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The goal of this project was improve the fundamental understanding of the wood-resin interaction, by looking at the relationship between the resin wetting onto wood and the resulting penetration into wood lumens. Wetting was analyzed with the sessile drop method, which observed the initial contact angle and change in contact angle over 35s. Penetration was measured within each individual tracheid. The Lucas-Washburn equation analyzed the wetting and penetration by calculating the penetration and comparing it to the measured penetration. Wetting of four resins was compared on 3 species, to improve the understanding of adhesive wetting behavior. This study agreed with previous research, that the non-aqueous resin exhibited favorable wetting and presumably better penetration than aqueous resins, with exception of urea-formaldehyde. Wetting and penetration of pMDI was studied on 5 wood species using the Lucas-Washburn equation. The wetting behaviors exhibited grain and species effects, which had implications on the resin availability for flake/strand-based composite products. The greater surface energy of loblolly pine most likely accounted for the significantly greater penetration of loblolly pine compared to Douglas-fir. The calculated penetration, via the Lucas-Washburn equation, exceeded the measured penetration, but it was concluded that the Lucas-Washburn equation predicted penetration reasonably well. Wetting and penetration of phenol-formaldehyde and subsequent adhesives was compared on 3 wood species using the Lucas-Washburn equation. All contact angles were unfavorable due to a skin formation. The Lucas-Washburn equation did not predict any penetration; however, penetration was observed with all systems. The findings suggest that the system was too complex for the Lucas-Washburn equation to be able to predict accurately. / Master of Science

Presented in this paper are experiments to test the hypothesis that drag reduction is possible over hydrophobic surfaces in the Wenzel state during laminar and turbulent flows. Quantification of surface drag reduction in rectangular channel flow over walls with specific hydrophobic or hydrophilic properties was obtained with pressure drop measurements along the channel for a range of Reynolds numbers between 350 and 5900. Several commercially available materials and coatings were chosen in order to span a range of contact angles between 30° and 135°. The results are within the bounds of the theoretical values calculated with the Colebrook equation, and do not show any reduction in wall shear stress as a function of material properties or surface chemistry. The differences between this experiment and others measuring pressure drop over hydrophobic surfaces is the macro-scale conditions and the hydrophobic surfaces being fully wetted. These experiments are further proof of the importance of a liquid-vapor interface for increasing the shear free area to produce drag reduction. / Master of Science

Die Benetzbarkeit und Nichtbenetzbarkeit von Oberflächen durch eine Flüssigkeit sind faszinierende und wichtige Phänomene in Wissenschaft und Technologie. Jüngst wurde entdeckt, dass Partikel die Benetzung einer Wasseroberfläche durch ein Öl unterstützen können. Es wurde eine Theorie entwickelt, das Prinzip der zu beschreiben. In der vorliegenden Doktorarbeit wurde diese Theorie im Experiment sowohl qualitativ als auch quantitativ untersucht, wobei zwei Arten von Kieselgelpartikeln Verwendung fanden. Mit Hilfe einer Reihe unregelmäßig geformter Partikel mit variierender Hydrophobie wurde der Einfluss der Oberflächenhydrophobie der Partikel auf die partikel-assistierte Benetzung untersucht. Es wurde herausgefunden, dass die Partikel mit höchster Hydrophilie Linsen aus reinem Öl bilden, während die Partikel in die Wasserphase abtauchen. Die Partikel mit größter Hydrophobie hingegen bewirken die Ausbildung von kleinen Bereichen, in denen Öl und Partikel eine stabile homogene Schicht formen. Für Partikel mit mittlerer Hydrophobie wurden beide Phänomene beobachtet. Diese drei verschiedenen Beobachtungen bestätigen, dass die Oberflächenhydrophobie der Partikel das Benetzungsverhalten des Öls auf der Wasseroberfläche bestimmen. Für die unregelmäßig geformten Partikel war aufgrund des unbekannten Kontaktwinkels ein direkter Vergleich zur Theorie nicht möglich. Um die Theorie quantitativ zu prüfen, wurden sphärische Partikel synthetisiert und ihre Oberflächen mit Hilfe von zehn Silanisierungsmittel modifiziert. Anschließend wurde ein Vergleich der experimentellen Ergebnisse mit dem entsprechenden theoretischen Phasendiagramm durchgeführt. Die Untersuchungen zeigten, dass die theoretischen Vorhersagen zum Großteil mit den experimentellen Ergebnissen übereinstimmen. Es wurden alle Fälle der Benetzung beobachtet, die auch in der theoretischen Beschreibung berücksichtigt wurden. Darüber hinaus wurden auch Abweichungen von der Theorie festgestellt. Haben die Partikel ähnliche Affinitäten zur Luft/Öl- und Öl/Wasser-Grenzfläche, hängt die Beschaffenheit der Benetzungsfilme zusätzlich vom Oberflächendruck ab. Deshalb könnte es notwendig sein, die einfache Theorie zu erweitern um den beschriebenen Beobachtungen Rechnung zu tragen. / Wetting and de-wetting of surfaces by a liquid are fascinating and important phenomena