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No / By extending the cleaving method to molecular systems, we perform direct calculations of the ice Ih-water interfacial free energy for the TIP4P model. The values for the basal, prism, and f11 20g faces are 23:3 0:8 mJm 2, 23:6 1:0 mJm 2, and 24:7 0:8 mJm 2, respectively. The closeness of these values implies a minimal role of thermodynamic factors in the anisotropic growth of ice crystals. These results are about 20% lower than the best experimental estimates. However, the Turnbull coefficient is about 50% higher than for real water, indicating a possible limitation of the TIP4P model in describing freezing. / EPSRC

Thesis (MEng)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The expansion of the global fuels industry has caused an increase in the quantity of hydrocarbons produced as a by-product of refinery gas-to-liquid processes. Conversion of hydrocarbons to higher value products is possible using bioprocesses, which are sustainable and environmentally benign. Due to the deficiency of oxygen in the alkane molecule, the supply of sufficient oxygen through aeration is a major obstacle for the optimization of hydrocarbon bioprocesses. While the oxygen solubility is increased in the presence of hydrocarbons, under certain process conditions, the enhanced solubility is outweighed by an increase in viscosity, causing a depression in overall volumetric oxygen transfer coefficient (KLa). The rate at which oxygen is transferred is defined in terms of a concentration driving force (oxygen solubility) and the overall volumetric oxygen transfer coefficient (KLa). The KLa term comprises an oxygen transfer coefficient (KL) and the gas-liquid interfacial area (a), which are dependent on the uid properties and system hydrodynamics. This behaviour is not well understood for hydrocarbon bioprocesses and in a bubble column reactor (BCR). To provide an understanding of oxygen transfer behaviour, a model hydrocarbon bioprocess was developed using a BCR with a porous sparger. To evaluate the interfacial area, the Sauter mean bubble diameter (D32) was measured using an image analysis algorithm and gas holdup (ϵG) was measured by the change in liquid height in the column. Together the D32 and ϵG were used in the calculation of interfacial area in the column. The KLa was evaluated with incorporation of the probe response lag, allowing more accurate representation of the KLa behaviour. The probe response lag was measured at all experimental conditions to ensure accuracy and reliability of data. The model hydrocarbon bioprocess employed C14-20 alkane-aqueous dispersions (2.5 - 20 vol% hydrocarbon) with suspended solids (0.5 - 6 g/l) at discrete super ficial gas velocity (uG) (1 - 3 cm/s). For systems with inert solids (corn our, dp = 13.36 m), the interfacial area and KLa were measured and the behaviour of KLa was described by separation of the in uences of interfacial area and oxygen transfer coefficient (KL). To further the understanding of oxygen transfer behaviour, non-viable yeast cells (dp = 5.059 m) were used as the dispersed solid phase and interfacial area behaviour was determined. This interfacial area behaviour was compared with the behaviour of systems with inert solids to understand the differences with change in solids type. In systems using inert solids, a linear relationship was found between G and uG. An empirical correlation fo rthe prediction of this behaviour showed an accuracy of 83.34% across the experimental range. The interfacial area showed a similar relationship with uG and the empirical correlation provided an accuracy of 78.8% for prediction across the experimental range. In inert solids dispersions, the KLa increased with uG as the result of an increase in interfacial area as well as increases in KL. An increase in solids loading indicated an initial increase in KLa, due to the in uence of liquid-film penetration on KL, followed by a decrease in KL at solids loading greater than 2.5 g/l, due to diffusion blocking effects. In systems with yeast dispersions, the presence of surfactant molecules in the media inhibited coalescence up to a yeast loading of about 3.5 g/l, and resulted in a decrease in D32. Above this yeast loading, the fine yeast particles increased the apparent viscosity of the dispersion sufficiently to overcome the in uence of surfactant and increase the D32. The behaviour of G in yeast dispersions was similar to that found with inert solids and demonstrated a linear increase with uG. However, in yeast dispersions, the interaction between alkane concentration and yeast loading caused a slight