, la lithographie colloïdale est intéressante en raison notamment du faible coût du procédé. Dans cette thèse, nous avons développé une nouvelle technique appelée « lithographie électro-colloïdale » qui est basée sur l'utilisation de particules colloïdales soumises à des champs électriques continus et alternatifs. Avec des temps de préparation courts et une instrumentation peu coûteuse, des surfaces structurées polymériques et métalliques ont été produites puis testées pour différentes applications (immobilisation de protéines, réseaux de microélectrodes, surfaces superhydrophobes). / Many lithography techniques have been developed to structure surfaces at the micrometer and sub-micrometer ranges. Among them, colloidal lithography is interesting because the process is inexpensive and does not require the use complex instruments. In this thesis, we have developed a new technique called « electro-colloidal lithography » which is based on the use of colloidal particles organized using alternating and direct electric fields. With short preparation times and inexpensive instruments, polymeric and metallic structured surfaces have been prepared and tested for different applications (protein immobilization, microelectrode arrays, superhydrophobic surfaces)

Ce travail de thèse, constitué de deux parties apparemment très différentes, a pour objectif commun de modéliser et simuler certaines interfaces non classiques en mécanique des fluides et en mécanique des solides. Dans la première partie qu'est la partie principale du travail, l'écoulement de Stokes d'un fluide dans un canal encadré par deux parois solides parallèles est étudié. La surface d'une paroi étant supposée lisse, la condition d'adhérence parfaite classique est adoptée pour l'interface fluide-solide homogène correspondante. La surface de l'autre paroi étant supposée rugueuse et capable de piéger de petites poches d'air, l'interface liquide-solide correspondante est donc hétérogène. La première partie de ce travail consiste à homogénéiser l'interface liquide-solide hétérogène de façon à remplacer cette dernière par une interface fluide-solide homogène imparfaite caractérisée par une longueur de glissement effective. Le problème essentiel de déterminer la longueur de glissement effective est résolu par le développement : (i) d'une approche semi-analytique dans le cas où la surface rugueuse est périodique; (ii) d'une approche basée sur la méthode de solution fondamentale dans le cas où la surface rugueuse est aléatoire. Les résultats obtenus par les approches développées sont systématiquement comparés avec ceux délivrés par la méthode des éléments finis. La deuxième partie du travail est de déterminer les modules élastiques effectifs d'un composite fibreux dans lequel les interfaces entre la matrice et les fibres sont imparfaites et décrites par le modèle membranaire. Une méthode numérique efficace basée sur la transformée de Fourier est ainsi développée et implantée pour traiter le cas général où la section d'une fibre peut avoir une forme quelconque / The present work, consisting of two seemingly very different parties, aims at modeling and simulating some non-classical interfaces in fluid mechanics and solid mechanics. In the first part which is the main part of the work, the Stokes flow of a fluid in a channel bounded by two parallel solid walls is studied. The surface of a solid wall being assumed to be smooth, the classic perfect adherence condition is adopted for the corresponding homogeneous fluid-solid interface. The surface of the other wall being taken to be rough and capable of trapping small pockets of air, the corresponding liquid-solid interface is heterogeneous. The first part of this work is to homogenize the heterogeneous liquid-solid interface so as to replace it by an imperfect homogeneous fluid-solid interface characterized by an effective slip length. The essential underlying problem of determining the effective slip length is achieved by developing: (i) a semi-analytical approach when the rough surface is periodic; (ii) an approach based on the fundamental solution method when the surface is randomly rough. The results obtained by the developed approaches are systematically compared with those issued from the finite element method. The second part of the work is to determine the effective elastic moduli of a fiber composite in which the interfaces between the matrix and fibers are imperfect and described by the membrane model. An efficient numerical method based on the fast Fourier transform is developed and implemented to treat the general case where the section of a fiber can be of any shape

The use of hydrophobic surfaces is important for many processes both in nature and industry. Interactions between hydrophobic species play a key role in industrial applications such as water-cleaning procedures and pitch control during papermaking but they also give information on how to design surfaces like hydrophobic mineral pigments. In this thesis, the influence of surface properties on wetting and interaction forces has been studied. Surfaces with close-packed particles, pore arrays, randomly deposited nanoparticles as well as reference surfaces were prepared. The atomic force microscope (AFM) was utilized for force and friction measurements while contact angles and confocal Raman microscopy experiments were mainly used for wetting studies. The deposition of silica particles in the size range of nano- to micrometers using the Langmuir-Blodgett (LB) technique resulted in particle coated surfaces exhibiting hexagonal close-packing and close to Wenzel state wetting after hydrophobization. Force measurements displayed long-range interaction forces assigned to be a consequence of air cavitation. Smaller roughness features provided larger forces and interaction distances interpreted as being due to fewer restrictions of capillary growth. Friction measurements proved both the surface structure and chemistry to be important for the observed forces. On hydrophobic pore array surfaces, the three-phase contact line of water droplets avoided the pores which created a jagged interface. The influence of the pores was evident in the force curves, both in terms of the shape, in which the three-phase contact line movements around the pores could be detected, as well as the depth of the pores providing different access and amount of air. When water/ethanol mixtures were used, the interactions were concluded to be due to ethanol condensation. Confocal Raman microscopy experiments with water and water/ethanol mixtures on superhydrophobic surfaces gave evidence for water depletion and ethanol/air accumulation close to the surface. Force measurements using superhydrophobic surfaces showed extremely long-range interaction distances. This work has provided evidence for air cavitation between hydrophobic surfaces in aqueous solution. It was also shown that the range and magnitude of interaction forces could, to some extent, be predicted by looking at certain surface features like structure,roughness and the overall length scales. / <p>QC 20121011</p>

In this study, dendronization and grafting via controlled polymerization techniques, atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP), have been explored. Modification of surfaces and cellulose using these techniques, which enable grafting of well-defined polymer architectures, has been investigated. The interest in using cellulose stems from its renewability, biocompatibility, high molecular weight, and versatile functionalization possibilities. Dendronization was performed using disulfide-cored didendrons of 2,2-bis(methylol)propionic acid (bis-MPA) on gold surfaces, for the formation of self-assembled monolayers. It was found that the height of the monolayer increased with increasing dendron generation and that the end-group functionality controlled the wettability of the modified surface. Superhydrophobic cellulose surfaces could be obtained when a ‘graft-on-graft’ architecture was obtained using ATRP from filter paper after subsequent post-functionalized using a perfluorinated compound. The low wettability could be explained by a combination of a high surface roughness and the chemical composition. Biobased dendronized polymers were synthesized through the ‘attach to’ route employing dendronization of soluble cellulose, in the form of hydroxypropyl cellulose (HPC). The dendronized polymers were studied as nanosized objects using atomic force microscopy (AFM) and it was found that the dendron end-group functionality had a large effect on the molecular conformation on surfaces of spun cast molecules. ATRP of vinyl monomers was conducted from an initiator-functionalized HPC and an initiator-functionalized first generation dendron, which was attached to HPC. The produced comb polymers showed high molecular weight and their sizes could be estimated via AFM of spun cast molecules on mica and from dynamic light scattering in solution, to around 100-200 nm. The comb polymers formed isoporous membranes, exhibiting pores of a few micrometers, when drop cast from a volatile solvent in a humid environment. HPC was also used to initiate ROP of ε-caprolactone, which was chain extended using ATRP to achieve amphiphilic comb block copolymers. These polymers could be suspended in water, cross-linked and were able to solubilize a hydrophobic compound. / QC 20100826