in science and technology. Recently, it was discovered that particles can assist the wetting of a water surface by an oil, and a theory describing the principle behind particle assisted wetting was developed. In this thesis, the theory was experimentally investigated qualitatively and quantitatively by using two series of silica particles. The influence of the surface hydrophobicity of the particles on particle assisted wetting was investigated by a series of irregular shaped particles with varying hydrophobicity. By applying mixtures of particles and oil to a water surface, it was found that for the most hydrophilic particles, only lenses of pure oil formed, with the particles being submerged into the aqueous phase. The most hydrophobic particles helped to form patches of stable homogenous mixed layers composed of oil and particles. For particles with intermediate hydrophobicity, lenses and patches of mixed layers were observed. These three different observations verified that the hydrophobicity of the particle surface determines the wetting behaviour of the oil at the water surface. For the irregular shaped particles with unknown contact angles with liquid interfaces, no direct comparison to the theory was possible. To test the theory quantitatively, a series of spherical particles was synthesized and their surfaces were modified by ten kinds of silane coupling agents; then the experimental results were compared with the corresponding theoretical phase diagram. It indicated that the theory agrees at large with the experimental results. All scenarios of wetting layers taken into account in the theoretical description were observed. In the fine print, deviations from the theory were also observed. If the particles have similar affinities to air/oil and oil/water interfaces, the experimentally observed morphology of the wetting layers depends in addition on the surface pressure. It might therefore be necessary to extend the simple theoretical picture to take these observations into accounts.

Wetting behavior of fluid/fluid/solid systems, largely influenced by surface properties and interactions between the three phases, plays a big role in nature and in industrial applications Traditionally, wetting studies have focused on liquid/vapor systems, especially the study of a sessile liquid droplet in air. Liquid/vapor systems can only probe the effects of surface properties and interactions between the solid and the wetting liquid. This type of characterization is inadequate for liquid/liquid systems, where surface wettability is additionally influenced by interactions between the two wetting liquids. The present study is the first to examine the effects of nanoscale roughness on wetting behavior in liquid/liquid systems and the modulation of roughness effects by fluid properties and the wetting order. This study examines both equilibrium and dynamic wetting behavior in liquid/liquid systems using well characterized substrates. Rough substrates were fabricated by coating glass substrates with nanometer sized polymer particles. Partial dissolution of the particles and molecular de-deposition of the polymer allowed for tuning of substrate roughness while retaining the original surface chemistry. The effectiveness of this fabrication technique was verified using electron microscopy and electrokinetic analysis. We examined the wetting behavior in three fluid/fluid systems: an air/water system, a decane/water system, and an octanol/water system. The oils were chosen based on their different polarities. Equilibrium wetting behavior was determined using contact angle measurements. Results indicate that for all systems where the primary wetting fluid was a liquid, an increase of the surface roughness resulted in Cassie-Baxter wetting. How hydrophilic a surface appears with regard to a water/fluid interface depended on the polarity of that fluid. The octanol/water system provided the strongest evidence regarding the effect of wetting order: a transition from Wenzel to Cassie-Baxter wetting was only observed when water was the primary wetting liquid. The observed transition was confirmed using a modified Wenzel/Cassie-Baxter model. The kinetics of droplet spreading was measured using high speed optical microscopy. After a droplet was placed on a solid surface, the motion of the contact line was imaged at a rate of 1000 fps. The wetted area was then extracted using custom Matlab® scripts. The spreading kinetics underwent a transition between two regimes: a visco-inertial regime and a slower spreading regime. Results indicated that surface roughness influenced spreading kinetics in both regimes. The overall spreading rate was always slower for rough surfaces than for smoother surfaces. In liquid/liquid systems, the duration of visco-inertial regime was dependent on the surface roughness as well; in general, it was shorter for smooth substrates compared to rough substrates. Increasing the viscosity of the non-aqueous fluid significantly increased the duration of the visco-inertial regime and decreased the overall spreading rate. This study provides insight into the competitive wetting of solid surfaces relevant in many industrial applications such as oil recovery or inkjet printing, and may guide the development of improved wetting models in an area that currently lacks an adequate theoretical description.