increase in dispersion viscosity and therefore G. An empirical correlation to predict G behaviour with increased uG was developed with an accuracy of 72.55% for the experimental range considered. Comparison of yeast and inert solids dispersions indicated a 37.5% lower G in yeast dispersions compared to inert solids as a result of the apparent viscosity introduced by finer solid particles. This G and D32 data resulted in a linear increase in interfacial area with uG with no significant in uence of alkane concentration and yeast loading. This interfacial area was on average 6.7% lower than interfacial area found in inert solid dispersions as a likely consequence of the apparent viscosity with finer particles. This study provides a fundamental understanding of the parameters which underpin oxygen transfer in a model hydrocarbon bioprocess BCR under discrete hydrodynamic conditions. This fundamental understanding provides a basis for further investigation of hydrocarbon bioprocesses and the prediction of KLa behaviour in these systems. / AFRIKAANSE OPSOMMING: Die uitbreiding van die internasionale brandstofbedryf het 'n toename veroorsaak in die hoeveelheid koolwaterstowwe geproduseer as 'n deur-produk van raffinadery gas-tot-vloeistof prosesse. Omskakeling van koolwaterstowwe na hoër waarde produkte is moontlik met behulp van bioprosesse, wat volhoubaar en omgewingsvriendelik is. As gevolg van die tekort aan suurstof in die alkaan molekule, is die verskaffing van voldoende suurstof deur deurlugting 'n groot uitdaging vir die optimalisering van koolwaterstof bioprosesse. Terwyl die suurstof oplosbaarheid verhoog in die teenwoordigheid van koolwaterstowwe, onder sekere proses voorwaardes is die verhoogde oplosbaarheid oortref deur 'n toename in viskositeit, wat 'n depressive veroorsaak in die algehele volumetriese suurstofoordragkoëffisiënt (KLa). Die suurstof oordrag tempo word gedefinieer in terme van 'n konsentrasie dryfkrag (suurstof oplosbaarheid) en KLa. Die KLa term behels 'n suurstofoordragkoëffisiënt (KL) en die gas-vloeistof oppervlakarea (a), wat afhanklik is van die vloeistof eienskappe en stelsel hidrodinamika. Hierdie gedrag is nie goed verstaan vir koolwaterstof bioprosesse nie, asook in kolom reaktors (BCR). Om 'n begrip van suurstof oordrag gedrag te voorsien, is 'n model koolwaterstof bioproses ontwikkel met 'n BCR met 'n poreuse besproeier. Om die oppervlakarea te evalueer, is die gemiddelde Sauter deursnit (D32) gemeet deur 'n foto-analise algoritme en gas vasvanging ( G) is gemeet deur die verandering in vloeibare hoogte in die kolom. Saam is die D32 en G gebruik in die berekening van die oppervlakarea in die kolom. Die KLa is geëvalueer met insluiting van die meter se reaksie sloering, om n meer akkurate voorstelling van die KLa gedrag te bereken. Die meter reaksie sloering was gemeet op alle eksperimentele toestande om die akkuraatheid en betroubaarheid van data te verseker. Die model koolwaterstof bioproses gebruik n-C14-20 alkaan-water dispersies (2.5 - 20 vol% koolwaterstof) solide partikels (0.5 - 6 g/l) op diskrete oppervlakkige gas snelhede (1 - 3 cm/s). Vir stelsels met inerte solides (koring meel, dp = 13.36 m), is die oppervlakarea en KLa gemeet en die gedrag van KLa beskryf deur skeiding van die invloede van oppervlakarea en KL. Om die begrip van suurstof oordrag se gedrag te bevorder, is nie-lewensvatbare gisselle (dp = 5.059 m) gebruik as die verspreide solide fase en oppervlakarea is bepaal. Hierdie oppervlakarea gedrag is vergelyk met die van stelsels met inerte solides om die verskille met verandering in solide tipes te verstaan. In stelsels met inerte solides, is 'n line^ere verwantskap gevind tussen G en uG. 'n Empiriese korrelasie vir die voorspelling van hierdie gedrag is opgestel met 'n akkuraatheid van 83.34% in die eksperimentele reeks. Die oppervlakarea het 'n soortgelyke verhouding met uG en die empiriese korrelasie verskaf 'n akkuraatheid van 78,8% vir die voorspelling van oppervlakarea oor die eksperimentele reeks. In inerte solide dispersies, het die KLa toegeneem met uG as die gevolg van 'n toename in grens oppervlak asook stygings in KL. 'n Toename in solides belading het n aanvanklike styging in KLa aangedui, as gevolg van die invloed van die vloeistof-film penetrasie op KL, gevolg deur 'n afname in KL op vastestowwe ladings groter as 2.5 g/l, te danke aan diffusie blokkeer effekte. In stelsels met gis dispersies, het die teenwoordigheid van benattings molekules in die media samesmelting geïnhibeer tot 'n gis lading van ongeveer 3.5 g/l, en het gelei tot 'n afname in D32. Bo hierdie gis lading, het die fyn gis partikels die skynbare viskositeit van die verspreiding verhoog genoegsaam om die invloed van benattings molekules te oorkom en die D32 te verhoog. Die gedrag van G in gis dispersies was soortgelyk aan die van inerte solides en dui op 'n lineêre toename met uG. Maar in gis dispersies, het die interaksie tussen alkaan konsentrasie en gis lading 'n effense toename veroorsaak in die verstrooiing viskositeit en dus in G. 