Hydrodynamic multiplicity in the trickle flow, or low interaction, regime is a well documented phenomenon. Multiple hydrodynamic states are often presented in the form of hysteresis loops where the hydrodynamic parameter studied are shown as a function of the operating history of the bed, i.e. liquid and gas flow rates. In extreme cases the lower leg, representing an increase in liquid flow rate on a pre-wetted and drained bed, is commonly referred to as the Levec mode. The upper extreme, referred to as the Kan-liquid mode, represents a decrease in liquid flow rate after operation in the high interaction regime. The many reported studies investigating liquid-solid mass transfer in trickle beds have generally used either the dissolution or electrochemical techniques. Numerous researchers have used their data to develop correlations predicting solid-liquid mass transfer coefficients. Most of these studies do not specify the multiplicity mode of operation. Only two studies (Sims et al. (1993) and Van der Merwe, Nicol&Al-Dahhan (2008)) use both the Levec and Kan-liquid operating modes. Both of these studies suggest that solid-liquid mass transfer also exhibit multiplicity behaviour although the trends suggested or speculated differ from each other. Sims et al. (1993) found that a Kan-liquid operated bed will outperform a Levec operated bed; however in contrast to this Van der Merwe et al. (2008) speculated that a Levec operated bed is better suited for liquid limited reactions due to enhanced liquid-solid mass transfer in the Levec mode as a result of faster interstitial velocity. This study showed that solid-liquid mass transfer coefficients, measured with both the dissolution and electrochemical technique, show multiplicity behaviour. Two distinct operating regions were found, which corresponds to the Levec and Kan-liquid modes. Measurements taken using the electrochemical technique yielded solid-liquid mass transfer coefficients larger than those measured using the dissolution method. The experimental results agree with the trend found by Sims et al. (1993) but the mass transfer coefficients in this study were significantly lower. Additionally it was shown that the difference in mass transfer coefficients, in the two modes, cannot be explained by merely compensating for the differences in wetting efficiency and interstitial velocity, suggesting that the Levec mode has a larger percentage of stagnant or poorly irrigated zones. It was also shown that mass transfer coefficients measured at the top of the column is higher than those measured at the bottom, suggesting that the flow structure is changing as a function of axial length. Lastly, with regards to electrochemical measurements of liquid-solid mass transfer, it was shown that measurements using a single particle electrode compared well to that of a multiple packing electrode. / Dissertation (MEng)--University of Pretoria, 2009. / Chemical Engineering / unrestricted

Die Benetzbarkeit und Nichtbenetzbarkeit von Oberflächen durch eine Flüssigkeit sind faszinierende und wichtige Phänomene in Wissenschaft und Technologie. Jüngst wurde entdeckt, dass Partikel die Benetzung einer Wasseroberfläche durch ein Öl unterstützen können. Es wurde eine Theorie entwickelt, das Prinzip der zu beschreiben. In der vorliegenden Doktorarbeit wurde diese Theorie im Experiment sowohl qualitativ als auch quantitativ untersucht, wobei zwei Arten von Kieselgelpartikeln Verwendung fanden. Mit Hilfe einer Reihe unregelmäßig geformter Partikel mit variierender Hydrophobie wurde der Einfluss der Oberflächenhydrophobie der Partikel auf die partikel-assistierte Benetzung untersucht. Es wurde herausgefunden, dass die Partikel mit höchster Hydrophilie Linsen aus reinem Öl bilden, während die Partikel in die Wasserphase abtauchen. Die Partikel mit größter Hydrophobie hingegen bewirken die Ausbildung von kleinen Bereichen, in denen Öl und Partikel eine stabile homogene Schicht formen. Für Partikel mit mittlerer Hydrophobie wurden beide Phänomene beobachtet. Diese drei verschiedenen Beobachtungen bestätigen, dass die Oberflächenhydrophobie der Partikel das Benetzungsverhalten des Öls auf der Wasseroberfläche bestimmen. Für die unregelmäßig geformten Partikel war aufgrund des unbekannten Kontaktwinkels ein direkter Vergleich zur Theorie nicht möglich. Um die Theorie quantitativ zu prüfen, wurden sphärische Partikel synthetisiert und ihre Oberflächen mit Hilfe von zehn Silanisierungsmittel modifiziert. Anschließend wurde ein Vergleich der experimentellen Ergebnisse mit dem entsprechenden theoretischen Phasendiagramm durchgeführt. Die Untersuchungen zeigten, dass die theoretischen Vorhersagen zum Großteil mit den experimentellen Ergebnissen übereinstimmen. Es wurden alle Fälle der Benetzung beobachtet, die auch in der theoretischen Beschreibung berücksichtigt wurden. Darüber hinaus wurden auch Abweichungen von der Theorie festgestellt. Haben die Partikel ähnliche Affinitäten zur Luft/Öl- und Öl/Wasser-Grenzfläche, hängt die Beschaffenheit der Benetzungsfilme zusätzlich vom Oberflächendruck ab. Deshalb könnte es notwendig sein, die einfache Theorie zu erweitern um den beschriebenen Beobachtungen Rechnung zu tragen. / Wetting and de-wetting of surfaces by a liquid are fascinating and important phenomena in science and technology. Recently, it was discovered that particles can assist the wetting of a water surface by an oil, and a theory describing the principle behind particle assisted wetting was developed. In this thesis, the theory was experimentally investigated qualitatively and quantitatively by using two series of silica particles. The influence of the surface hydrophobicity of the particles on particle assisted wetting was investigated by a series of irregular shaped particles with varying hydrophobicity. By applying mixtures of particles and oil to a water surface, it was found that for the most hydrophilic particles, only lenses of pure oil formed, with the particles being submerged into the aqueous phase. The most hydrophobic particles helped to form patches of stable homogenous mixed layers composed of oil and particles. For particles with intermediate hydrophobicity, lenses and patches of mixed layers were observed. These three different observations verified that the hydrophobicity of the particle surface determines the wetting behaviour of the oil at the water surface. For the irregular shaped particles with unknown contact angles with liquid interfaces, no direct comparison to the theory was possible. To test the theory quantitatively, a series of spherical particles was synthesized and their surfaces were modified by ten kinds of silane coupling agents; then the experimental results were compared with the corresponding theoretical phase diagram. It indicated that the theory agrees at large with the experimental results. All scenarios of wetting layers taken into account in the theoretical description were observed. In the fine print, deviations from the theory were also observed. If the particles have similar affinities to air/oil and oil/water interfaces, the experimentally observed morphology of the wetting layers depends in addition on the surface pressure. It might therefore be necessary to extend the simple theoretical picture to take these observations into accounts.

Ces travaux ont pour but d’étudier le comportement au mouillage spontané (statique et dynamique) ainsi que le mouillage forcé, sous l’effet de la compression, de différentes structures textiles hydrophobes. Le mouillage forcé a permis d’évaluer la robustesse de l’hydrophobicité des structures textiles. En parallèle, un nouveau dispositif automatisé et plus approprié à l’étude du mouillage forcé a été mis au point. Les principaux résultats ont montré qu’une bonne hydrophobicité ne conduit pas forcément à une bonne robustesse : spontanément, la structure floquée est la seule à favoriser une configuration de Cassie-Baxter, cependant, sa robustesse est plus faible que celle des tissus. Les différents essais ont mis en évidence l’influence importante et majeure de certains paramètres, appropriés à chaque structure textile, sur son hydrophobicité et sa robustesse comme la densité et la finesse des poils pour les tissus floqués. Ils ont également montré que certains facteurs pouvaient améliorer l’hydrophobicité mais pas sa robustesse ou inversement. Ainsi, la robustesse de l’hydrophobicité n’est pas prévisible à partir des mesures du mouillage spontané. / This work aims to study the spontaneous (static and dynamic) and the forced (under the effect of compression) wetting behaviour of different water-repellent textile structures. Forced wetting allowed to evaluate the robustness of the hydrophobicity of textile structures. In parallel, a new automated and more suitable device was developed for the study of forced wetting. The main results showed that a good hydrophobicity does not necessarily lead to a good robustness: spontaneously, the flocked structure is the only one to foster the Cassie-Baxter state, however, its hydrophobicity’s robustness is lower than that of the tissue. The different tests have highlighted the important and major influence of some parameters, adapted to each textile structure, on its hydrophobicity and its robustness such as the density and fineness of bristles for flocked fabrics. They also showed that some factors can improve the hydrophobicity but not its robustness or vice versa. Thus, the robustness of the hydrophobicity is not predictable from the measures of spontaneous wetting.