'n Empiriese korrelasie is ontwikkel om G gedrag te voorspel en het 'n akkuraatheid van 72,55% vir die eksperimentele verskeidenheid beskou. Vergelyking van gis en inerte patrikel dispersies wys 'n 37.5% laer G in gis dispersies in vergelyking met inerte vaste stowwe as 'n gevolg van die skynbare viskositeit bekendgestel deur fyner vastestowwe partikels. Hierdie G en D32 data het gelei tot 'n linere toename in grens oppervlak met uG met geen beduidende invloed van alkaan konsentrasie en gis lading nie. Die oppervlakarea was gemiddeld 6.7% laer as oppervlakarea gevind in inerte partikel dispersies as 'n waarskynlike gevolg van die skynbare viskositeit met fyner partikels. Hierdie studie bied 'n fundamentele begrip van die veranderlikes wat die suurstof oordrag definieer in 'n model koolwaterstof bioproses BCR onder diskrete hidrodinamiese voorwaardes. Hierdie fundamentele begrip bied n basis vir verdere ondersoek van koolwaterstof bioprosesse en en die voorspelling van KLa gedrag in hierdie stelsels.

Fillers are often incorporated in polymer matrices in order to improve cost, mechanical, thermal, and transport properties. This work explores the hypothesis that pollen, a natural particle, has the potential to be an effective biorenewable reinforcing filler due to its unique surface architectures, high strength, chemical stability, and low density. Pollens from sources such as ragweed plants are ubiquitous natural materials that are based on sustainable, non-food resources. Pollen is a remarkable example of evolutionary-optimized microscale particle with structures and/or chemistries tailored for effective adhesion to a variety of surfaces and protection of genetic material under different dynamic and environmental conditions. The pollen shell is perhaps the most chemically resistant naturally occurring material. As many pollens achieve pollination simply by being carried by wind, they are very light-weight. These properties make pollen an attractive option as a natural filler for polymers. This research aims to characterize pollen interfacial properties and utilize pollen as an effective reinforcing filler in polymer materials. In this work, interfacial properties are characterized using Fourier transform infrared spectroscopy (FTIR), the BET method, and inverse liquid chromatography (ILC). These techniques were useful in determining the effect of surface treatments and further chemical modifications on pollen interfacial properties. Characterizing these properties allowed for improved understanding and utilization of pollen as a filler by revealing the enhanced surface interactions and surface properties of acid-base treated pollens when compared to as received untreated pollens. Epoxy and polyvinyl acetate (PVAc) matrices were used to demonstrate the effectiveness of pollen as a filler, as a function of pollen loading and surface treatments/chemical modifications. Scanning electron microscopy (SEM) was used to determine interfacial morphology, a high throughput mechanical characterization device (HTMECH) was used to determine mechanical properties, and differential scanning calorimetry (DSC) was used to determine glass transition behavior. In epoxy, pollen was an effective load bearing filler only after modifying its surface with acid-base hydrolysis. In PVAc, pollen was an effective load bearing filler only after an additional functionalization with a silane coupling agent. Finally, the species of pollen incorporated in PVAc matrices was varied in order determine the effect of the size of surface nano- and micro- structures on wetting, adhesion, and composite properties. Composites containing pollen displayed enhanced wetting and interfacial adhesion when compared to composites with smooth silica particles. Additionally, it was observed that pollen with smaller surface structures were wetted more effectively by the polymer matrix than pollen with larger structures. However, mechanical properties did not suggest significant changes in interfacial adherence with varied pollen microstructure size. The results of this work highlight the feasibility and potential of utilizing pollen as a natural filler for creating high strength, light-weight polymer composites with sustainable filler.