Brazing and soldering, as advanced manufacturing processes, are of significant importance to industrial applications. It is widely accepted that joining by brazing or soldering is possible if a liquid metal wets the solids to be joined. Wetting, hence spreading and capillary action of liquid metal (often called filler) is of significant importance. Good wetting is required to distribute liquid metal over/between the substrate materials for a successful bonding. Topographically altered surfaces have been used to exploit novel wetting phenomena and associated capillary actions, such as imbibitions (a penetration of a liquid front over/through a rough, patterned surface). Modification of surface roughness may be considered as a venue to tune and control the spreading behavior of the liquids. Modeling of spreading of liquids on rough surface, in particular liquid metals is to a large extent unexplored and constitutes a cutting edge research topic. In this dissertation the imbibitions of liquid metal has been considered as pertained to the metal bonding processes involving brazing and soldering fillers. First, a detailed review of fundamentals and the recent progress in studies of non-reactive and reactive wetting/capillary phenomena has been provided. An imbibition phenomenon has been experimentally achieved for organic liquids and molten metals during spreading over topographically modified intermetallic surfaces. It is demonstrated that the kinetics of such an imbibition over rough surfaces follows the Washburn-type law during the main spreading stage. The Washburn-type theoretical modeling framework has been established for both isotropic and anisotropic non-reactive imbibition of liquid systems over rough surfaces. The rough surface domain is considered as a porous-like medium and the associated surface topographical features have been characterized either theoretically or experimentally through corresponding permeability, porosity and tortuosity. Phenomenological records and empirical data have been utilized to verify the constructed model. The agreement between predictions and empirical evidence appears to be good. Moreover, a reactive wetting in a high temperature brazing process has been studied for both polished and rough surfaces. A linear relation between the propagating triple line and the time has been established, with spreading dominated by a strong chemical reaction.

The study of multiphase flow in porous media is highly relevant to many problems of great scientific importance, such as CO2 storage and enhanced oil recovery. Even though significant progress has been made in these areas, many challenges still remain. For instance, the leakage of stored CO2 may occur due to the capillary trapping failure of cap rock. Approximately 70% of oil cannot be easily recovered from underground, because the oil is held in tight porous rocks. Although CO2 storage and enhanced oil recovery are engineering processes at a geological scale, they are predominantly controlled by the transport and displacement of CO2 and reservoir fluids in aquifers and reservoirs, which are further controlled by wetting and fluid properties at pore scale. This work focuses on experimental investigations of pore-scale wetting and displacement of fluids and CO2 in porous core samples. Pore wetting, which has been measured based on contact angle, is a principal control on multiphase flow through porous media. However, contact angle measurement on other than flat surfaces still remains a challenge. In order to indicate the wetting in a small pore, a new pore contact angle measurement technique is developed in this study to directly measure the contact angles of fluids and CO2 in micron-sized pores. The equilibrium and dynamic contact angles of various liquids are directly measured in single glass capillaries, by studying the effects of surface tension, viscosity and chemical structure. The pore contact angles are compared with the contact angles on a planar substrate. The pore contact angle of a confined liquid in a glass capillary differs from the contact angle measured on a flat glass surface in an open space. Surface tension is not the only dominant factor affecting contact angle. The static contact angle in a glass pore also varies with liquid chemical structure. Viscosity and surface tension can significantly affect the dynamic pore contact angle. A new empirical correlation is developed based on our experimental data to describe dynamic pore wetting. The CO2-fluid contact angle in porous media is an important factor affecting the feasibility of long-term permanent CO2 storage. It determines CO2 flow and distribution in reservoirs or aquifers, and thus ultimately finally the storage capacity. CO2-fluid contact angles were measured in small water-wet pores and oil-wet pores, investigating the effect of CO2 phase (gas/liquid/supercritical). The CO2 phase significantly affects the CO2-fluid contact angle in an oil-wet pore. Supercritical CO2-fluid contact angles are larger than gas CO2-fluid contact angles, but are smaller than liquid CO2-fluid contact angles. However, this significant CO2 phase effect on contact angle was not observed in a water-wet pore. Another key issue considered in this study is two-phase flow displacement in porous media. This strongly relates to the important macroscopic parameters for multiphase flow transport in porous media, such as capillary pressure and relative permeability. Here CO2-water displacements are studied by conducting CO2 flooding experiments in a sandstone core sample, considering the effects of CO2 phase, pressure and CO2 injection rate. The capillary pressure-saturation curve, water production behaviour and relative permeability are investigated for gas CO2-water, liquid CO2-water and supercritical CO2-water displacements in porous media. The pressure-dependant drainage capillary pressures are obtained as a result of CO2-water interfacial tension. Various water production behaviours are obtained for gas CO2-water and liquid CO2-water displacements, mainly due to the effect of CO2 dissolution. The significant irregular capillary pressure-saturation curves and water production behaviors can be observed for the supercritical CO2-water displacements. The water and CO2 relative permeabilities for CO2-water displacements in a porous media are then predicted.