Just as conventional mechatronic systems rely on switches and relays, machines that are soft and elastically deformable will require compliant materials that can support field-controlled reconfiguration. In this dissertation, I present several novel approaches to shape programmability that primarily rely on condensed soft matter and are stimulated by electric or magnetic fields. I begin with electric-field-driven methods for achieving shape programmability of elastomer-based systems. These include dielectric elastomer actuators and electrostatic beams that undergo extreme stretch. Classical theories in elasticity and electrostatics are used to examine the mechanical responses and instabilities of these soft, hyperelastic systems. Such modeling techniques are also used to examine another switching mode based on the snap through behavior of a buckled ferromagnetic beam under magnetic load. I will then discuss a unique approach to shape programmability that is based on electrochemistry and exploits the coalescence and separation of anchored liquid metal drops. In this case, electrical signals under 10V are utilized to manipulate surface energies and transition between bi-stable states. Experiments and Surface Evolver simulations show that oxidation and reduction on opposing poles of the coalesced drops create an interfacial tension gradient that eventually leads to limit-point instability. Theory derived from bipolar electrochemistry and vertical electrical sounding predicts droplet motion and separation based on geometry and bath conductivity, facilitating the optimization of reconfigurable devices using this phenomenon. I conclude with the application of the bi-stable droplets to a simple toggle switch capable of changing circuit conductivity by over three orders of magnitude.

<p>Electromigration in thin films is a well known failure mode for scaled microelectronics. While our understanding of electromigration physics has improved immensely in the last few decades, there are still some gaps in literature. In particular, the influence of interfaces on the mass transport rate is not well understood. Through reliability studies conducted on passivated metals films, marked improvement in electromigration lifetimes was observed. Specifically, some choices of materials for passivation appear to perform better than others. Qualitatively this improvement in electromigration performance is attributed to surface adhesion. However, a theoretical connection is largely missing in the literature. Lane et al. through in-situ electromigration experiments and separate interfacial debond experiments on sandwich specimens showed that a correlation exists between the void growth rate and the debond energy. However, a fundamental understanding of the relation between the two is missing. In this study we explore the connection between interfacial adhesion and void growth in a current driven system. Several experiments with varying test conditions are carried out on Blech-like test structures with different capping layers. The influence of these capping layers is captured through direct void growth measurements. Comparison of activation energy associated with electromigration was made against existing literature. It was found to be consistent with values reported for surface/interface dominated diffusion mechanisms. Further, an extension is proposed to the phase growth relations derived in existing literature to include the effect of surface adhesion. Interfacial adhesion energy ratios are extracted from the electromigration experiments for two of the test structures (Cu-Ta and Cu-SiNx) tested in this study. This ratio is compared to values reported in literature for the two interfaces and they show good agreement with experimental data.<br></p>

<div>Fluid interfaces containing surface-active species (e.g., surfactants, polymers, and particles) have rheological properties that are vital to the kinetic stability of emulsions. Many practical applications of emulsions necessitate superb stability during storage, such as in emulsion-based therapeutic delivery systems. While in other cases, stabilized systems are entirely unwanted (e.g., separating oil and aqueous phases in enhanced oil recovery and bilge water applications).</div><div><br></div><div>Techniques for modulating emulsion stability are highly desired and are largely determined by the mechanics of the interfacially-trapped species. However, the utility of these techniques is often limited by difficulties in measuring and interpreting the rheological characteristics of complex fluid interfaces. Lack of control over interface formation during emulsification magnifies this problem, further obscuring relationships between interfacial rheology and bulk emulsion stability. Thus, the objectives of this research were to (1) elucidate these fundamental relationships through emulsion stability and interfacial rheological measurements, and (2) present innovative methodologies for modulating the kinetic stability of model oil-in-water emulsions using physical chemistry principles.</div><div><br></div><div>Objective 1 was addressed by studying correlations between the dilatational rheology of single- and multi-component oil-water interfaces and the susceptibility to coalescence of the bulk systems they comprised. Oscillating pendant drop tensiometry was used to probe interfacial viscoelastic behavior, while dynamic light scattering and optical microscopy were used to characterize coalescence susceptibility in bulk oil-in-water emulsions. The magnitude of the low-frequency dilatational elastic modulus was shown to positively correlate with oil droplet coalescence resistance over time. Objective 2 was addressed by analyzing how physical chemistry principles can be applied to control various emulsion droplet destabilization phenomena and produce desirable bulk behavior. To this aim, two emulsion destabilization studies were performed; one related to the nanoparticle-induced flocculation of oil droplets in a dilute, electrostatically-stabilized emulsion and one related to the convective flows generated by the asymmetric dilatational rheology of coalescing droplets. <br></div><div><br></div><div>The knowledge garnered from this body of work is highly relevant to academic and industrial emulsion formulators who seek inexpensive, yet robust methods for predicting, characterizing and tailoring the kinetic stability of oil-in-water emulsions.</div>

Thermal management in electronic devices is one of the biggest challenges faced by the semiconductor industry. Thermal Interface Materials (TIMs) are used in electronics to fill air gaps between the surfaces of integrated circuit (IC) chips to dissipate heat. Polymer-graphene composites, a very promising choice as TIMs also have a drawback of high interfacial thermal resistance and a low thermal conductivity of polymer. It is known from the theoretical models that application of pressure may affect the thermal conductivity in a desirable manner, but quantitative simulations were not available. In this paper, the pressure dependence of thermal conductivity of epoxy and interfacial resistance at epoxy-graphene interface is studied using non-equilibrium molecular dynamics (NEMD) simulations. The results show that the thermal conductivity of epoxy increases with increase in pressure, and they compare well with the predictions using a theoretical model. The interfacial thermal resistance at epoxy-graphene interface reduces with increase in pressure. The reduction is sharp in the beginning and slowly reaches saturation as pressure increases. At 10 GPa compressive pressure, a 90-95% decrease in interfacial thermal resistance is observed.

The weathering of apatite is the foundation of the phosphorus cycle and essential to life, yet little is known about the nanoscale mechanisms driving apatite weathering. Deciphering nanoscale dissolution in apatite is a significant step to understand phosphate weathering behavior, that was key to the development of life. Determining what controls apatite weathering can impact many areas of environmental and medical mineralogy such as dentistry, contaminant scavenging, geochronology, and paleoenvironment studies. The aim of this study was to characterize apatite dissolution across scales with an emphasis on the nanoscale mechanisms. Recent research on the weathering of silicate minerals at the nanoscale has provided telling evidence of a relatively new chemical weathering model referred to as coupled interfacial dissolution-precipitation (CIDR) mechanism. We hypothesize that this mechanism could be broadened to phosphate minerals. To investigate crystals of Durango fluorapatite (FAP) and hydroxyl-chlorapatite (HAP) were hydrolyzed in flow-through devices with pH 3 HNO3 solutions. Apatites used in the study were chemically and structurally characterized via Single Crystal-XRD, with particular emphasis on the anion composition and atomic arrangement. Determination of the mechanisms of dissolution was carried at multiple scales using ICP-OES chemical analysis (macroscale), SEM (microscale) and STEM-HAADF-EDS/EELS on FIB liftouts (nanoscale). At the macroscale, The anionic composition of the apatite controlled its weathering rate. As expected, HAP dissolution occurred at faster rates compared to FAP. SEM characterization of the crystal surfaces pre- and post-dissolution revealed the development of etch pits during dissolution, however, more pronounced for FAP than HAP. Observation of the mineral/solution interface at the nanoscale using STEM-HAADF revealed the development of a nanometric amorphous layer likely depleted in Ca compared to P. The observation of a sharp crystalline/amorphous transition and 5 to 15 nanometers thick amorphous surface altered layer, associated with a depletion in Ca suggests that similar to silicate, apatite is subject to a coupled interfacial dissolution-reprecipitation mechanism. This potential discovery could transform our understanding of phosphate behavior in medical and environmental mineralogy fields.

The development of organic photovoltaics (OPVs) has attracted a lot of attention due to their potential to create a low cost flexible solar cell platform. In general, an OPV is comprised of a number of layers of thin films that include the electrodes, active layers and barrier films. Thus, with all of the interfaces within OPV devices, the potential for failure exists in numerous locations if adhesion at the interface between layers is inherently low or if a loss of adhesion due to device aging is encountered. To date, few studies have focused on the basic properties of adhesion in organic photovoltaics and its implications on device reliability. In this dissertation, we investigated the adhesion between interfaces for a model multilayer barrier film (SiNx/PMMA) used to encapsulate OPVs. The barrier films were manufactured using plasma enhanced chemical vapor deposition (PECVD) and the interfacial fracture toughness (Gc, J/m2) between the SiNx and PMMA were quantified. The fundamentals of the adhesion at these interfaces and methods to increase the adhesion were investigated. In addition, we investigated the adhesive/cohesive behavior of inverted OPVs with different electrode materials and interface treatments. Inverted OPVs were fabricated incorporating different interface modification techniques to understand their impact on adhesion determined through the interfacial fracture toughness (Gc, J/m2). Overall, the goal of this study is to quantify the adhesion at typical interfaces used in inverted OPVs and barrier films, to understand methods that influence the adhesion, and to determine methods to improve the adhesion for the long term mechanical reliability of OPV devices.